Self-crosslinking urethane (meth)acrylate

Abstract

This invention relates to urethane (meth)acrylates containing a chromophore portion in their backbone. These urethane (meth)acrylates are self-crosslinking (or self-reactive), meaning they can be polymerized after exposure to chemical radiation without the addition of a photoinitiator.

Description

[Technical Field]

[0001] This invention relates to urethane (meth)acrylates containing a chromophore portion in their backbone. These urethane (meth)acrylates are self-crosslinkable (or self-reactive or inherently reactive), meaning they can be polymerized after exposure to chemical radiation without the addition of radical initiators or initiation systems. [Background technology]

[0002] Urethane (meth)acrylates (also known as (meth)acrylate-functionalized polyurethane oligomers and polymers) are widely used resin components in a variety of applications, including ultraviolet and electron beam (UV / EB) curable materials. This versatility stems from the wide range of physical and mechanical properties that can be obtained from such resins. This broad range of properties, in turn, is due to the combination of the diverse skeletal functional groups available for the manufacture of urethane (meth)acrylates and the high photoreactivity and thermal reactivity of pendant or telechelic (meth)acrylate functional groups.

[0003] In conventional chemical beam curing systems containing urethane (meth)acrylates, the radicals that initiate curing are generated by the photodegradation of the photoinitiator. A wide variety of low molecular weight photoinitiators are commercially available and well known to those skilled in the art. The disadvantage of using low molecular weight photoinitiators is that low molecular weight photofragments inevitably remain in the cured composition. This is true whether it is a fragmentation photoinitiator (Norrish type I) or a hydrogen abstraction bimolecular photoinitiator (Norrish type II). Low molecular weight photofragments often cause undesirable odors, volatile organic compounds, and extractable / leached molecules. Oligomer / polymer photoinitiators are available in a more limited range and may be used to reduce extractable components and odors associated with the photoinitiator package. The use of oligomer / polymer photoinitiators is not an ideal solution. This is because the trade-offs generally include a decrease in curing speed, limitations in resin compatibility, and increased formulation costs due to a decrease in the active content of the polymer photoinitiator system. In some cases, polymer photopolymerization initiators may have undesirable effects on the properties of the cured material due to the properties of the initiator polymer backbone, which may not be optimized for the intended application.

[0004] U.S. Patent Publication 2014 / 0316060 discloses a polymer comprising both a dye and a photopolymerization initiator.

[0005] U.S. Patent No. 7,148,265 discloses polymers containing α,β-unsaturated polymers and photoinitiators bonded to these polymers. The photoinitiators are selected from imidazole dimers, anthraquinones, naphthaquinones, ketals, triazine compounds, or combinations thereof. While photoinitiators bonded to oligomers may participate in crosslinking when irradiated with UV light via a radical coupling mechanism, this polymer-radical-based coupling curing mechanism is inefficient, especially in systems targeting high crosslink density and rapid curing rates (common in many UV-curable applications). Therefore, incorporating (meth)acrylate functional groups into the aforementioned essentially photosensitive urethanes is beneficial to produce oligomers that exhibit high curing rates and can generate relatively high crosslink density.

[0006] As a result of extensive research, the applicant has overcome the aforementioned challenges by combining a base oligomer resin with a photoinitiator package to produce so-called self-crosslinking urethane (meth)acrylates. Such oligomers can be formulated without the need for additional photoinitiators because the photoinitiator is incorporated into the primary oligomer backbone. This approach differs fundamentally from conventional polymer photoinitiators, where the high molecular weight portion of the photoinitiator does not play a designed functional role in the mechanical properties of the cured system. In the self-crosslinking urethane (meth)acrylates of the present invention, the oligomer resin containing the photoinitiator is specifically designed to impart those mechanical properties to the cured product, similar to the typical oligomer portion of UV-curable systems. Thus, because the self-crosslinking urethane (meth)acrylate is the main resin oligomer, there is no degradation of mechanical properties or compatibility issues with the main resin oligomer. Ideally, compounders can use their preferred urethane (meth)acrylate for specific applications, but can use this chemical approach to impart self-crosslinking properties. [Overview of the Initiative]

[0007] To overcome the aforementioned drawbacks, photoinitiators can be incorporated into the urethane (meth)acrylate backbone. In such cases, the photoinitiator is still part of the polymer / oligomer, but it is incorporated into the optimized functional portion of the final cured product. Therefore, no portion of the formulation is wasted due to the unoptimized polymer content associated with separately added polymer photoinitiators. When photoinitiators are incorporated into high molecular weight oligomer / polymer components in this way, the aforementioned desirable effects such as low odor, low or no photoinitiator extract, and ease of formulation can be achieved while eliminating the limitations associated with conventional polymeric and low molecular weight photoinitiators. In terms of compatibility, introducing the photoinitiator into the urethane (meth)acrylate backbone ensures the solubility and compatibility of the photoinitiator, unlike when polymer photoinitiators are added. This is because polymer photoinitiators may not be compatible with the components of the curable composition to be initiated. Both Norrish type I and type II photoinitiators can be incorporated into urethane (meth)acrylate using this method, but Norrish type II photoinitiator is preferred to truly eliminate extractable photofragments.

[0008] The inventors have found it beneficial to include (meth)acrylate groups in polymers / oligomers containing a bound photoinitiator group. Preferred in the present invention are pendant or telechelic (meth)acrylate functional groups. Such designed oligomers / polymers offer many desirable features. As described above, bound Norrish II type photoinitiators are particularly preferred because they provide a system with low odor, zero extractable light fragments, and optimized mechanical properties. By introducing (meth)acrylate groups into the same polymer / oligomer as the initiating chromophore, the resulting product rapidly reacts upon chemical irradiation to form a cured product via the highly reactive (meth)acrylate groups and the introduced photoinitiator moiety.

[0009] Therefore, the present invention is - At least one (meth)acrylate functionalization moiety ("ACR"); - At least two polyurethane parts ("UU"); - At least one chromophore segment ("Q"); - Selectively select one chain extension ("EXT") This relates to self-crosslinking urethane (meth)acrylates, including those containing such acrylates.

[0010] The present invention also provides a method for preparing a self-crosslinking urethane (meth)acrylate, a) Hydroxyl-functionalized (meth)acrylate components; b) Polyisocyanate components; c) Hydroxyl-functionalized photopolymerization initiator component; d) Selectively polyol components The present invention relates to a method that includes reacting [a certain substance].

[0011] The present invention A) Self-crosslinking urethane (meth)acrylate according to the present invention; and B) Selectively polymerizable components other than A) The present invention further relates to curable compositions containing the following:

[0012] The present invention relates to a method for preparing a cured product, which preferably involves curing a curable composition according to the present invention by exposing the curable composition to electromagnetic radiation and / or electron beam radiation that induces chemical reactions, such as ultraviolet light, near-ultraviolet light, visible light, infrared light, and near-infrared light, and more particularly by exposing a polymerizable composition to an LED light source.

[0013] The present invention further relates to substrates to which the curable composition according to the present invention has been applied and cured, and in particular, the substrates are food and beverage packaging, pharmaceutical packaging, textiles, nails, teeth, medical devices, food and beverage processing equipment, water pipes, or toys.

[0014] The present invention further relates to the use of self-crosslinkable urethane (meth)acrylate according to the present invention as a photoinitiation system in curable compositions, particularly UV or LED curable compositions.

[0015] The present invention further relates to the use of self-crosslinking urethane (meth)acrylate according to the present invention for obtaining a cured product with a reduced amount of extractable substance. [Brief explanation of the drawing]

[0016] [Figure 1] Plots of optical DSC analysis of the self-crosslinking urethane (meth)acrylates of Examples 5-8, both on their own and as blends with di(trimethylolpropane)tetraacrylate in a 1:1 weight ratio. [Figure 2] Surface hardening (top) and through-hardening (bottom) of the self-crosslinkable urethane (meth)acrylates of Examples 23 and 27, as a 1:1 weight ratio blend with di(trimethylolpropane)tetraacrylate, as measured by FT-IR. [Figure 3] DMA plots of comparative standard UA (top) and the self-crosslinkable urethane acrylate of Example 23 (bottom). [Modes for carrying out the invention]

[0017] definition In this application, the term "comprise(s) a / an~" means "comprise(s) one or more~ (including one or more ~)".

[0018] Unless otherwise stated, weight percentages in a compound or composition are expressed based on the weight of the compound or composition.

[0019] Unless otherwise specified, molecular weights in this specification are number-average molecular weights measured using gel permeation chromatography with polystyrene standards.

[0020] As used herein, the term “independently selected” with respect to the selection of groups in a structure means that if there are multiple groups in the structure, they do not all have to be the same, as long as they are selected from the enumerated options. For example, the statement “R3 may be independently selected as a direct bond or a linker” means, for example, that one R3 in the structure may be a direct bond and another R3 may be a linker.

[0021] As used herein, the term "urethane (meth)acrylate" means an oligomer comprising one or more urethane bonds and one or more (meth)acrylate groups.

[0022] As used herein, the term “self-crosslinking urethane (meth)acrylate” means a urethane (meth)acrylate having at least one chromophore moiety in its backbone. Such urethane (meth)acrylates can be polymerized after exposure to electromagnetic radiation (other than electron beams) that induces a chemical reaction, without the addition of a radical initiator or initiation system (e.g., a photopolymerization initiator, peroxide, azo compound, or redox system).

[0023] The term "(meth)acrylate group" is used herein without distinction to refer to either an acrylate group or a methacrylate group. An acrylate group corresponds to the acryloyl group of the formula -C(=O)-CH=CH2. A methacrylate group corresponds to the methacryloyl group of the formula -C(=O)-C(CH3)=CH2.

[0024] As used herein, the term “residue” refers to the group of atoms remaining in the product after a functional group that reacts with another compound to form a linkage has been removed. For example, the residue in a diol having the structure HO-R3-OH is understood to be R3.

[0025] The term "C1-C6" refers to the number of carbon atoms in a particular group or linker. For example, a C1-C6 alkylene is an alkylene containing 1 to 6 carbon atoms.

[0026] The term "linker" refers to a polyvalent group containing at least one carbon atom and / or at least one heteroatom such as O, N, or S. A linker can link at least two parts of a compound, and in particular, 2 to 6 parts of a compound. For example, a linker that links two parts of a compound is called a divalent linker, and a linker that links three parts of a compound is called a trivalent linker.

[0027] The term "aliphatic compound, group, or linker" refers to a non-aromatic compound, group, or linker. Compounds, groups, or linkers containing a non-aromatic ring (i.e., an alicyclic ring) are included in the term aliphatic compound, group, or linker. Compounds, groups, or linkers containing a non-aromatic ring may be saturated or unsaturated, cyclic or acyclic. For example, they may be substituted with one or more groups selected from alkyl, hydroxyl, halogen (Br, Cl, I), isocyanate, carbonyl (=O), amine, carboxylic acid, -C(=O)-OR', -C(=O)-OC(=O)-R', where each R' is independently C1-C6 alkyl. They may also contain one or more bonds selected from ethers, esters, amides, urethanes, ureas, carbonates, organosiloxanes, and mixtures thereof.

[0028] The term “aromatic compound, group, or linker” means a compound, group, or linker comprising at least one aromatic ring (i.e., a ring following Hückel’s aromaticity rule, such as phenyl), particularly one, two, or three, preferably one or two aromatic rings. Aromatic aliphatic compounds, groups, or linkers comprising both aromatic and non-aromatic moieties are included in the term “aromatic compound, group, or linker.” Aromatic aliphatic compounds, groups, or linkers may be substituted with one or more groups, as defined in the term “aliphatic compound, group, or linker.” They may contain one or more bonds, as defined in the term “aliphatic compound, group, or linker.”

[0029] The term "hydrocarbon linker" refers to a linker containing carbon and hydrogen atoms. Unless otherwise specified, a hydrocarbon linker should not contain any atoms other than carbon and hydrogen.

[0030] The term "acyclic compound, group, or linker" means a compound, group, or linker that does not contain a ring.

[0031] "Cyclic compound, group, or linker" means a compound, group, or linker that contains at least one aromatic or non-aromatic ring.

[0032] The term "saturated compound, group, or linker" means a compound, group, or linker that does not contain double or triple carbon-carbon bonds.

[0033] The term "unsaturated compound, group, or linker" means a compound, group, or linker containing one or more double or triple carbon-carbon bonds, in particular one or more double carbon-carbon bonds.

[0034] The term "polyether linker" refers to a linker that contains one or more ether bonds.

[0035] The term "polyester linker" refers to a linker containing one or more ester bonds.

[0036] The term "polycarbonate linker" refers to a linker containing one or more carbonate bonds.

[0037] The term "polyorganosiloxane linker" refers to a linker containing one or more organosiloxane bonds.

[0038] A "polycaprolactone linker" refers to a linker containing one or more units derived from the ring-opening of ε-caprolactone, i.e., one or more units of the formula -O-(C=O)~(CH2)5-. A polycaprolactone linker is a specific example of a polyester linker.

[0039] The term "polydiene linker" refers to a linker derived from the polymerization of polydienes such as butadiene or isoprene. "Polydiene linker" also includes fully or partially hydrogenated polydiene linkers obtained by the hydrogenation of polydiene linkers.

[0040] The term "isocyanurate linker" refers to the isocyanurate portion, i.e., the following formula: This refers to a linker that includes the portion specified by TIFF2026518308000001.tif29170.

[0041] The term "alkyl" is derived from the formula -C n H 2n+1 This refers to a monovalent saturated acyclic hydrocarbon group (wherein n is 1 to 20). Alkyl groups 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, and 2-ethylhexyl.

[0042] The term "heteroatom-containing alkyl" means an alkyl group containing one or more heteroatoms independently selected from O, N, or S.

[0043] The term "cycloalkyl" refers to a monovalent saturated hydrocarbon group containing a ring. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and isobornyl.

[0044] The term "heterocycloalkyl" refers to a cycloalkyl group having at least one ring atom that is a heteroatom selected from O, N, or S.

[0045] The term "alkenyl" refers to a monovalent acyclic hydrocarbon group containing at least one carbon-carbon double bond. Alkenyls can be linear or branched.

[0046] The term "alkynyl" refers to a monovalent acyclic hydrocarbon group containing at least one carbon-carbon triple bond. Alkynnyls can be linear or branched.

[0047] The term "aryl" refers to an optionally substituted polyunsaturated aromatic group. An aryl may contain a single ring (i.e., phenyl) or multiple rings, at least one of which is aromatic. If an aryl contains multiple rings, the rings may be fused or linked via direct bonds (e.g., biphenyl). The aromatic ring may optionally contain one or two additional fused rings (i.e., cycloalkyl, heterocycloalkyl, or heteroaryl). The term "aryl" also encompasses partially hydrogenated derivatives of the aforementioned carbocyclic systems, such as phenyl, naphthyl, biphenyl, phenantrenyl, and naphthacenyl.

[0048] The term "heteroaryl" refers to an aryl group having at least one ring atom that is a heteroatom selected from O, N, or S.

[0049] The term "aralkyl" refers to an aryl group substituted with an alkyl group. An example of an aralkyl group is a toryl.

[0050] The term "alkalil" refers to an alkyl group substituted with an aryl group. An example of an alkalil group is benzyl(-CH2-phenyl).

[0051] The term "halogen" refers to an atom selected from Cl, Br, F, and I.

[0052] The term "alkoxy" refers to the -O-alkyl group, where alkyl is defined above.

[0053] The term "aryloxy" refers to the -O-aryl group, where aryl is defined as described above.

[0054] The term "thioalkyl" refers to the -S-alkyl group, where alkyl is defined above.

[0055] The term "thioaryl" refers to the -S-aryl group, where aryl is defined as above.

[0056] The term "aralkyloxy" refers to the base of the formula -O-aralkyl, where aralkyl is defined above.

[0057] The term "alkaloxy" refers to the group of the formula -O-alkal, where alkal is defined above.

[0058] The term "alkylene" is derived from formula C m H 2m+2 This refers to a polyvalent linker derived from an alkane (where m is between 1 and 50) by removing one hydrogen atom from each bond site of the linker. Alkylenes can have a valency of 2, 3, 4 or more.

[0059] The term "alkenylene" refers to a polyvalent aliphatic linker containing at least one carbon-carbon double bond.

[0060] The term "heteroatom-containing alkylene" means an alkylene containing one or more heteroatoms independently selected from O, N, or S.

[0061] The term "oxyalkylene" refers to the group of the formula -O-alkylene-.

[0062] The term "alkoxylated alkylene" is derived from the formula -(alkylene-O) n39 -Alkylene-(O-Alkylene) n40means a group of, in the formula, n 39 and n 40 are independently from 0 to 100, provided that at least one of n 39 and n 40 is not 0.

[0063] The term "thioalkylene" means a group of the formula -S-alkylene-.

[0064] The term "ketoalkylene" means a group of the formula -C(=O)-alkylene-.

[0065] The term "aminoalkylene" means a group of the formula -N(R 40 )-alkylene-, in the formula, R 40 is H or an organic group.

[0066] The term "carboxyalkylene" means a group of the formula -C(=O)-O-alkylene- or -O-C(=O)-alkylene-.

[0067] The term "amidoalkylene" means a group of the formula -C(=O)-N(R 41 )-alkylene- or -N(R 41 )-C(=O)-alkylene-, in the formula, R 41 is H or an organic group.

[0068] The term "heteroatom-containing alkenylene" means an alkenylene containing one or more heteroatoms independently selected from O, N or S.

[0069] The term "cycloalkylene" means a polyvalent linker containing a non-aromatic ring. Examples of cycloalkylene groups include cyclopentylene, cyclohexylene and cyclohexylenedimethylene (i.e., -CH2-Cy-CH2, where Cy is cyclohexylene).

[0070] The term "heterocycloalkylene" refers to a polyvalent linker containing a non-aromatic ring having at least one ring atom that is a heteroatom selected from O, N, or S.

[0071] The term "arirene" refers to a polyvalent linker containing at least one aromatic ring.

[0072] The term "heteroarylene" refers to a polyvalent linker containing an aromatic ring having at least one ring atom that is a heteroatom selected from O, N, or S.

[0073] The term "alkylamino" refers to an alkyl group that is substituted with at least one amino group.

[0074] The term "alkylthiol" refers to an alkyl group that is substituted with at least one thiol group.

[0075] The term "hydroxyalkyl" refers to an alkyl group that is substituted with at least one hydroxyl group.

[0076] The term "haloalkyl" refers to an alkyl group that is substituted with at least one halogen.

[0077] The term "perfluoroalkyl" refers to an alkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[0078] The term "polyol" refers to a compound that contains at least two hydroxyl groups.

[0079] As used herein, the term “polyol residue” means the portion obtained by removing the hydroxyl group from a polyol.

[0080] As used herein, the term "polyacid" means a compound having at least two carboxylic acid groups.

[0081] As used herein, the term “residue of polyacid” means the portion obtained by removing the carboxylic acid group from a polyacid.

[0082] As used herein, the term "polyamine" means a compound having at least two primary and / or secondary amino groups.

[0083] As used herein, the term “polyamine residue” means the portion obtained by removing the primary and / or secondary amino groups of a polyamine.

[0084] As used herein, the term "hydroxy acid" means a compound having at least one hydroxyl group and at least one carboxylic acid group.

[0085] As used herein, the term “hydroxy acid residue” means the portion obtained by removing the hydroxyl group and the carboxylic acid group from a hydroxy acid.

[0086] As used herein, the term "hydroxyamine" means a compound having at least one hydroxyl group and at least one primary and / or secondary amino group.

[0087] As used herein, the term “hydroxyamine residue” means the portion obtained by removing the hydroxyl group and the primary and / or secondary amino group of a hydroxyamine.

[0088] The term "hydroxyl group" refers to the -OH group.

[0089] The term "amino group" is -NR a1 R b1 It means base, and here, R a1 and R b1 This is independently H or an optionally substituted alkyl group. "Primary amino group" refers to -NR a1R b1 means a radical, where R a1 and R b1 are H. The term "secondary amino group" means a -NR a1 R b1 radical, where R a1 is H and R b1 is optionally substituted alkyl.

[0090] The term "carboxylic acid group" means a -COOH group.

[0091] The term "isocyanate group" means a -N=C=O group.

[0092] The term "direct bond" means a covalent bond.

[0093] The term "ester bond" means a -C(=O)-O- or -O-C(=O)- bond.

[0094] The term "ether bond" means an -O- bond.

[0095] The term "organosiloxane bond" means a -Si(R c1 )2-O- bond, where R c1 is an organic group, particularly an organic group selected from alkyl, alkoxy and aryl.

[0096] The term "carbonate bond" means an -O-C(=O)-O- bond.

[0097] The term "urethane or carbamate bond" means an -NH-C(=O)-O- or -O-C(=O)-NH- bond.

[0098] The term "polyisocyanate" means a compound containing at least two isocyanate groups.

[0099] The term "compound, group or linker which may be substituted" means a compound, group or linker which may be substituted with one or more groups selected from halogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, aralkyl, alkaryl, aralkyloxy, alkaryloxy, haloalkyl, -OH, -SH, hydroxyalkyl, thioalkyl, thioaryl, alkylthiol, amino, alkylamino, isocyanate, nitrile, oxo(=O), -C(=O)-R', -O-C(=O)-R', -C(=O)-OR', -C(=O)-N(R')2, -NR'-C(=O)-R', -C(=O)-O-C(=O)-R' and -SO2-N(R')2 (each R' is independently H or an optionally substituted group selected from alkyl, aryl and alkylaryl).

[0100] Self-crosslinkable urethane (meth)acrylate The self-crosslinkable urethane (meth)acrylate of the present invention can be described as an oligomer containing (i.e., composed of) different moieties (or subunits) that are linked to each other to form a backbone. As is often the case with oligomers, the self-crosslinkable urethane (meth)acrylate of the present invention may actually correspond to a mixture of compounds having a molecular weight or degree of polymerization (DP) distribution.

[0101] The self-crosslinkable urethane (meth)acrylate of the present invention may contain at least three different types of moieties: a (meth)acrylate functionalized moiety ACR, a polyurethane moiety UU, a chromophore moiety Q, and optionally a chain extension moiety EXT as detailed below. Such moieties may be bonded to each other in any order, and at least some of the said moieties may be repeated any number of times throughout the oligomer backbone.

[0102] (Meth)acrylate functionalized moiety ACR The self-crosslinkable urethane (meth)acrylate of the present invention comprises at least one (meth)acrylate-functionalized moiety ACR. The self-crosslinkable urethane (meth)acrylate of the present invention may comprise one or more (meth)acrylate-functionalized moieties ACR. In this case, the (meth)acrylate-functionalized moieties may be identical or different from one another.

[0103] As used herein, a (meth)acrylate-functionalized moiety means a moiety functionalized with at least one (meth)acrylate group.

[0104] Each (meth)acrylate-functionalized molar ACR may independently have 1 to 5 (meth)acrylate groups, particularly 1 to 3 (meth)acrylate groups, and more specifically 1 (meth)acrylate group.

[0105] Each (meth)acrylate-functionalized moiety ACR may correspond to a residue (without an OH group) of a hydroxyl-functionalized (meth)acrylate compound. Examples of suitable hydroxyl-functionalized (meth)acrylate compounds are described in detail in component a) of the method for preparing the self-crosslinkable urethane (meth)acrylate of the present invention.

[0106] In particular, each (meth)acrylate functionalization moiety ACR is independently expressed by the following formula (I): TIFF2026518308000002.tif34170[In the formula, R4 is a linker with a (w'+1) valency; R5 is either H or methyl; w' is between 1 and 5, especially between 1 and 3, and more specifically, 1. It may be subject to these conditions.

[0107] In formula (I), R4 may be a (w'+1)-valent linker selected from aliphatic or aromatic hydrocarbon linkers, polyether linkers, polyester linkers, polycarbonate linkers, polyorganosiloxane linkers, polydiene linkers, isocyanurate linkers, and combinations thereof.

[0108] In particular, R4 may be a (w'+1) valency linker selected from aliphatic or aromatic hydrocarbon linkers, polyether linkers, polyester linkers, and combinations thereof.

[0109] More specifically, R4 may be a (w'+1) valent linker selected from alkylene, alkoxylated alkylene, polycaprolactone linker, and combinations thereof.

[0110] In one embodiment, R4 is given by equations (IIa) to (VIa): -(CR 22 R' 22 ) m - (IIa) -[(CR 23 R' 23 ) n -O] o -(CR 23 R' 23 ) n - (IIIa) -[(CR 24 R' 24 ) p -O] q -(CR 25 R' 25 ) r -[O-(CR 26 R' 26 ) p’ ] q’ - (IVa) -[(CR 27 R' 27 ) s -C(=O)O] t -(CR 28 R' 28 ) u -* (Va) -[(CR 29 R' 29 ) v -OC(=O)-(CR 30 R' 30 ) w -C(=O)-O] x -(CR 29 R' 29 ) v - (VIa) [In the formula, R 22 , R' 22 , R 25 , R' 25 , R 29 , R' 29 , R 30 and R' 30 is 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 is independently H or methyl; m is between 2 and 50; n, p, and p' are independently between 2 and 4; o is between 1 and 20; q and q' are independently between 0 and 20, provided that at least one of q and q' is not 0; r is between 2 and 20; s is between 3 and 12; t is between 1 and 20; u is between 2 and 8; v is between 2 and 20; w is between 2 and 30; x ranges from 1 to 20; The symbol * represents a bond site to the (meth)acrylate group. It can be a divalent linker selected from one of the following.

[0111] In particular, R4 can be a divalent linker selected from alkylene such as 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,12-dodecylene, 1,18-octadecylene, 2-methyl-1,3-propanediyl, 2,2-diethyl-1,3-propanediyl, 3-methyl-1,5-pentanediyl, 3,3-dimethyl-1,5-pentanediyl, 2,2-dimethyl-1,3-propanediyl, 2,4-diethyl-1,5-pentanediyl; alkoxylated derivatives of the aforementioned alkylene; esterified derivatives of the aforementioned alkylene; 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), i.e., residues of di-, tri-, tetra- or polyoxyalkylene (excluding OH groups); and residues of polyester polyol (excluding OH groups).

[0112] In another embodiment, R4 can be a trivalent linker according to one of the following formulas (12), (13), (19) and (20), or a tetravalent linker according to one of the following formulas (14) and (15): TIFF2026518308000003.tif102170[wherein each R h 、R i and R’ i is independently H or alkyl; R k 、R’ k and R’’ k is independently alkylene or alkenylene].

[0113] The total amount of the (meth)acrylate functionalized moiety ACR in the self-crosslinkable urethane (meth)acrylate of the present invention can account for 5 to 85%, particularly 10 to 80%, more specifically 15 to 75% of the total weight of the self-crosslinkable urethane (meth)acrylate.

[0114] In one embodiment, the total amount of the (meth)acrylate-functionalized moiety ACR in the self-crosslinkable urethane (meth)acrylate of the present invention may account for 50-85%, particularly 55-80%, and more specifically 60-75%, of the total weight of the self-crosslinkable urethane (meth)acrylate. Such an amount can be obtained, for example, when the (meth)acrylate-functionalized moiety is derived from (poly)caprolactone (meth)acrylate.

[0115] In another embodiment, the total amount of the (meth)acrylate-functionalized moiety ACR in the self-crosslinkable urethane (meth)acrylate of the present invention may account for 5 to 40%, particularly 10 to 35%, and more specifically 15 to 30%, of the total weight of the self-crosslinkable urethane (meth)acrylate. Such amounts can be obtained, for example, when the (meth)acrylate-functionalized moiety is derived from a hydroxyalkyl (meth)acrylate.

[0116] Polyurethane part UU The self-crosslinkable urethane (meth)acrylate of the present invention comprises at least two polyurethane moieties UU. The polyurethane moieties may be identical or different from each other.

[0117] As used herein, a polyurethane portion means a portion having at least two urethane bonds (-NH-C(=O)-O-) linked to one another by a linker.

[0118] Each polyurethane portion UU may independently have 2 to 3 polyurethane bonds.

[0119] Each polyurethane moiety UU can be derived from a polyisocyanate compound. As used herein, the term “derived from a polyisocyanate compound” means that the polyurethane moiety UU corresponds to a moiety obtained when a polyisocyanate is reacted with a hydroxyl-functionalized compound, i.e., the -NCO group of the polyisocyanate compound is converted to a urethane bond (-NH-C(=O)-O-).

[0120] Examples of suitable polyisocyanate compounds are described in detail in component b) of the method for preparing the self-crosslinkable urethane (meth)acrylate of the present invention.

[0121] In particular, each polyurethane portion UU is independently defined by the following formula (VIIa) or (VIIb): TIFF2026518308000004.tif58170[In the formula, R1 and R1' are independently either aliphatic linkers or aromatic linkers. It can follow one of the following.

[0122] The self-crosslinkable urethane (meth)acrylate of the present invention may comprise different types of polyurethane moieties, for example, one or more polyurethane moieties of formula (VIIa) and one or more polyurethane moieties of formula (VIIb).

[0123] In formula (VIIa), R1 may correspond to a diisocyanate residue (without the -NCO group). In particular, R1 is represented by the following formula: TIFF2026518308000005.tif31170[In formula: Alk is linear or branched alkylene, particularly methylene, 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 2,2,4- or 2,4-,4-trimethylhexylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,12-dodecylene, and 1,18-octadecylene; Ar is an optionally substituted arylene, in particular an optionally substituted arylene selected from phenylene, trilene, biphenylene, naphthylene, and anthracenylene; Cy is an optionally substituted cycloalkylene, in particular an optionally substituted cyclohexylene. One of the following can be selected.

[0124] In formula (VIIb), R1' may correspond to a triisocyanate residue (without the -NCO group). In particular, R1' is represented by the following formula: TIFF2026518308000006.tif74170[In the formula, Alk * These are linear or branched alkylenes, particularly methylene, methanetriyl, and undecane-1,6,11-triyl; Ar * is an optionally substituted arylene, in particular an optionally substituted arylene selected from phenylene, trilene, and biphenylene; R1 is as defined above for equation (VIIa), and in particular, 1,6-hexamethylene. One of the following can be selected.

[0125] In a preferred embodiment, each polyurethane portion UU is independently, - Part of equation (VIIa) [In the formula, R1 is given by the following formula: TIFF2026518308000007.tif21170 (in the formula, Alk is linear or branched alkylene, particularly methylene, 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 2,2,4- or 2,4-,4-trimethylhexylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,12-dodecylene, and 1,18-octadecylene; Cy is an optionally substituted cycloalkylene, in particular an optionally substituted cyclohexylene. [One of the following will be selected]; - Part of equation (VIIb) [In the formula, R'1 is the following: This corresponds to TIFF2026518308000008.tif41170, where R1 is a linear or branched alkylene, particularly 1,6-hexylene. - and mixtures thereof It can be selected from the following.

[0126] The total amount of polyurethane portion UU in the self-crosslinkable urethane (meth)acrylate of the present invention may account for 10-65%, particularly 15-60%, and more specifically 20-55% of the total weight of the self-crosslinkable urethane (meth)acrylate.

[0127] Color-developing marker Q The self-crosslinkable urethane (meth)acrylate of the present invention comprises at least one chromophore portion Q. The self-crosslinkable urethane (meth)acrylate of the present invention may comprise multiple chromophore portions Q. In this case, the chromophore portions may be identical or different from one another.

[0128] As used herein, a chromophore moiety means a moiety containing a group that absorbs light and can generate reactive species useful for initiating polymerization reactions. In particular, the chromophore moiety may be a Norrish-type II chromophore moiety, i.e., a chromophore moiety that does not fragment when exposed to radiation and therefore does not normally initiate radical chain polymerization unless a co-initiator such as an amine synergist is present. When exposed to radiation, the interaction between the type II chromophore moiety and the co-initiator generates radical species, which can initiate polymerization of the UV-curable resin.

[0129] In preferred embodiments, the self-crosslinkable urethane (meth)acrylates of this specification include at least one Norrish II type chromophore portion. In particular, each chromophore portion Q may be a Norrish II type chromophore portion.

[0130] Each chromophore portion Q may correspond to a residue (without an OH group) of a hydroxyl-functionalized photoinitiator compound. Examples of suitable hydroxyl-functionalized photoinitiators are detailed in component c) of the method for preparing the self-crosslinkable urethane (meth)acrylate of the present invention.

[0131] In particular, each chromophore moiety Q can independently contain at least one monovalent or divalent photoinitiator moiety PI selected from a benzophenone moiety, a thioxanthone moiety, a xanthone moiety, an acridone moiety, a camphorquinone moiety, a benzyl moiety, a coumarin moiety, a ketocoumarin moiety, their derivatives, and combinations thereof, preferably at least one monovalent or divalent photoinitiator moiety PI selected from a benzophenone moiety or a thioxanthone moiety.

[0132] More specifically, each chromophore moiety Q contains at least one monovalent photoinitiator moiety PI corresponding to one of the following formulas (VIII), (XI), (XIV), (XVII), (XVIII) or (XIX), or at least one divalent photoinitiator moiety PI corresponding to one of the following formulas (IX), (X), (XII), (XIII), (XV) or (XVI): TIFF2026518308000009.tif183170[wherein, each E is independently S, O or NR, particularly S; R is H, optionally substituted alkyl or optionally substituted aryl; each R a is independently H, F, Cl, Br, I, -OR b , -SR b , -N(R b )2, -NO2, -CN, -C(=O)R b , -O-C(=O)R b , -C(=O)OR b , -C(=O)N(R b )2, -NR b -C(=O)-R b , -SO2-N(R b )2, or an optionally substituted group selected from the group consisting of alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl and heteroaryl; or two adjacent R a groups may form a 5- to 8-membered ring together with the carbon atom to which they are attached; each R bEach R is independently H, or an optionally substituted group selected from alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkalyl and heteroaryl, preferably each R b [These are independently substituted groups selected from alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl, and heteroaryl.]

[0133] More specifically, each chromophore portion Q may independently include at least one monovalent photoinitiator portion PI corresponding to one of formulas (VIII) or (XI) (wherein E is S), or at least one divalent photoinitiator portion PI corresponding to one of formulas (IX), (X), (XII), or (XIII) (wherein E is S).

[0134] More specifically, each chromophore portion Q includes at least one monovalent photoinitiator portion PI corresponding to one of the following formulas (VIIIa) or (XIa), or at least one divalent photoinitiator portion PI corresponding to one of the following formulas (IXa), (Xa), (XIIa), or (XIIIa): TIFF2026518308000010.tif88170[In the formula, R' a and R' d independently, is alkyl, Ar, -S-Ar or -O-Ar, where Ar is aryl, in particular methyl, Ph, -S-Ph or -O-Ph, and Ph is phenyl; R' b These are alkyl groups, especially methyl groups; R' c , R' e and R' f independently, is a halogen, alkoxy, alkyl or -C(=O)-Ar, where Ar is an aryl, in particular F, Cl, methyl, ethyl, isopropyl or -C(=O)-Ph, and Ph is phenyl; x1 and x4 are independently 0, 1, 2, or 3, in particular 0 or 1; x2, x3, and x5 are independently 0, 1, or 2, in particular 0 or 1; x6 is either 0 or 1.

[0135] More specifically, each chromophore portion Q may independently include at least one monovalent photoinitiator portion PI corresponding to formula (VIII) or (XI) (wherein E is S), or at least one divalent photoinitiator portion PI corresponding to formula (X) or (XIII) (wherein E is S).

[0136] More specifically, each chromophore portion Q may independently include at least one monovalent photoinitiator portion PI corresponding to formula (VIIIa) or (XIa) defined above, or at least one divalent photoinitiator portion PI corresponding to formula (Xa) or (XIIIa) defined above.

[0137] Each photoinitiator portion PI may be independently linked to one or more linkers, thereby forming a chromophore portion Q.

[0138] In particular, each chromophore portion Q is independently expressed by the following equations (XXa), (XXb), or (XXc): TIFF2026518308000011.tif43170[In the formula, L0 is a (s'+t'+2) valence linker; Each L1 is an independently divalent linker; Each L2 is an independent (u'+2) valence linker; Each PI 1 This is independently a monovalent photoinitiator moiety PI as defined above; Each PI 2 This is independently the divalent photoinitiator moiety PI defined above; s' is 0, 1, or 2; in particular, it is 0 or 1; t' is 1, 2, 3, or 4; in particular, 2 or 3; Each u' is independently 0 or 1, especially 0. It can follow one of the following.

[0139] In formulas (XXa) and (XXc), each L1 and L2 may independently be selected from a direct bond or a linker containing 1 to 20, preferably 1 to 10, carbon atoms, the linker optionally containing one or more heteroatoms, such as O, N, or S. In particular, each L1 and L2 may independently be directly bonded or -O-, -S-, -NR l -, -C(=O)-, -OC(=O)-, -C(=O)-O-, -NR l -C(=O)-, -C(=O)-NR l -, -OC(=O)-O-, and combinations thereof (where R in the formula) l The linker may be selected from hydrocarbon linkers, which may contain one or more bonds selected from H, alkyl, or aryl.

[0140] In formula (XXb), L0 may be a linker containing 1 to 20, preferably 1 to 10, carbon atoms, the linker optionally containing one or more heteroatoms, such as O, N, or S. In particular, L0 may be -O-, -S-, -NR l -, -C(=O)-, -OC(=O)-, -C(=O)-O-, -NR l -C(=O)-, -C(=O)-NR l -, -OC(=O)-O-, and combinations thereof (where R in the formula) l The hydrocarbon linker may contain one or more bonds selected from H, alkyl, or aryl.

[0141] The self-crosslinkable urethane (meth)acrylate of the present invention may comprise at least one chromophore portion Q according to formula (XXa) defined above. The chromophore portion Q according to formula (XXa) may have a single photoinitiator portion PI and a single bonding point to the backbone of the self-crosslinkable urethane (meth)acrylate.

[0142] In formula (XXa), L1 is preferably selected from direct bonding, C1-C6 alkylene, C1-C6 oxyalkylene, C1-C6 thioalkylene, C1-C6 ketoalkylene, C1-C6 aminoalkylene, C1-C6 carboxyalkylene, C1-C6 amidealkylene, or a combination thereof. In particular, L1 is directly bonded, alkylene of formula (C-1), oxyalkylene of formula (C-2), thioalkylene of formula (C-3), ketoalkylene of formula (C-4), aminoalkylene of formula (C-5), carboxyalkylene of formula (C-6), amidealkylene of formula (C-7), alkylene-aminoalkylene of formula (C-8), oxyalkylene-aminoalkylene of formula (C-9), oxyalkylene-amidealkylene of formula (C-10): TIFF2026518308000012.tif104170[In the formula, Each R m , R' m , R o , R' o , R p , R' p , R q , R' q , R r , R' r , R s , R' s , R t and R' t is independently H or an optionally substituted alkyl, particularly H; R'' r and R* r is independently H or an optionally substituted alkyl; f, g, h, j, and j' are independently 1, 2, 3, 4, 5, or 6, especially 1 or 2; i and i' are independently 1, 2, 3, 4, or 5, especially 1; The symbol ● represents the connection point to the PI section. It can be selected from the following.

[0143] In formula (XXa), L1 is preferably selected from a direct bond, alkylene of formula (C-1), oxyalkylene of formula (C-2), aminoalkylene of formula (C-5), amidealkylene of formula (C-7), alkylene-aminoalkylene of formula (C-8), oxyalkylene-aminoalkylene of formula (C-9), or oxyalkylene-amidealkylene of formula (C-10).

[0144] In equation (XXa), PI 1 Preferably, it follows formula (VIII) or (XI) defined above, where E in formula (XI) is preferably S. In formula (XXa), PI 1 This more preferably follows formula (VIIIa) or (XIa) defined above.

[0145] In particular, the self-crosslinkable urethane (meth)acrylate of the present invention is of the following formula (XXa1) or (XXa2) TIFF2026518308000013.tif54170[In the formula, R' a is alkyl, Ar, -S-Ar or -O-Ar, where Ar is aryl, in particular methyl, Ph, -S-Ph or -O-Ph, and Ph is phenyl; R' b These are alkyl groups, especially methyl groups; R' c is a halogen, alkoxy, alkyl or -C(=O)-Ar, where Ar is an aryl, in particular F, Cl, methyl, ethyl, isopropyl or -C(=O)-Ph, and Ph is phenyl; x1 is 0, 1, 2, or 3, especially 0 or 1; x2 is 0, 1, or 2, especially 0 or 1; x3 is 0, 1, or 2, especially 0 or 1; L1 is selected from direct bonding, alkylene of formula (C-1), oxyalkylene of formula (C-2), aminoalkylene of formula (C-5), amidealkylene of formula (C-7), alkylene-aminoalkylene of formula (C-8), oxyalkylene-aminoalkylene of formula (C-9), or oxyalkylene-amidealkylene of formula (C-10). It may include at least one chromophore portion Q corresponding to [the specified value].

[0146] More specifically, the self-crosslinkable urethane (meth)acrylate of the present invention is defined by the following formulas (XXa3) to (XXa17): It may contain at least one chromophore portion Q corresponding to one of TIFF2026518308000014.tif201170.

[0147] In a preferred embodiment, the self-crosslinkable urethane (meth)acrylate of the present invention comprises at least one chromophore portion Q according to formula (XXb) or (XXc) as defined above.

[0148] The self-crosslinkable urethane (meth)acrylate of the present invention may comprise at least one chromophore portion Q according to formula (XXc) defined above. The chromophore portion Q according to formula (XXc) may have a single photoinitiator portion PI and at least two, preferably two, bonding sites to the backbone of the self-crosslinkable urethane (meth)acrylate.

[0149] In formula (XXc), each L2 is preferably independently selected from a direct bond, a C1-C6 alkylene, a C1-C6 oxyalkylene, a C1-C6 thioalkylene, a C1-C6 ketoalkylene, a C1-C6 aminoalkylene, a C1-C6 carboxyalkylene, a C1-C6 amidealkylene, or a combination thereof. In particular, each L2 can be selected from direct bonding, alkylene of formula (C-1) defined above, oxyalkylene of formula (C-2) defined above, thioalkylene of formula (C-3) defined above, ketoalkylene of formula (C-4) defined above, aminoalkylene of formula (C-5) defined above, carboxyalkylene of formula (C-6) defined above, amidealkylene of formula (C-7) defined above, alkylene-aminoalkylene of formula (C-8) defined above, oxyalkylene-aminoalkylene of formula (C-9) defined above, and oxyalkylene-amidealkylene of formula (C-10) defined above. More specifically, each L2 can be independently selected from direct bonding, amidealkylene of formula (C-7) defined above, or oxyalkylene-amidealkylene of formula (C-10) defined above.

[0150] In equation (XXc), each u' is preferably 0.

[0151] In equation (XXc), PI 2 Preferably, it follows formulas (IX), (X), (XII), or (XIII) defined above, where E in formulas (XII) and (XIII) is preferably S. In formula (XXc), PI 2 This more preferably follows the formulas (IXa), (Xa), (XIIa), or (XIIIa) defined above.

[0152] Specifically, the self-crosslinkable urethane (meth)acrylate of the present invention is defined by the following formulas (XXc1)~(XXc4): TIFF2026518308000015.tif53170[In the formula, R' dis alkyl, Ar, -S-Ar or -O-Ar, where Ar is aryl, in particular methyl, Ph, -S-Ph or -O-Ph, and Ph is phenyl; R' e and R' f independently, is a halogen, alkoxy, alkyl or -C(=O)-Ar, where Ar is an aryl, in particular F, Cl, methyl, ethyl, isopropyl or -C(=O)-Ph, and Ph is phenyl; x4 is 0, 1, 2, or 3, especially 0 or 1; x5 is 0, 1, or 2, especially 0 or 1; x6 is either 0 or 1; Each L2 is independently selected from a direct bond, an amide alkylene of formula (C-7) defined above, or an oxyalkylene-amide alkylene of formula (C-10) defined above. It may include at least one chromophore portion Q from one of the following.

[0153] More specifically, the self-crosslinkable urethane (meth)acrylate of the present invention is defined by the following formulas (XXc5)~(XXc13): It may include at least one chromophore portion Q from one of TIFF2026518308000016.tif191170.

[0154] The self-crosslinkable urethane (meth)acrylate of the present invention may comprise at least one chromophore portion Q according to formula (XXb) defined above. The chromophore portion Q according to formula (XXb) defined above may have at least one photoinitiator portion PI and at least two bonding points to the backbone of the self-crosslinkable urethane (meth)acrylate.

[0155] In one embodiment, the self-crosslinkable urethane (meth)acrylate of the present invention may include at least one chromophore portion Q according to formula (XXb). The chromophore portion Q has at least two photoinitiator portions PI and at least two bonding points to the backbone of the self-crosslinkable urethane (meth)acrylate.

[0156] In particular, the self-crosslinkable urethane (meth)acrylate of the present invention may include at least one chromophore portion Q according to formula (XXb). The chromophore portion Q has a number of photoinitiator portions PI equal to the number of bond points to the backbone of the self-crosslinkable urethane (meth)acrylate.

[0157] More specifically, the self-crosslinkable urethane (meth)acrylate of the present invention is of formula (XXI): TIFF2026518308000017.tif38170[In the formula, n1 is 0, 1, 2, 3, or 4; n2 is 0, 1, 2, 3, or 4; The sum n1 + n2 is equal to 1, 2, 3, or 4; Each PI 1 This is independently a monovalent photoinitiator moiety PI as defined above; Each X independently, -NR 1 -, -O-, -S-, *-C(=O)-O- or *-C(=O)-NR 1 -and; Each V is independently bonded in direct, #-O-CH2-, #-C(=O)-O-CH2-, and #-NR 5 -CH2- or #-C(=O)-NR 5 -CH2-; Each W is independently a direct bond, -CH2-OC(=O)-# or -C(=O)-O-#; Each R 1 These are independently H, alkyl, or aryl; R 2 This is a direct link or linker; Each R 3 They are, independently, direct links or linkers; Each R 4 independently, H, an optionally substituted alkyl, or an optionally substituted alkenyl; Each R 5 These are independently H, alkyl, aryl, or the following formulas: TIFF2026518308000018.tif14170 (in the formula, X, R 3 and PI 1(As defined above, the symbol} represents the bond point to the nitrogen atom.) It is a base by; The symbol * is R 3 Represents the connection point to; The symbol # is R 2 [Represents a connection point to] It may include at least one chromophore portion Q.

[0158] In equation (XXI), the value of n1 is 0, 1, 2, 3, or 4. In particular, the value of n1 can be 0, 1, or 2, and more specifically, n1 can be 0.

[0159] In equation (XXI), the value of n² is 0, 1, 2, 3, or 4. In particular, the value of n² can be 2, 3, or 4, and more specifically, n² can be 2 or 3.

[0160] In equation (XXI), the sum n1 + n2 is equal to 1, 2, 3, or 4. In particular, the sum n1 + n2 may be equal to 2, 3, or 4, and more specifically, the sum n1 + n2 may be equal to 2 or 3. When the sum n1 + n2 is equal to 1, n1 is preferably 0, n2 is preferably 1, and V is preferably #-NR 5 -CH2- or #-C(=O)-NR 5 -CH2- and R 5 Preferably, the formula is as follows: This is based on TIFF2026518308000019.tif14170.

[0161] In one embodiment, the value of n1 may be 0, and the value of n2 may be 1, 2, 3, or 4. In particular, the value of n1 may be 0, and the value of n2 may be 2 or 3. In another embodiment, the value of n2 may be 0, and the value of n1 may be 2, 3, or 4. In particular, the value of n2 may be 0, and the value of n1 may be 2. In yet another embodiment, the value of n1 may be 1, 2, or 3, and the value of n2 may be 1, 2, or 3. In particular, the value of n1 may be 1, and the value of n2 may be 1 or 2.

[0162] In a preferred embodiment, n2 is non-zero, and R 2 The formula is as follows: TIFF2026518308000020.tif16170[where, PI 1 V, X, R 3 and R 4 This is as defined herein, and the symbol # is R 2 [Represents a connection point to] It has at least one part that corresponds to [this].

[0163] R 2 may have at least one part of equation (1a), where V is #-O-CH2- and R 4 This is H. Such a moiety can be derived from ring-opening of a glycidyl ether group.

[0164] R 2 may have at least one part of equation (1a), where V is #-(C=O)-O-CH2- and R 4 This is H. Such a moiety can be derived from ring-opening of a glycidyl ester group.

[0165] R 2 may have at least one part of equation (1a), where V is #-NR 5 -CH2- and R 4 H is R 5 This is as defined above. Such a part can be derived from ring-opening of the glycidylamine group.

[0166] R 2 This may have at least one part of equation (1a), where V is #-(C=O)-NR 5 -CH2- and R 4 H is R 5 This is as defined above. Such a part can be derived from ring-opening of the glycidylamide group.

[0167] R 2 may have at least one part of equation (1a), where V is a direct bond and R 4This is H, an optionally substituted alkyl group, or an optionally substituted alkenyl group. Such a moiety can be derived from ring-opening of an epoxy group, which is derived from the epoxidation of an acyclic carbon-carbon double bond.

[0168] R 2 R may have one, two, three, or four parts of equation (1a). These parts may be identical or different from one another. For example, R 2 It may have two, three or four parts of equation (1a), where V is #-O-CH2- and R 4 It is H. Or, R 2 This can have two, three, or four parts of equation (1a), where V is #-(C=O)-O-CH2- and R 4 It is H. Or, R 2 may have one or two parts of equation (1a), where V is #-NR 5 -CH2- and R 4 It is H. Or, R 2 This may have one or two parts of equation (1a), where V is #-(C=O)-NR 5 -CH2- and R 4 It is H. Or, R 2 This can have two or three parts of equation (1a), where V is a direct bond and R 4 is H or an optionally substituted alkyl group. Alternatively, R 2 may have at least two parts of formula (1a), where the parts are V and / or R 4 They differ from one another due to their properties.

[0169] In another embodiment, n1 is non-zero, and R 2 This is given by the following equation (2a): TIFF2026518308000021.tif25170[where, PI 1 X, W and R 3 This is as defined herein, and the symbol # is R 2 [Represents a connection point to] It has at least one part by

[0170] Such parts can be derived from ring-opening of alicyclic epoxide groups.

[0171] R 2 can have at least one part of equation (2a), where W is -CH2-OC(=O)-#.

[0172] R 2 may have at least one part of equation (2a), where W is -C(=O)-O-#.

[0173] R 2 may have at least one part of equation (2a), where W is a direct bond.

[0174] R 2 It may have two, three, or four parts of equation (2a). These parts may be the same or different from one another. For example, R 2 It may have two, three, or four parts of equation (2a), where W is -CH2-OC(=O))-#. Alternatively, R 2 It may have two, three, or four parts of equation (2a), where W is -C(=O)-O-#. Alternatively, R 2 It may have at least two parts of equation (2a), where these parts are different from each other due to the properties of W.

[0175] In yet another embodiment, both n1 and n2 are non-zero, R 2 It has at least one part according to formula (1a) and at least one part according to formula (2a). In particular, R 2 This is one part by equation (1a) (where V is a direct bond and R 4 It may have a part (where W is a direct bond) and a part by equation (2a) (where W is a direct bond). Alternatively, R 2 This is one part according to equation (1a) (where V is #-O-CH2- and R 4 It may have a part (where W is a direct bond) and a part by equation (2a) (where W is a direct bond). Alternatively, R2 This is the two parts by equation (1a) (where V is #-(C=O)-O-CH2- and R 4 It may have a part (where W is a direct bond) and a part according to equation (2a).

[0176] In particular, equation (XXI) is equivalent to the following equations (XXII)~(XXXV): TIFF2026518308000022.tif244170TIFF2026518308000023.tif235170[In the formula, PI 1 X, R 2 , R 3 , R 4 and R 5 This is as defined herein; n3, n4, n7, n 14 and n 15 These are independently 2, 3, or 4, preferably 2 or 3; n5 and n6 are independently 1 or 2, preferably 2; n8 is 1, 2, or 3, preferably 2; n9 is 1, 2, or 3, preferably 1; n 10 , n 11 , n 16 , n 17 , n 18 , n 19 , n 20 , n 21 , n 22 and n 23 Each is independently 1 or 2, preferably 1; n 12 and n 13 [These are independently 1, 2, or 3, preferably 1.] It could be equivalent to one of these.

[0177] A chromophore portion comprising one of formulas (XXII), (XXIII), (XXIV), (XXVI), (XXVII), (XXVIII), and (XXIX) is preferred. A chromophore portion comprising one of formulas (XXII), (XXIII), (XXIV), and (XXVI) is particularly preferred.

[0178] In equations (XXI) to (XXXV), each R 3 These are, independently, direct connections or linkers.

[0179] In particular, each R 3 The linker may independently be a directly bonded or divalent linker containing 1 to 15, preferably 1 to 10, carbon atoms. The linker may optionally further contain one or more heteroatoms, such as O, N, or S. For example, the linker may be -O-, -S-, -NR l -, -C(=O)-, -OC(=O)-, -C(=O)-O-, -NR l -C(=O)-, -C(=O)-NR l -, -OC(=O)-O-, -NR l -C(=O)-O-, -OC(=O)-NR l -and their combinations (R l The hydrocarbon linker may contain one or more bonds selected from H, alkyl, or aryl.

[0180] More specifically, each R 3 Independently, - direct binding; - Acyclic linkers that may be saturated or unsaturated, in particular acyclic linkers having 1 to 6, 1 to 4, or 1 to 2 carbon atoms; or - Aromatic or non-aromatic monocyclic or polycyclic cyclic linkers, particularly cyclic linkers having 6-10, 7-9, or 7-8 carbon atoms. It is possible.

[0181] More specifically, each R 3 These can be independently selected from directly bonded, C1-C6 alkylene, C1-C6 oxyalkylene, C1-C6 alkenylene, C1-C6 thioalkylene, C1-C6 ketoalkylene, or C1-C6 aminoalkylene.

[0182] More specifically, each R 3These are independently, directly bonded, alkylene of formula (C-11), oxyalkylene of formula (C-12), thioalkylene of formula (C-13), ketoalkylene of formula (C-14), or aminoalkylene of formula (C-15): TIFF2026518308000024.tif38170[In the formula, Each R m , R' m , R o , R' o , R p , R' p , R q , R' q , R r and R' r is independently H or an optionally substituted alkyl, particularly H; R'' r is H or an optionally substituted alkyl group; f, g, h, and j are independently 1, 2, 3, 4, 5, or 6, especially 1 or 2; i is 1, 2, 3, 4, or 5, especially 1; The symbol ● is PI 1 Represents the connection point to a part; The symbol § represents a connection point to the X portion. It can be selected from the following.

[0183] More specifically, each R 3 These can be independently selected from direct bonding, alkylene of formula (C-11), oxyalkylene of formula (C-12) defined above, and aminoalkylene of formula (C-15) defined above.

[0184] More specifically, each R 3 These can be independently selected from direct bonding, alkylene of formula (C-11), and oxyalkylene of formula (C-12) as defined above.

[0185] In equations (XXI) to (XXXV), each linker R 3It is linked to X. X can correspond to a residue of an epoxide reactive group, i.e., a group that can open an epoxide ring. Examples of epoxide reactive groups are alcohols, thiols, primary and secondary amines, carboxylic acids, and amides.

[0186] In equations (XXI) to (XXXV), each X is independently -NR 1 -, -O-, -S-, *-C(=O)-O- or *-C(=O)-NR 1 -and; each R 1 is independently H, alkyl, or aryl; the symbol * is R 3 This represents a connection point to [a specific location].

[0187] In particular, each X independently, -NR 1 It can be -, -O- or *-C(=O)-O-. More specifically, each X is independently -NR 1 -or *-C(=O)-O-

[0188] In equations (XXI) to (XXXV), each R 2 R is independently a direct link or a linker. 2 When it is a linker, the linker may be divalent, trivalent, or tetravalent. 2 When it is a linker, the linker may be aliphatic or aromatic, especially aliphatic. 2 It may contain 0 to 20 carbon atoms, especially 0 to 15, and more specifically 0 to 10 carbon atoms. 2 It may contain 0 to 2 oxygen atoms, especially 0 to 1, and more specifically, 0 oxygen atoms. 2 R may contain 0 to 2 heteroatoms, particularly 0 to 1, or more specifically 0, selected from O, N, or S. 2 The molecular weight may be less than 500 g / mol, particularly less than 400 g / mol, more specifically less than 300 g / mol, even more specifically 250 g / mol, and even more specifically less than 200 g / mol.

[0189] In particular, each R 2The linker can be independently a direct bond or a linker selected from the group consisting of alkylene, heteroatom-containing alkylene, alkenylene, heteroatom-containing alkenylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, and combinations thereof.

[0190] More specifically, each R 2 The linker can be independently a direct bond or a linker selected from the group consisting of alkylene, heteroatom-containing alkylene, cycloalkylene, arylene, heteroarylene, and combinations thereof.

[0191] In one embodiment, R 2 The linker may be an arylene, a heteroarylene, or a combination thereof. In such cases, R 2 It is preferably arylene.

[0192] For example, R 2 This is expressed by the following equations (3) to (9): TIFF2026518308000025.tif113170[wherein L is a direct link or linker; R e , R' e and R'' e These are independently selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkoxy, -C(=O)O-alkyl, and halogen atoms; R f is either H or methyl; a, a', c, and c' are independently either 0 or 1; b is either 1 or 2. It can be represented by one of the following.

[0193] In particular, R 2 R can be expressed by one of the formulas (3) or (4) defined above, preferably by formula (4). 2When expressed by equation (4), L is selected from direct bonds, alkylenes, -CR'3R'4-, -C(=O)-, -C(=O)-O-Alk-OC(=O)-, -SO-, -SO2-, -C(=CCl2)-, and -CR'5R'6-Ph-CR'7R'8-; Here, R'3 and R'4 may independently be H, alkyl, cycloalkyl, aryl, haloalkyl, and perfluoroalkyl, or R'3 and R'4 may form a ring together with the carbon atoms to which they are bonded; R'5, R'6, R'7, and R'8 are independently selected from H, alkyl, cycloalkyl, aryl, haloalkyl, and perfluoroalkyl; Alk is an alkylene; Ph is phenylene which may be substituted with one or more groups selected from alkyl, cycloalkyl, aryl, and halogen atoms.

[0194] More specifically, R 2 This may correspond to a residue of an aromatic polyol, polyacid, polyamine, hydroxy acid, or hydroxyamine (without OH, COOH, and / or amino groups), which may be substituted.

[0195] For example, R 2These can be residues of substituted aromatic polyols, polyacids, polyamines, hydroxyacids, or hydroxyamines containing 1 to 3, preferably 1 or 2, aromatic rings, such as pyrocatechol, resorcinol, cardol, (hydroxymethyl)phenol, benzenedimethanol, hydroxybenzoic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, bisphenol, biphenyldiol, phloroglucinol, pyrogallol, tris(hydroxyphenyl)methane, tris(hydroxyphenyl)ethane, trimellitic acid, gallic acid, condensation products of optionally substituted aromatic alcohols and formaldehyde (also called novolacs), phenylenediamine, toluylenediamine, xylenediamine, diaminobiphenyl, diaminodiphenyl ether, diaminodiphenylmethane, diaminodiphenylsulfone, aminophenol, and (aminophenoxy)phenol.

[0196] More specifically, R 2 is a bisphenol residue that may be substituted. Suitable examples of bisphenols are bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C2, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol-Z, dinitrobisphenol A, tetrabromobisphenol A, and combinations thereof.

[0197] In another embodiment, R 2 This can be an aliphatic linker, for example, alkylene, heteroatom-containing alkylene, cycloalkylene, heterocycloalkylene, or a combination thereof. In such cases, R 2 Preferably, this is an alkylene, a heteroatom-containing alkylene, a cycloalkylene, or a combination thereof.

[0198] For example, R 2 This is represented by the following equations (10)~(20): TIFF2026518308000026.tif147170[In the formula, R' e And L are as defined above for equation (4); Each R g , R' g , R h , R i and R' i is independently H or alkyl; Each R j These are independently H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkoxy, -C(=O)O-alkyl, and halogen atoms; R k , R' k and R'' k These are independently alkylenes or alkenylenes; d is between 1 and 12; e and e' are independently either 0 or 1. It can be represented by one of the following.

[0199] In particular, R 2 This can be represented by one of the formulas (10), (11), (12), (13), (15), (16), (17), or (19) defined above, preferably by one of the formulas (10), (11), or (12).

[0200] More specifically, R 2 This may correspond to a residue of an aliphatic polyol, polyacid, polyamine, hydroxy acid, or hydroxyamine (without OH, COOH, and / or amino groups), which may be substituted.

[0201] For example, R 2These include ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 1,3- or 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, and 3-methyl-1,5-pentanediol. 3,3-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 3,3-butylethyl-1,5-pentanediol, cyclohexanediol, cyclohexane-1,4-dimethanol, norbornenedimethanol, norbornanedimethanol, tricyclodecanediol, tricyclodecanedimethanol, hydrogenated bisphenol A, B, F or S, trimethylolmethane, trimethylolethane, trimethylolpropane, di(trimethylolpropane) Ropane), pentaerythritol, glycerol, dianhydrohexitol (i.e., isosorbide, isomannide, isoidide), hydroxylated vegetable oil, tris(2-hydroxyethyl) isocyanurate, 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,12-dodecamethylenediamine, isophoronediamine, diamino The residues may be substituted aliphatic polyols, polyacids, polyamines, hydroxyacids, or hydroxyamines, selected from cyclohexane, methylcyclohexanediamine, bis(aminomethyl)cyclohexane, diaminodecahydronaphthalene, dimethyldiaminodicyclohexylmethane, diaminodicyclohexylmethane, bis(aminomethyl)norbornane, malonic acid, succinic acid, 2-methylsuccinic acid, 2,2-dimethylsuccinic acid, glutaric acid, 3,3-diethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, citric acid, 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid, glycolic acid, 12-hydroxystearic acid, ethanolamine, and diethanolamine.

[0202] Alternatively, R 2 This corresponds to a residue of an epoxidized polyunsaturated compound, i.e., a compound having at least two epoxidized non-aromatic carbon-carbon double bonds. As used herein, the term “residue of an epoxidized polyunsaturated compound” means a residue obtained by removing a terminal group containing an epoxide ring from a compound. For example, an epoxidized polyunsaturated compound may have the following formula: If TIFF2026518308000027.tif18170 is present, the residues of the epoxidized polyunsaturated compound are given by the following formula: This corresponds to TIFF2026518308000028.tif12170.

[0203] Alternatively, R 2 This corresponds to the residue of the epoxidized oil. As used herein, the term “residue of the epoxidized oil” means the residue obtained by removing terminal groups containing epoxide rings from a compound. For example, if the epoxidized oil is of the following formula: TIFF2026518308000029.tif41170[In the formula, Each R 4 independently, H, an optionally substituted alkyl, or an optionally substituted alkenyl; R k , R' k and R'' k [These are independently alkylenes or alkenylenes.] If it has the following formula, the residue of the epoxidized oil is: This corresponds to TIFF2026518308000030.tif41170.

[0204] In equations (XXI), (XXVI), (XXIX), and (XXXV), each R 4 These are independently H, an optionally substituted alkyl, or an optionally substituted alkenyl.

[0205] In one embodiment, each R 4is H. In another embodiment, each R 4 is an optionally substituted alkyl or optionally substituted alkenyl. In yet another embodiment, R 4 Part of the group is H, and R 4 The other parts of the group are optionally substituted alkyl or optionally substituted alkenyl. Preferably, each R 4 H is H.

[0206] In equations (XXIV), (XXV), and (XXVIII), each R 5 These are independently H, alkyl, aryl, or the following formulas: TIFF2026518308000031.tif14170[where, X, R 3 and PI 1 This is as defined above, and the symbol} represents the bond point to the nitrogen atom. It is a basis of [the system].

[0207] In particular, each R 5 is H, alkyl, or the following formula: This may be based on TIFF2026518308000032.tif14170.

[0208] In equations (XXI) to (XXXV), each PI 1 Preferably, independently of formula (VIII) or (XI) defined above, where E in formula (XI) is preferably S. In formula (XXa), each PI 1 This more preferably follows independently of formula (VIIIa) or (XIa) defined above.

[0209] In a particularly preferred embodiment, the self-crosslinking urethane (meth)acrylate is of the following formulas: (XXII), (XXIII), (XXIV), or (XXVI): TIFF2026518308000033.tif117170[In the formula, n3, n4, n5, and n7 are independently 2, 3, or 4, preferably 2 or 3; Each PI 1Each PI is independently a monovalent photoinitiator molar PI according to formula (VIII) or (XI) defined above, preferably each PI 1 is a monovalent photoinitiator molar PI according to formula (VIIIa) or (XIa) defined above; Each X independently, -NR 1 -, -O- or *-C(=O)-O-, preferably -NR 1 -or *-C(=O)-O-; Each R 1 is independently H or alkyl; Each R 2 These are, independently, alkylenes or heteroatom-containing alkylenes; Each R 3 These are independently, directly bonded, alkylene of formula (C-11) as defined above, oxyalkylene of formula (C-12) as defined above, or aminoalkylene of formula (C-15) as defined above, preferably directly bonded, alkylene of formula (C-11) or oxyalkylene of formula (C-12); Each R 4 is H; Each R 5 These are independently H, alkyl, or the following formulas: TIFF2026518308000034.tif14170 (in the formula, X, R 3 and PI 1 (As defined above, the symbol} represents the bond point to the nitrogen atom.) It is a base by; The symbol * is R 3 [Represents a connection point to] It includes at least one chromophore portion Q from one of the following.

[0210] In a particularly preferred embodiment, the self-crosslinking urethane (meth)acrylate is defined by the following formulas (XXb1) to (XXb9): It contains at least one chromophore portion Q from one of TIFF2026518308000035.tif201170 or TIFF2026518308000036.tif78170.

[0211] In another embodiment, the self-crosslinkable urethane (meth)acrylate of the present invention may comprise at least one chromophore portion Q of formula (XXb). The chromophore portion Q comprises a single photoinitiator portion PI and at least two bonding points to the backbone of the self-crosslinkable urethane (meth)acrylate.

[0212] In particular, the self-crosslinkable urethane (meth)acrylate of the present invention is derived from the following formulas (XXXVI) to (XXXXI): TIFF2026518308000037.tif231170[In the formula, Each PI is independently a monovalent or divalent photoinitiator moiety PI as defined above; Each PI 1 This is independently a monovalent photoinitiator moiety PI as defined above; Each L3 is independently selected from either a direct bond or a linker containing 1 to 20 carbon atoms; Each Y is independently either H or alkyl; Each Z and Z' is independently a linker containing 1 to 20 carbon atoms; each n 24 , n 26 , n 28 and n 31 is independently 0 or 1, especially 1; each n 29 , n 32 , n 34 and n 36 It is independently 1, 2, or 3, especially 1; each n 27 and n 33 They are independently 1, 2, or 3; especially 1 or 2; each n 25 and n 30 They are independently 1 or 2; n 35 is 1, 2, or 3, especially 2; n 37 is either 1 or 2, especially 2. It may include at least one chromophore portion Q from one of the following.

[0213] In equation (XXXVI), n25 It is preferably 1 or 2.

[0214] In equation (XXXVII), n 27 It is preferably 1 or 2.

[0215] In equation (XXXVIII), n 29 When n is 1, 30 It is preferably 2.

[0216] In equation (XXXVIII), n 30 When n is 1, 29 It is preferably 2 or 3.

[0217] In equation (XXXIX), n 32 When n is 1, 33 It is preferably 2.

[0218] In equation (XXXIX), n 33 When n is 1, 32 It is preferably 2 or 3.

[0219] In equation (XXXX), n 34 When n is 1, 35 It is preferably 2.

[0220] In equation (XXXX), n 35 When n is 1, 34 It is preferably 2 or 3.

[0221] In equation (XXXXI), n 36 When n is 1, 37 It is preferably 2.

[0222] In equation (XXXX), n 37 When n is 1, 36 It is preferably 2 or 3.

[0223] In formulas (XXXVI) to (XXXXI), each L3 is independently selected from either a direct bond or a linker containing 1 to 20 carbon atoms.

[0224] In particular, each L3 can be independently selected from direct linkage, C1-C6 alkylene, C1-C6 oxyalkylene, C1-C6 alkenylene, C1-C6 thioalkylene, C1-C6 ketoalkylene, C1-C6 ketoalkenylene, C7-C13 ketoarylene, and C6-C13 ketocycloalkylene.

[0225] More specifically, each L3 independently has a direct bond to an alkylene of formula (C-16), an oxyalkylene of formula (C-17), a thioalkylene of formula (C-18), a ketoalkylene of formula (C-19), an aminoalkylene of formula (C-20), or an alkylene of formula (C-21): TIFF2026518308000038.tif49170[In the formula, Each R m , R' m , R n , R' n , R o , R' o , R p , R' p , R q , R' q , R r and R' r is independently H or an optionally substituted alkyl, particularly H; R'' r and R'' n is independently H or an optionally substituted alkyl; f, g, h, and j are independently 1, 2, 3, 4, 5, or 6, especially 1 or 2; i and k are independently 1, 2, 3, 4, or 5, especially 1; The symbol ● is PI or PI 1 Represents the connection point to a part; The symbol § is PI or PI 1 [Represents connection points to parts other than the main body] It can be selected from the following.

[0226] In formulas (XXXVIII) and (XXXIX), each Y is independently either H or alkyl.

[0227] In particular, each Y can independently be an alkyl, more specifically, a methyl or ethyl.

[0228] In equations (XXXVI) to (XXXIX), each Z is an independent linker containing 1 to 20 carbon atoms.

[0229] In particular, each Z can be an alkylene independently.

[0230] More specifically, each Z is independently expressed by the following equations (C-22), (C-23), or (C-24): TIFF2026518308000039.tif54170[In the formula, each R v , R' v , R w , R' w , R x , R' x is independently H or alkyl, especially H; R'' w is H or alkyl, especially alkyl; h' is 1, 2, 3, 4, 5, or 6, especially 2; Each i'' is independently 1, 2, or 3, especially 1; Each j'' is independently 1, 2, or 3, especially 1; symbol TIFF2026518308000040.tif7170 represents a bond point to a nitrogen or oxygen atom. It could be an alkylene due to one of these factors.

[0231] More specifically, each Z can independently be an alkylene of equation (C-22) defined above.

[0232] In formulas (XXXX) and (XXXXI), each Z' is independently a linker containing 1 to 20 carbon atoms.

[0233] In particular, each Z' can be independently selected from aliphatic or aromatic hydrocarbon linkers, polyether linkers, polyester linkers, polycarbonate linkers, polyorganosiloxane linkers, polydiene linkers, isocyanurate linkers, and combinations thereof.

[0234] More specifically, each Z' can be independently selected from aliphatic or aromatic hydrocarbon linkers, polyether linkers, polyester linkers, and combinations thereof.

[0235] More specifically, each Z' can be an alkylene, an alkoxylated alkylene, or a polycaprolactone linker.

[0236] In a particularly preferred embodiment, the self-crosslinking urethane (meth)acrylate of the present invention is a given of the following formulas (XXXXII)~(XXXXIV): TIFF2026518308000041.tif58170[In the formula, Each PI 1 Each PI is independently a monovalent photoinitiator molar PI according to formula (VIII) or (XI) defined above, preferably each PI 1 is a monovalent photoinitiator molar PI according to formula (VIIIa) or (XIa) defined above; Each L3 is independently a direct bond, an alkylene of formula (C-16) defined above, an oxyalkylene of formula (C-17) defined above, a thioalkylene of formula (C-18) defined above, or an alkylene of formula (C-21) defined above; Each Z is independently an alkylene of equation (C-22) defined above; Each Z' is independently an alkylene or polyether linker. It may include at least one chromophore portion Q from one of the following.

[0237] In a particularly preferred embodiment, the self-crosslinking urethane (meth)acrylate is defined by the following formulas (XXb10) to (XXb26): It contains at least one chromophore portion Q from one of TIFF2026518308000042.tif216170 or TIFF2026518308000043.tif139170.

[0238] The total amount of chromophore portion Q in the self-crosslinkable urethane (meth)acrylate of the present invention may account for 0.5 to 20%, particularly 1 to 15%, and more specifically 1.5 to 10%, of the total weight of the self-crosslinkable urethane (meth)acrylate.

[0239] Chain extension part EXT The self-crosslinkable urethane (meth)acrylate of the present invention may optionally include at least one chain extension portion EXT. The self-crosslinkable urethane (meth)acrylate of the present invention may optionally include a plurality of chain extension portions EXT. In this case, the chain extension portions may be identical or different from each other.

[0240] Alternatively, the self-crosslinkable urethane (meth)acrylate of the present invention may substantially not contain the chain extension portion EXT.

[0241] As used herein, the chain extension portion means the portion other than the (meth)acrylate functionalized portion ACR, the polyurethane portion UU, and the chromophore portion Q. Therefore, the chain extension portion EXT does not contain the photoinitiator portion PI as defined above, does not contain (meth)acrylate groups, and does not contain urethane bonds. The self-crosslinkable urethane (meth)acrylate may have a chain extension portion introduced to increase its number-average molecular weight and / or to modify its mechanical properties and / or to introduce a hydrogen-donating functional group that acts as a co-initiator for the chromophore portion Q.

[0242] Each chain extension portion EXT may correspond to a polyol residue (without an OH group), and preferably, each chain extension portion EXT may correspond to a diol residue (without an OH group).

[0243] Examples of suitable polyols are described in detail in component d) of the method for preparing the self-crosslinkable urethane (meth)acrylate of the present invention.

[0244] The self-crosslinkable urethane (meth)acrylate may include at least one chain extension portion EXT which is a linker selected from aliphatic or aromatic hydrocarbon linkers, polyether linkers, polyester linkers, polycarbonate linkers, polyorganosiloxane linkers, polydiene linkers, and combinations thereof (preferably a divalent or trivalent linker).

[0245] Self-crosslinkable urethane (meth)acrylate may contain at least one chain extension portion EXT which is a polyol residue (without an OH group), particularly a diol residue (without an OH group).

[0246] The self-crosslinkable urethane (meth)acrylate may contain at least one chain extension portion EXT which is a polyol residue selected from polymer polyol residues, nonpolymer polyol residues, or amino-functional polyol residues.

[0247] In particular, the self-crosslinkable urethane (meth)acrylate may contain at least one chain extension portion EXT which is a polymer polyol residue or a non-polymer polyol residue, preferably a polymer diol residue or a non-polymer diol residue.

[0248] As used herein, the term "polymer polyol" means a polymer having two or more isocyanate-reactive hydroxyl groups per molecule. As used herein, the term "polymer diol" means a polymer having two isocyanate-reactive hydroxyl groups per molecule. As used herein, the term "nonpolymer polyol" means a nonpolymer compound having two or more isocyanate-reactive hydroxyl groups per molecule. As used herein, the term "nonpolymer diol" means a nonpolymer compound having two isocyanate-reactive hydroxyl groups per molecule. In the context of the present invention, the term "polymer" means a compound containing five or more repeating units per molecule, and the term "nonpolymer compound" means a compound containing up to four repeating units per molecule (and therefore both monomer compounds and oligomer compounds containing two to four repeating units per molecule). For example, ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol are all examples of nonpolymer diols, while polyethylene glycol, which contains five or more oxyalkylene repeating units, is an example of a polymer diol.

[0249] The self-crosslinkable urethane (meth)acrylate may contain at least one chain extension portion EXT, which is a polymer polyol residue (without an OH group). Alternatively, the self-crosslinkable urethane (meth)acrylate of the present invention may substantially not contain the chain extension portion EXT, which is a polymer polyol residue (without an OH group).

[0250] The molecular weight of the polymer polyol residues may be modified as needed or desired to achieve specific properties of the self-crosslinkable urethane (meth)acrylate. The number-average molecular weight of the polymer polyol residues may be at least 300 g / mol, at least 350 g / mol, or at least 400 g / mol. The number-average molecular weight of the polymer polyol may be less than 5000 g / mol, less than 4500 g / mol, or less than 4000 g / mol. For example, the polymer polyol may have a number-average molecular weight of 300-5000 g / mol, 350-4500 g / mol, or 400-4000 g / mol.

[0251] The polymer portion of a polymer polyol may be composed of multiple repeating units, such as oxyalkylene units, ester units, carbonate units, acrylic units, and alkylene units, or combinations thereof.

[0252] In particular, the self-crosslinkable urethane (meth)acrylate of the present invention may contain at least one chain extension portion EXT which is a polymer diol residue (without an OH group).

[0253] More specifically, the self-crosslinkable urethane (meth)acrylate may include at least one chain extension portion EXT which is a polymer diol residue selected from polyether diol residues, polyester diol residues, polycarbonate diol residues, polyorganosiloxane diol residues (e.g., polydimethylsiloxane diol residues), and polydiene diol residues including fully or partially hydrogenated polydiene diols (e.g., polybutadiene diol residues).

[0254] More specifically, the self-crosslinkable urethane (meth)acrylate may contain at least one chain extension portion EXT which is a polyetherdiol or polyesterdiol residue, preferably a polyetherdiol residue.

[0255] More specifically, the self-crosslinkable urethane (meth)acrylate may contain at least one chain extension portion EXT, which is a residue of a polyetherdiol selected from polyethylene glycol, poly(1,2-propylene glycol), poly(1,3-propylene glycol), poly(1,4-butylene glycol) and combinations thereof, or a residue of a polyesterdiol selected from poly(caprolactone), poly(lactide), poly(alkylene glycol adipate), and poly(alkylene glycol succinate).

[0256] The self-crosslinkable urethane (meth)acrylate of the present invention may contain at least one chain extension portion EXT which is a residue of a nonpolymer polyol (without an OH group). Alternatively, the self-crosslinkable urethane (meth)acrylate of the present invention may substantially not contain the chain extension portion EXT which is a residue of a nonpolymer polyol (without an OH group).

[0257] In particular, self-crosslinkable urethane (meth)acrylate may contain at least one chain extension portion EXT, which is a residue of a nonpolymer diol.

[0258] More specifically, the self-crosslinkable urethane (meth)acrylate may contain at least one chain extension portion EXT, which is a residue of a nonpolymer aliphatic diol.

[0259] More specifically, self-crosslinking urethane (meth)acrylates include ethylene glycol, di-, tri- or tetraethylene glycol, 1,2- or 1,3-propylene glycol, di-, tri- or tetra(1,2-propylene glycol), di-, tri- or tetra(1,3-propylene glycol), 1,2-, 1,3- or 1,4-butylene glycol, di-, tri- or tetra(1,4-butylene glycol), 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 3-butyl-3-ethyl-1,5-pentanediol, 2,2,4-trimethyl The material may contain at least one chain extension portion EXT which is a residue of a nonpolymer aliphatic diol selected from 1,5-pentanediol, cyclohexanediol, cyclohexane-1,4-dimethanol, norbornenedimethanol, norbornanedimethanol, tricyclodecanediol, tricyclodecanedimethanol, hydrogenated bisphenol A, B, F or S, dianhydrohexitol (i.e., isosorbide, isomannide, isoidide), hydrogenated dimeric fatty acids (i.e., diols obtained by dimerizing one or more unsaturated fatty acids such as oleic acid or linoleic acid, and then hydrogenating the resulting product to convert the carboxylic acid group to a hydroxyl group, e.g., Pripol® 2033 from Croda) and its alkoxylated (i.e., ethoxylated and / or propoxylated) derivatives having up to four oxyalkylene units.

[0260] Self-crosslinking urethane (meth)acrylate is given by the following formula (XXXXV): TIFF2026518308000044.tif12170[In the formula, R3 is in formula (Iib)~(Vib): A divalent linker selected from one of the following: -(CR 22 R' 22 )m- (Iib) -[(CR 23 R' 23 )nO]o-(CR 23 R' 23 )n- (IIIb) -[(CR 24 R' 24 )pO]q-(CR 25 R' 25 )r-[O-(CR 26 R' 26 )p']q'- (Ivb) -[(CR 27 R' 27 )sC(=O)-O]t-(CR 28 R' 28 )u-[O-(CR 28 R' 28 )u]u'-[OC(=O)~(CR 27 R' 27 )s]t'- (Vb) -[(CR 29 R' 29 )vOC(=O)~(CR 30 R' 30 )wC(=O)-O]x-(CR 29 R' 29 )v- (Vib) R 22 , R' 22 , R 25 , R' 25 , R 29 , R' 29 , R 30 and R' 30 is 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 is independently H or methyl; m is between 2 and 50; n, p, and p' are independently 2 to 4; o is between 1 and 20; q and q' are independently between 0 and 20, provided that at least one of q and q' is not 0; r is between 2 and 20; s is between 3 and 12; t and t' are independently between 1 and 20; u is between 2 and 8; u' is between 0 and 10; v is between 2 and 20; w is between 2 and 30; x is between 1 and 20. It may include at least one chain extension portion EXT that corresponds to the above.

[0261] The self-crosslinking urethane (meth)acrylate may contain at least one chain extension portion EXT containing a tertiary amine group. The tertiary amine group acts as an amine synergistic portion and can enhance the speed and efficiency of photoinitiation by the chromophore portion contained in the backbone of the self-crosslinking urethane (meth)acrylate.

[0262] The chain extension portion EXT, which contains a tertiary amine group, may be a residue (without an OH group) of an amino-functional polyol.

[0263] Therefore, self-crosslinkable urethane (meth)acrylates are amino-functional polyol residues, particularly triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, Nt-butyldiethanolamine, trimethanolamine, N-methyldimethanolamine, 3-(dimethylamino)-1,2-propanediol, 3-(diethylamino)-1,2-propanediol, 3-(dipropyl Amino)-1,2-propanediol, 2-(dimethylamino)propane-1,3-diol, bis(2-hydroxyethyl)dodecylamine, bis(2-hydroxyethyl)octadecylamine, N,N-dioctadecyl-N',N'-bis(2-hydroxyethyl)-1,3-diaminopropane, 3-morpholino-1,2-propanediol, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1-yl-1,2-propanediol, and the following formula (XXXXVI): TIFF2026518308000045.tif34170[In the formula, R y and R' y This is independently a substituted group selected from alkyl, alkenyl, alkynyl, aryl, aralkyl, alkalyl, and heteroaryl groups; Each R z This is independently a substituted group selected from H, F, Cl, Br, I, -OR*, -SR*, -N(R*)2, -NO2, -CN, -C(=O)R*, -OC(=O)R*, -C(=O)OR*, -C(=O)N(R*)2, -NR*-C(=O)-R*, -SO2-N(R*)2, or alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl and heteroaryl; Each R* is independently H, or an optionally substituted group selected from alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkalyl, and heteroaryl; L'3 is as defined above for L3; Each Z'' is independent and is defined above for Z; n 38 [is 0 or 1] It may include at least one chain extension portion EXT, which is a residue of an amino-functionalized polyol selected from aminobenzamide diols.

[0264] In a preferred embodiment, the self-crosslinkable urethane (meth)acrylate of the present invention may comprise at least one chain extension portion EXT which is a residue of a polymer polyol, and at least one chain extension portion EXT which comprises a tertiary amine group.

[0265] The total amount of chain extensions EXT in the self-crosslinkable urethane (meth)acrylate of the present invention may account for 0 to 84.5%, particularly 0.1 to 75%, and more specifically 1 to 65%, of the total weight of the self-crosslinkable urethane (meth)acrylate.

[0266] In one embodiment, the total amount of chain extension portions EXT in the self-crosslinkable urethane (meth)acrylate of the present invention may be less than 0.2%, particularly less than 0.1%, and more specifically 0% of the total weight of the self-crosslinkable urethane (meth)acrylate. Such an amount can be obtained, for example, when the self-crosslinkable urethane (meth)acrylate substantially contains no chain extension portions.

[0267] In one embodiment, the total amount of chain extension portions EXT in the self-crosslinkable urethane (meth)acrylate of the present invention may account for 0.1 to 20%, particularly 0.2 to 15%, and more specifically 0.5 to 10%, of the total weight of the self-crosslinkable urethane (meth)acrylate. Such amounts can be obtained, for example, when the self-crosslinkable urethane (meth)acrylate contains chain extension portions derived from a nonpolymeric polyol.

[0268] In another embodiment, the total amount of chain extension portions EXT in the self-crosslinkable urethane (meth)acrylate of the present invention may account for 15 to 84.5%, particularly 20 to 75%, and more specifically 25 to 65%, of the total weight of the self-crosslinkable urethane (meth)acrylate. Such amounts can be obtained, for example, when the self-crosslinkable urethane (meth)acrylate contains chain extension portions derived from a polymer polyol.

[0269] Structure of self-crosslinking urethane (meth)acrylate The structure of self-crosslinking urethane (meth)acrylate can be linear or branched, depending on the properties of the reactants used to produce the self-crosslinking urethane (meth)acrylate.

[0270] When the polyurethane portion UU is derived from an isocyanate, and both the chromophore portion Q and any chain extension portion EXT are derived from a diol, the resulting self-crosslinkable urethane (meth)acrylate is linear.

[0271] When the polyurethane portion UU is derived from triisocyanate, or when the chromophore portion Q is derived from triol or tetraol, the resulting self-crosslinkable urethane (meth)acrylate is branched.

[0272] Each (meth)acrylate-functionalized moiety ACR can be a terminal portion bonded to a single urethane moiety UU. Therefore, the (meth)acrylate-functionalized moiety ACR can function as an end cap portion of a self-crosslinking urethane (meth)acrylate.

[0273] Each chromophore portion Q may be bonded to at least one polyurethane moiety UU. If the chromophore portion Q is derived from a photoinitiator compound having a single OH group, the chromophore portion Q may be a terminal portion bonded to a single polyurethane moiety UU. If the chromophore portion Q is derived from a photoinitiator compound having at least two OH groups, the chromophore portion Q may be bonded to at least two different polyurethane moieties UU (one for each OH group present in the photoinitiator compound).

[0274] Each chain extension portion EXT can be bonded to two different polyurethane portions UU.

[0275] Each polyurethane portion UU can be positioned between two, three, or four portions independently selected from the (meth)acrylate functionalization portion ACR, the chromophore portion Q, and the chain extension portion EXT.

[0276] When a self-crosslinkable urethane (meth)acrylate comprises one or more chromophore portions Q and one or more chain extension portions EXT, the Q and EXT portions may be randomly positioned with respect to the polyurethane portion UU. For example, one or more chain extension portions and chromophore portions Q may be randomly arranged along the polyurethane skeleton and may be bonded to each other by the polyurethane portion UU. By changing the synthesis method used to prepare the self-crosslinkable urethane (meth)acrylate, it is also possible for the oligomer to have a more ordered structure. For example, the chain extension portions EXT may be clustered near the center of the polyurethane skeleton, and the chromophore portions may be positioned toward each end of the polyurethane skeleton, or vice versa.

[0277] The self-crosslinkable urethane (meth)acrylate may contain a chromophore moiety Q bonded to at least two different polyurethane moieties UU. This is the case when the chromophore moiety Q is derived from a photoinitiator compound having two, three, or four OH groups.

[0278] In particular, self-crosslinking urethane (meth)acrylate has the following structure (A): TIFF2026518308000046.tif54170[In the formula, ACR, UU, Q and EXT are as defined above; a is an integer between 1 and 100; b is an integer between 0 and 100; c is an integer equal to 0, 1, or 2, preferably 0 or 1. It can be equivalent to this.

[0279] A self-crosslinkable urethane (meth)acrylate may contain at least one chromophore moiety Q bonded to a single polyurethane moiety UU. This is the case when the chromophore moiety Q is derived from a photoinitiator compound having a single OH group.

[0280] In particular, self-crosslinking urethane (meth)acrylate has the following structure (B): TIFF2026518308000047.tif32170[In the formula, Each D is independently Q or EXT; Each T is independently either ACR or Q; ACR, UU, Q, and EXT are as described in any one of claims 1 to 30; a' is an integer between 0 and 100; b' is an integer between 0 and 100; Here, at least one of a' and b' is not 0; Q is at least one of D and T. It can be equivalent to this.

[0281] When a' is non-zero, the self-crosslinkable urethane (meth)acrylate contains at least one polyurethane moiety UU derived from triisocyanate. In such cases, the self-crosslinkable urethane (meth)acrylate may or may not contain at least one polyurethane moiety UU derived from diisocyanate (i.e., b' may be non-zero or b' may be equal to 0). Preferably, when a' is non-zero, at least one chromophore moiety Q is derived from a monool or a diol.

[0282] The self-crosslinking urethane (meth)acrylate does not need to contain an effective amount of dye portion, and preferably, the self-crosslinking urethane (meth)acrylate does not contain any dye portion.

[0283] As used herein, “effective amount of dye portion” is understood to mean that the amount of dye portion in a self-crosslinking urethane (meth)acrylate is sufficient to impart a color different from the color of a self-crosslinking urethane (meth)acrylate that does not contain such dye portion, and that the difference in color is detectable to the naked eye.

[0284] Examples of dye portions include portions derived from azo dyes, phthalocyanine dyes, anthraquinone dyes, dicyanovinyl dyes or tricyanovinyl dyes, methine dyes, aniline dyes, and indoaniline dyes, such as those described in U.S. Patent Publication No. 2014 / 0316060.

[0285] Self-crosslinking urethane (meth)acrylate does not need to contain a carboxyl group (i.e., a carboxylic acid or carboxylate salt).

[0286] The number-average molecular weight of self-crosslinkable urethane (meth)acrylate may be 500 to 50,000 g / mol, or 1,000 to 10,000 g / mol, or 2,000 to 8,000 g / mol. The number-average molecular weight of self-crosslinkable urethane (meth)acrylate may be modified as needed to impart specific properties to the oligomer itself and the cured composition prepared from the oligomer. Generally speaking, if the self-crosslinkable urethane (meth)acrylate contains at least one chain extension portion EXT, the number-average molecular weight is usually somewhat higher. For example, if the self-crosslinkable urethane (meth)acrylate contains at least one chain extension portion EXT, its number-average molecular weight may be 3,000 g / mol to 50,000 g / mol. If the self-crosslinkable urethane (meth)acrylate does not contain a chain extension portion EXT, its number-average molecular weight may be, for example, 500 g / mol to 5,000 g / mol.

[0287] Self-crosslinking urethane (meth)acrylates are obtained by reacting the following components (in one step or in a series of steps): a) Hydroxyl-functionalized (meth)acrylate components; b) Polyisocyanate components; c) Hydroxyl-functionalized photoinitiator components; and d) Optionally, a polyol component.

[0288] Components a), b), c), and d) may be as detailed in the following method for preparing self-crosslinkable urethane (meth)acrylates.

[0289] Method for preparing self-crosslinking urethane (meth)acrylate The present invention also relates to a method for preparing self-crosslinking urethane (meth)acrylate. The self-crosslinking urethane (meth)acrylate obtained by the method of the present invention may be as defined above.

[0290] The method for preparing self-crosslinking urethane (meth)acrylate is as follows: a) With hydroxyl-functionalized (meth)acrylate components; b) Polyisocyanate components; c) Hydroxyl-functionalized photoinitiator component; d) Optionally, the polyol component and This includes reacting the two.

[0291] The reactions between components a), b), c), and d) may be carried out in a single step or in a series of steps. If a series of steps is used, the method may include a first step of reacting components b) and c) with optionally component d) to form an isocyanate-terminated prepolymer, and a second step of reacting the isocyanate-terminated prepolymer with component a). Alternatively, the method may include a first step of reacting components a) and b) to form an isocyanate-functionalized (meth)acrylate compound, and a second step of reacting the isocyanate-functionalized (meth)acrylate compound with component c) and optionally component d).

[0292] This method may be carried out in the presence of one or more additional components e), as detailed below.

[0293] This method can be carried out at a temperature of 30 to 90°C, preferably 50 to 80°C.

[0294] This method may be carried out until the NCO value is less than 1% by weight, preferably less than 0.5%, and more preferably less than 0.1%, based on the total weight of the reaction mixture. If necessary, additional amounts of component a) may be introduced into the reaction mixture to reach the target NCO value.

[0295] Components a), b), c), d), and e) may be as detailed below.

[0296] a) Hydroxyl-functionalized (meth)acrylate components One of the components used to prepare the self-crosslinkable urethane (meth)acrylate of the present invention is a hydroxyl-functionalized (meth)acrylate component (also called component a).

[0297] A hydroxyl-functionalized (meth)acrylate component comprises or consists of at least one hydroxyl-functionalized (meth)acrylate compound. A hydroxyl-functionalized (meth)acrylate component may comprise or consist of a mixture of hydroxyl-functionalized (meth)acrylate compounds.

[0298] Hydroxyl-functionalized (meth)acrylate compounds are compounds having at least one (meth)acrylate group and a single OH group.

[0299] The reaction of component a) used to prepare the self-crosslinking urethane (meth)acrylate with other components may result in the introduction of one or more (meth)acrylate-functionalized moieties ACR into the backbone of the self-crosslinking urethane (meth)acrylate. The preferred embodiments of the (meth)acrylate-functionalized moieties ACR disclosed above also apply to component a).

[0300] Component a) may contain a hydroxyl-functionalized (meth)acrylate compound having 1 to 5 (meth)acrylate groups, particularly 1 to 3 (meth)acrylate groups, and more specifically 1 (meth)acrylate group.

[0301] In particular, component a) is given by the following equation (Ia): TIFF2026518308000048.tif34170[In the formula, R4, R5, and w' may include hydroxyl-functionalized (meth)acrylate compounds as defined above for the (meth)acrylate-functionalized moiety ACR. All preferred embodiments of R4, R5, and w' described above for the (meth)acrylate-functionalized moiety ACR also apply to compounds of formula (Ia).

[0302] Examples of suitable hydroxyl-functionalized (meth)acrylate compounds include hydroxyalkyl (meth)acrylates (e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, or 1,6-hexanediol mono(meth)acrylate), 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, tris(2-hydroxyethyl) isocyanurate mono- and di(meth)acrylate, di-, tri-, tetra- or polyethylene glycol Mono(meth)acrylate, di-, tri-, tetra- or poly(1,2-propylene glycol) mono(meth)acrylate, di-, tri-, tetra- or poly(1,3-propylene glycol) mono(meth)acrylate, di-, tri-, tetra- or poly(1,4-butylene glycol) mono(meth)acrylate, glycerin mono- and di(meth)acrylate, 2-hydroxy-1-acrylooxy-3-(meth)acrylooxypropane, trimethylolpropane mono- and di(meth)acrylate, di(trimethylolpropane) mono-, di- and tri(meth)acrylate, trimethylolethane mono- and di(meth)acrylate, pentaerythritol mono-, di- and tri(meth)acrylate, dipentaerythritol Mono-, di-, tri-, tetra-, and penta(meth)acrylates, as well as their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives and the above hydroxyl-functionalized (meth)acrylate compounds (i.e., (poly)caprolactone (meth)acrylate, for example, the following formula: CH2=CR5-C(=O)-O-CH2-CH2-[O-(C=O)~(CH2)5] nThis includes (poly)caprolactone derivatives, as well as combinations thereof, obtained by ring-opening polymerization of ε-caprolactone initiated by one of the (poly)caprolactone 2-hydroxyethyl (meth)acrylates with -OH [wherein R5 is H or methyl, and t is 1 to 20].

[0303] Preferably, component a) may include a hydroxyl-functionalized (meth)acrylate compound selected from hydroxyalkyl (meth)acrylates, (poly)caprolactone (meth)acrylates, and mixtures thereof.

[0304] The total amount of component a) used to prepare the self-crosslinkable urethane (meth)acrylate of the present invention may be 5 to 85% by weight of component a), particularly 10 to 80% by weight, and more specifically 15 to 75% by weight, based on the total amount of components a), b), c), and d).

[0305] In one embodiment, the total amount of component a) used to prepare the self-crosslinkable urethane (meth)acrylate of the present invention may be 50 to 85% by weight of component a), particularly 55 to 80% by weight, and more specifically 60 to 75% by weight, based on the total amount of components a), b), c), and d). Such an amount may be used, for example, when component a) contains (poly)caprolactone (meth)acrylate.

[0306] In another embodiment, the total amount of component a) used to prepare the self-crosslinkable urethane (meth)acrylate of the present invention may be 5 to 40% by weight of component a), particularly 10 to 35% by weight, and more specifically 15 to 30% by weight, based on the total amount of components a), b), c), and d). Such an amount may be used, for example, when component a) contains a hydroxyalkyl (meth)acrylate.

[0307] b) Polyisocyanate components One of the components used to prepare the self-crosslinkable urethane (meth)acrylate of the present invention is a polyisocyanate component (also called component b).

[0308] The polyisocyanate component comprises or consists of at least one polyisocyanate compound. The polyisocyanate component may comprise or consist of a mixture of polyisocyanate compounds.

[0309] Polyisocyanate compounds are compounds having at least two isocyanate-(N=C=O) groups.

[0310] The reaction of component b) used to prepare the self-crosslinkable urethane (meth)acrylate with other components may result in the introduction of one or more polyurethane moieties (UUs) into the backbone of the self-crosslinkable urethane (meth)acrylate. The preferred embodiments of the polyurethane moieties (UUs) disclosed above also apply to component b).

[0311] Component b) may contain a polyisocyanate compound having 2 to 3 isocyanate groups.

[0312] In particular, component b) may include a diisocyanate compound according to the following formula (VIIa) and / or a triisocyanate compound according to the following formula (VIIb): TIFF2026518308000049.tif38170 [wherein R1 and R1' are as defined above for the polyurethane moiety UU]. All preferred embodiments of R1 and R1' described above for the polyurethane moiety UU also apply to the compounds of formulas (VIIa) and (VIIb).

[0313] Suitable examples of diisocyanate compounds according to formula (VIIa) include 2,4- and 2,6-toluene diisocyanate (TDI), isophorone diisocyanate (IPDI, equivalent to 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate), methylene diisocyanate, ethylene diisocyanate, 1,2- or 1,3-propylene diisocyanate, 1,2-, 1,3- or 1,4-butylene diisocyanate, 1,5-pentamethylene diisocyanate (PDI), and 1,6-hexamethylene diisocyanate (HD). I) 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate (TMDI), 1,10-decylene diisocyanate, 1,12-dodecylene diisocyanate, 1,18-octadecylene diisocyanate, 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 2,2'-, 2,4'- and 4,4'-dicyclohexylmethane diisocyanate (H12MDI), benzidine diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, dianisidine diisocyanate Nate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylenediisocyanate, 1,4- and 1,5-naphthalenediisocyanate (NDI), 1,4- and 9,10-anthracene diisocyanate, 1,3- and 1,4-cyclohexane diisocyanate, 1-methyl-2,4-diisocyanatocyclohexane, 1-methyl-2,6-diisocyanatocyclohexane, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, m-tetramethylxylenediisocyanate, This includes m-xylene diisocyanate, 4-methoxy-1,3-phenylenediisocyanate, 4-ethoxy-1,3-phenylenediisocyanate, 5,6-dimethyl-1,3-phenylenediisocyanate, 2,4'- or 4,4'-diisocyanate diphenyl ether, lysine diisocyanate, dimeric acid diisocyanate, dimers of the above diisocyanates (especially uretdione or allophanate dimers), and polyureas or polyurethane prepolymers functionalized with isocyanate functional groups, as well as combinations thereof.

[0314] Suitable examples of triisocyanate compounds according to formula (VIIb) include 1,6,11-undecane triisocyanate, triphenylmethane triisocyanate, 2,4,6-tolurene triisocyanate, 2,4,4'-triisocyanate diphenyl ether, trimers of the diisocyanates detailed above for formula (VIIa) (especially isocyanurates or biuret trimers), polymer derivatives of the diisocyanates detailed above for formula (VIIa), and combinations thereof.

[0315] As used herein, the isocyanurate trimer of the diisocyanate of formula O=C=N-R1-N=C=O is defined by the following formula: TIFF2026518308000050.tif52170[where, R 1 [This is defined above.] It corresponds to this.

[0316] As used herein, the biuret trimer of diisocyanate of formula O=C=N-R1-N=C=O is given by the following formula: TIFF2026518308000051.tif54170[where, R 1 [This is defined above.] It corresponds to this.

[0317] Preferably, component b) comprises a polyisocyanate compound selected from isophorone diisocyanate, 2,2'-, 2,4'- and 4,4'-dicyclohexylmethane diisocyanate, isocyanurate trimers of hexamethylene diisocyanate, and combinations thereof.

[0318] The total amount of component b) used to prepare the self-crosslinkable urethane (meth)acrylate of the present invention may be 10 to 65% by weight of component b), particularly 15 to 60% by weight, and more specifically 20 to 55% by weight, based on the total amount of components a), b), c), and d).

[0319] c) Hydroxyl-functionalized photoinitiator component One of the components used to prepare the self-crosslinkable urethane (meth)acrylate of the present invention is a hydroxyl-functionalized photoinitiator component (also called component c).

[0320] The hydroxyl-functionalized photoinitiator component comprises or consists of at least one hydroxyl-functionalized photoinitiator. The hydroxyl-functionalized photoinitiator component may comprise or consist of a mixture of hydroxyl-functionalized photoinitiators.

[0321] The reaction of component c) used to prepare the self-crosslinking urethane (meth)acrylate with other components may result in the introduction of one or more chromophore moieties Q into the backbone of the self-crosslinking urethane (meth)acrylate. The preferred embodiments of chromophore moieties Q disclosed above also apply to component c).

[0322] A hydroxyl-functionalized photoinitiator is a compound having at least one hydroxyl group (in particular, one, two, three, or four hydroxyl groups) and at least one chromophore moiety (in particular, one, two, three, or four chromophore moieties). The at least one chromophore moiety of the hydroxyl-functionalized photoinitiator is as defined above for chromophore moiety Q.

[0323] Hydroxyl-functionalized photoinitiators may be monools (i.e., photoinitiators having a single OH group), diols (i.e., photoinitiators having two OH groups), triols (i.e., photoinitiators having three OH groups), or tetraols (i.e., photoinitiators having four OH groups).

[0324] In particular, hydroxyl-functionalized photoinitiators are - A single OH group and a single chromophore moiety; - Two OH groups and a single chromophore moiety; - Three OH groups and a single chromophore moiety; - Four OH groups and a single chromophore moiety; - Two OH groups and two chromophore moieties; - Three OH groups and three chromophore moieties; or - 4 OH groups and 4 chromophore moieties It may have.

[0325] In a preferred embodiment, component c) may comprise at least one hydroxyl-functionalized photoinitiator having at least two OH groups and at least one chromophore moiety.

[0326] Each chromophore portion may independently comprise at least one monovalent or divalent photoinitiator portion PI selected from benzophenone portions, thioxanthone portions, xanthone portions, acridone portions, camphorquinone portions, benzyl portions, coumarin portions, ketocoumarin portions, their derivatives, and combinations thereof, preferably a monovalent or divalent photoinitiator portion PI selected from benzophenone portions or thioxanthone portions.

[0327] In particular, each chromophore portion may independently contain a monovalent photoinitiator portion PI corresponding to one of formulas (VIII), (XI), (XIV), (XVII), (XVIII), or (XIX), or at least one divalent photoinitiator portion PI corresponding to one of formulas (XII), (XIII), (XV), or (XVI). Formulas (VIII), (IX), (X),(XI), (XII), (XIII), (XIV), (XV), (XVI), (XVII), (XVIII), and (XIX) are as defined above for chromophore portion Q.

[0328] More specifically, each chromophore portion may independently include at least one monovalent photoinitiator portion PI corresponding to one of formulas (VIII) or (XI) (wherein E is S), or at least one divalent photoinitiator portion PI corresponding to one of formulas (IX), (X), (XII), or (XIII) (wherein E is S).

[0329] More specifically, each chromophore portion may include at least one monovalent photoinitiator portion PI corresponding to one of formulas (VIIIa) or (XIa) as defined above for the chromophore portion Q, or at least one divalent photoinitiator portion PI corresponding to one of formulas (IXa), (Xa), (XIIa), or (XIIIa) as defined above for the chromophore portion Q.

[0330] More specifically, each chromophore portion includes at least one monovalent photoinitiator portion PI corresponding to formula (VIII) or (XI) (wherein E is S), or at least one divalent photoinitiator portion PI corresponding to formula (X) or (XIII) (wherein E is S).

[0331] More specifically, each chromophore portion may include at least one monovalent photoinitiator portion PI corresponding to formula (VIIIa) or (XIa) as defined above for the chromophore portion Q, or at least one divalent photoinitiator portion PI corresponding to formula (Xa) or (XIIIa) as defined above for the chromophore portion Q.

[0332] One or more OH groups and one or more chromophore moieties of the hydroxyl-functionalized photoinitiator may be linked by one or more linkers.

[0333] In particular, component c) is given by the following formulas (XXd), (XXe), or (XXf): TIFF2026518308000052.tif72170[where, L0, L1, L2, PI 1 PI 2 The material may contain at least one hydroxyl-functionalized photoinitiator, where s', t', and u' are defined above for the chromophore portion Q by one of formulas (XXa), (XXb), and (XXc).

[0334] Component c) may comprise at least one hydroxyl-functionalized photoinitiator according to formula (XXd) defined above. The hydroxyl-functionalized photoinitiator according to formula (XXd) may have a single chromophore moiety and a single OH group.

[0335] In equation (XXd), L1 and PI 1 The chromophore portion Q according to equation (XXa) may be as defined above. L1 and PI, as explained above, apply to the chromophore portion Q according to equation (XXa). 1 All preferred embodiments of the formula also apply to compounds of formula (XXd).

[0336] In particular, component c) is formula (XXd1) or (XXd2) TIFF2026518308000053.tif54170[where, R' a , R' b , R' c The photoinitiator may include at least one hydroxyl-functionalized photoinitiator, where x1, x2, x3 and L1 are as defined above for the chromophore portion Q according to one of formulas (XXa1) and (XXa2).

[0337] More specifically, component c) is given by the following equations (XXd3)~(XXd17): It may contain at least one hydroxyl-functionalized photoinitiator corresponding to one of TIFF2026518308000054.tif225170.

[0338] In a preferred embodiment, component c) may comprise at least one hydroxyl-functionalized photoinitiator according to one of formulas (XXe) or (XXf).

[0339] Component c) may comprise at least one hydroxyl-functionalized photoinitiator according to formula (XXf) defined above. The hydroxyl-functionalized photoinitiator according to formula (XXf) defined above may have a single chromophore moiety and at least two OH groups, preferably two OH groups.

[0340] In equation (XXf), L2, u' and PI 2 The chromophore part Q according to equation (XXc) may be as defined above. L2, u', and PI explained above regarding the chromophore part Q according to equation (XXc) 2 All preferred embodiments of the same formula also apply to the photoinitiator of formula (XXf).

[0341] Component c) is given by the following equations (XXf1)~(XXf4) TIFF2026518308000055.tif56170[where, R' d , R' e , R' f x4, x5, x6 and L2 may comprise at least one hydroxyl-functionalized photoinitiator corresponding to one of the following: [x4, x5, x6 and L2 are defined above for the chromophore portion Q by one of the formulas (XXc1) to (XXc4)].

[0342] More specifically, component c) is given by the following equations (XXf5)~(XXf13): It may contain at least one hydroxyl-functionalized photoinitiator from one of TIFF2026518308000056.tif228170.

[0343] Component c) may comprise at least one hydroxyl-functionalized photoinitiator according to formula (XXe) defined above. The hydroxyl-functionalized photoinitiator according to formula (XXe) comprises at least one photoinitiator portion PI 1 It may have at least two OH groups.

[0344] In one embodiment, component c) may comprise at least one hydroxyl-functionalized photoinitiator according to formula (XXe), wherein the hydroxyl-functionalized photoinitiator comprises at least two photoinitiator portions PI 1 It has at least two OH groups.

[0345] In particular, component c) may include at least one hydroxyl-functionalized photoinitiator according to formula (XXe), wherein the hydroxyl-functionalized photoinitiator has a number of photoinitiator moieties equal to the number of OH groups. 1It holds.

[0346] More specifically, component c) is given by formula (XXIa): TIFF2026518308000057.tif38170[where n1, n2, PI 1 V, W, X, R 2 , R 3 and R 4 This may include at least one hydroxyl-functionalized photoinitiator, with respect to the chromophore portion Q by formula (XXI) as defined above.

[0347] In particular, the hydroxyl-functionalized photoinitiators of formula (XXIa) are as follows: (XXIIa)~(XXXVa): TIFF2026518308000058.tif246170TIFF2026518308000059.tif235170[where n3, n4, n5, n6, n7, n8, n9, n 10 , n 11 , n 12 , n 13 , n 14 , n 15 , n 16 , n 17 , n 18 , n 19 , n 20 , n 21 , n 22 , n 23 PI 1 X, R 2 , R 3 and R 4 This is defined above for the chromophore part Q by one of equations (XXII) to (XXXV); Each R 5 These are independently H, alkyl, aryl, or the following formulas: TIFF2026518308000060.tif16170 (in the formula, X, R 3 and PI 1 This is a group as defined above, and the symbol} represents a bond point to the nitrogen atom. It could be equivalent to one of these.

[0348] Regarding the chromophore portion Q from one of the equations (XXII) to (XXXV), the n3, n4, n5, n6, n7, n8, n9, n explained above are n 10 , n 11 , n 12 , n 13 , n 14 , n 15 , n 16 , n 17 , n 18 , n 19 , n 20 , n 21 , n 22 , n 23 PI 1 X, R 2 , R 3 , R 4 and R 5 All preferred embodiments of the same apply to the photoinitiators of formulas (XXIIa) to (XXXVa).

[0349] Hydroxyl-functionalized photoinitiators comprising one of the formulas (XXIIa), (XXIIIa), (XXIVa), (XXVIa), (XXVIIa), (XXVIIIa), or (XXIXa) are preferred. Hydroxyl-functionalized photoinitiators comprising one of the formulas (XXIIa), (XXIIIa), (XXIVa), or (XXVIa) are particularly preferred.

[0350] More specifically, component c) is formula (XXIIa), (XXIIIa), (XXIVa), or (XXVIa): TIFF2026518308000061.tif117170[In the formula, n3, n4, n5, and n7 are independently 2, 3, or 4, preferably 2 or 3; Each PI 1 Each PI is independently a monovalent photoinitiator molar PI according to formula (VIII) or (XI) defined above, preferably each PI 1 is a monovalent photoinitiator molar PI according to formula (VIIIa) or (XIa) defined above; Each X independently, -NR 1 -, -O- or *-C(=O)-O-, preferably -NR 1-or *-C(=O)-O-; Each R 1 is independently H or alkyl; Each R 2 These are, independently, alkylenes or heteroatom-containing alkylenes; Each R 3 These are independently, directly bonded, alkylene of formula (C-11) as defined above, oxyalkylene of formula (C-12) as defined above, or aminoalkylene of formula (C-15) as defined above, preferably directly bonded, alkylene of formula (C-11) or oxyalkylene of formula (C-12) as defined above; Each R 4 is H; Each R 5 These are independently H, alkyl, or the following formulas: TIFF2026518308000062.tif14170 (in the formula, X, R 3 and PI 1 (As defined above, the symbol} represents the bond point to the nitrogen atom.) It is a base by; The symbol * is R 3 [Represents a connection point to] It contains a hydroxyl-functionalized photoinitiator, one of the following.

[0351] More specifically, component c) is given by the following equations (XXe1)~(XXe9): It comprises at least one hydroxyl-functionalized photoinitiator from one of TIFF2026518308000063.tif203170 or TIFF2026518308000064.tif89170.

[0352] In another embodiment, component c) may comprise at least one hydroxyl-functionalized photoinitiator according to formula (XXe), wherein the hydroxyl-functionalized photoinitiator comprises a single photoinitiator moiety PI and at least two OH groups.

[0353] In particular, component c) is given by the following equation (XXXVIa)~(XXXXIa): TIFF2026518308000065.tif237170[where, PI, PI 1 , L3, Y, Z, Z', n 24 , n 25 , n 26 , n 27 , n 28 , n 29 , n 30 , n 31 , n 32 , n 33 , n 34 , n 35 , n 36 and n 37 This is defined above for the chromophore part Q by equations (XXXVI) to (XXXXI). It may contain a hydroxyl-functionalized photoinitiator, one of the following.

[0354] Regarding the chromophore part Q according to one of the equations (XXXVI) to (XXXXI), the PI and PI explained above are relevant. 1 , L3, Y, Z, Z', n 24 , n 25 , n 26 , n 27 , n 28 , n 29 , n 30 , n 31 , n 32 , n 33 , n 34 , n 35 , n 36 and n 37 All preferred embodiments of the same apply to the photoinitiators of formulas (XXXVIa) to (XXXXIa).

[0355] More specifically, component c) is given by the following equation (XXXXIIa)~(XXXXIVa): TIFF2026518308000066.tif56170[In the formula, Each PI 1 Each PI is independently a monovalent photoinitiator molar PI according to formula (VIII) or (XI) defined above, preferably each PI 1 is a monovalent photoinitiator molar PI according to formula (VIIIa) or (XIa) defined above; Each L3 is independently a direct bond, an alkylene of formula (C-16) defined above, an oxyalkylene of formula (C-17) defined above, a thioalkylene of formula (C-18) defined above, or an alkylene of formula (C-21) defined above; Each Z is independently an alkylene of equation (C-22) defined above; Each Z' is independently an alkylene or polyether linker. It may contain a hydroxyl-functionalized photoinitiator, one of the following.

[0356] More specifically, component c) is given by the following equation (XXe10)~(XXe26): It may contain a hydroxyl-functionalized photoinitiator, one of TIFF2026518308000067.tif205170 or TIFF2026518308000068.tif120170.

[0357] The total amount of component c) used to prepare the self-crosslinkable urethane (meth)acrylate of the present invention may be 0.5 to 20% by weight, particularly 1 to 15% by weight, and more specifically 1.5 to 10% by weight of component c), based on the total amount of components a), b), c), and d).

[0358] d) Optional polyol components One of the components that can be optionally used to prepare the self-crosslinkable urethane (meth)acrylate of the present invention is a polyol component (also called component d).

[0359] The polyol component contains or consists of at least one polyol. The polyol component may contain or consist of a mixture of polyols.

[0360] A polyol is a compound having at least two hydroxyl groups (in particular, two, three, or four hydroxyl groups).

[0361] Polyol component d) is different from components a), b), and c). Therefore, component d) does not need to contain a hydroxyl-functionalized (meth)acrylate compound, a polyisocyanate compound, and a hydroxyl-functionalized photoinitiator.

[0362] The reaction of component d) used to prepare the self-crosslinkable urethane (meth)acrylate with other components may result in the introduction of one or more chain extension portions EXT into the backbone of the self-crosslinkable urethane (meth)acrylate. The preferred embodiments of the chain extension portions EXT disclosed above also apply to component d).

[0363] Component d) may be used in a method for preparing a self-crosslinkable urethane (meth)acrylate to increase its number-average molecular weight and / or to modify its mechanical properties and / or to introduce a hydrogen-donating functional group that acts as a co-initiator for the chromophore portion Q.

[0364] Alternatively, component d) may not be used in the method for preparing the self-crosslinking urethane (meth)acrylate.

[0365] Component d) may include at least one polyol (preferably a diol or triol) selected from aliphatic polyols, aromatic polyols, polyether polyols, polyester polyols, polycarbonate polyols, polyorganosiloxane polyols, polydiene polyols, and combinations thereof.

[0366] Component d) may include at least one polyol, particularly a diol, as defined above for the chain extension portion EXT.

[0367] Component d) may comprise at least one polyol selected from polymer polyols, nonpolymer polyols, or amino-functional polyols, as defined above for the chain extension portion EXT.

[0368] In particular, component d) may include at least one polymer polyol or at least one nonpolymer polyol, preferably at least one polymer diol or at least one nonpolymer diol.

[0369] Component d) may contain at least one polymer polyol, or it may not contain a polymer polyol at all.

[0370] The molecular weight of the polymer polyol may be modified as needed or desired to achieve specific properties of the self-crosslinkable urethane (meth)acrylate. The number-average molecular weight of the polymer polyol may be at least 330 g / mol, at least 350 g / mol, or at least 400 g / mol. The number-average molecular weight of the polymer polyol may be less than 5000 g / mol, less than 4500 g / mol, or less than 4000 g / mol. For example, the polymer polyol may have a number-average molecular weight of 330 to 5000 g / mol, 350 to 4500 g / mol, or 400 to 4000 g / mol.

[0371] The polymer portion of a polymer polyol may be composed of multiple repeating units, such as oxyalkylene units, ester units, carbonate units, acrylic units, and alkylene units, or combinations thereof.

[0372] In particular, component d) may contain at least one polymer diol.

[0373] More specifically, component d) may include at least one polymer diol selected from polydiene diols, including polyether diols, polyester diols, polycarbonate diols, polyorganosiloxane diols (e.g., polydimethylsiloxane diol), and fully or partially hydrogenated polydiene diols (e.g., polybutadiene diol).

[0374] More specifically, component d) may include at least one polyetherdiol or at least one polyesterdiol.

[0375] More specifically, component d) may include at least one polyether diol selected from polyethylene glycol, poly(1,2-propylene glycol), poly(1,3-propylene glycol), and poly(1,4-butylene glycol), or at least one polyester diol selected from poly(caprolactone), poly(lactide), poly(alkylene glycol adipate), and poly(alkylene glycol succinate).

[0376] Component d) may contain at least one nonpolymeric polyol, or it may substantially not contain a nonpolymeric polyol.

[0377] In particular, component d) may contain at least one nonpolymeric diol.

[0378] More specifically, component d) may contain at least one nonpolymer aliphatic diol.

[0379] More specifically, component d) is ethylene glycol, di-, tri- or tetraethylene glycol, 1,2- or 1,3-propylene glycol, di-, tri- or tetra(1,2-propylene glycol), di-, tri- or tetra(1,3-propylene glycol), 1,2-, 1,3- or 1,4-butylene glycol, di-, tri- or tetra(1,4-butylene glycol), 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanedio L, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 3-butyl-3-ethyl-1,5-pentanediol, 2,2,4-trimethyl The materials may include at least one nonpolymeric aliphatic diol selected from 1,5-pentanediol, cyclohexanediol, cyclohexane-1,4-dimethanol, norbornenedimethanol, norbornanedimethanol, tricyclodecanediol, tricyclodecanedimethanol, hydrogenated bisphenol A, B, F or S, dianhydrohexitol (i.e., isosorbide, isomannide, isoidide), hydrogenated dimeric fatty acids (i.e., diols obtained by dimerizing one or more unsaturated fatty acids such as oleic acid or linoleic acid, and then hydrogenating the resulting product to convert the carboxylic acid group to a hydroxyl group, e.g., Pripol® 2033 from Croda), and their alkoxylated (i.e., ethoxylated and / or propoxylated) derivatives having up to four oxyalkylene units.

[0380] Component d) is given by the following formula (XXXXVa): TIFF2026518308000069.tif8170[In the formula, R3 is as defined above for the chain extension portion EXT by formula (XXXXV)] It may contain polyols equivalent to [the specified polyol].

[0381] Component d) may include at least one polyol containing a tertiary amine group (referred to as an amino-functional polyol). The tertiary amine group acts as an amine synergistic moiety, which can increase the speed and efficiency of photoinitiation by the chromophore moiety contained in the backbone of the self-crosslinking urethane (meth)acrylate.

[0382] In particular, component d) includes triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, Nt-butyldiethanolamine, trimethanolamine, N-methyldimethanolamine, 3-(dimethylamino)-1,2-propanediol, 3-(diethylamino)-1,2-propanediol, 3-(dipropylamino)-1,2-propanediol, 2-(dimethylamino)propane-1,3-diol, bis(2-hydroxyethyl)dodecylamine, bis(2-hydroxyethyl)octadecylamine, N,N-dioctadecyl-N',N'-bis(2-hydroxyethyl)-1,3-diaminopropane, 3-morpholino-1,2-propanediol, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1-yl-1,2-propanediol, and the following formula (XXXXVI): TIFF2026518308000070.tif34170[where, R y , R' y , R z , L'3, Z'' and n 38 It may include at least one amino-functional polyol selected from aminobenzamide diols as defined by the chain extension portion by formula (XXXXVI).

[0383] The total amount of component d) used to prepare the self-crosslinkable urethane (meth)acrylate of the present invention may be 0 to 84.5% by weight, particularly 0.1 to 75% by weight, and more specifically 1 to 65% by weight of component d), based on the total amount of components a), b), c), and d).

[0384] In one embodiment, the total amount of component d) used to prepare the self-crosslinkable urethane (meth)acrylate of the present invention may be less than 0.2% by weight, particularly less than 0.1% by weight, and more specifically 0% by weight, based on the total amount of components a), b), c), and d). Such an amount may be used, for example, when the method for preparing the self-crosslinkable urethane (meth)acrylate of the present invention substantially does not contain component d).

[0385] In one embodiment, the total amount of component d) used to prepare the self-crosslinkable urethane (meth)acrylate of the present invention may be 0.1 to 20% by weight, particularly 0.2 to 15% by weight, and more specifically 0.5 to 10% by weight of component d), based on the total amount of components a), b), c), and d). Such an amount may be used, for example, when component d) contains a nonpolymeric polyol.

[0386] In another embodiment, the total amount of component d) used to prepare the self-crosslinkable urethane (meth)acrylate of the present invention may be 15 to 84.5% by weight, particularly 20 to 75% by weight, and more specifically 25 to 65% by weight of component d), based on the total amount of components a), b), c), and d). Such an amount may be used, for example, when component d) contains a polymer polyol.

[0387] e) Any other components The method for preparing self-crosslinking urethane (meth)acrylate may also include the use of components other than components a), b), c), and d).

[0388] This method can be carried out in the presence of a catalyst. Alternatively, this method may not require the presence of a catalyst.

[0389] The catalyst, if present, can be any substance capable of catalyzing the reaction between a hydroxyl group and an isocyanate group to form a urethane bond. The catalyst can accelerate the rate of such a reaction occurring at a given temperature and / or achieve the target degree of completion of such a reaction at a lower temperature than the temperature at which the target degree of completion would be achieved in the absence of the urethane catalyst.

[0390] Any tin-based catalyst known in the art may be used (e.g., dibutyltin dilaurate). However, according to one embodiment, a non-tin catalyst or a combination of non-tin catalysts is used.

[0391] Suitable examples of non-tin catalysts include, for example, one or more non-tin catalysts selected from the group consisting of bismuth carboxylate complexes (such as bismuth octoate or bismuth neodecanoate); zirconium acetylacetonate complexes; hafnium acetylacetonate complexes; titanium acetylacetonate complexes; zirconium beta-diketiminate complexes; hafnium beta-diketiminate complexes; titanium beta-diketiminate complexes; zirconium amidinate complexes; hafnium amidinate complexes; titanium amidinate complexes; zinc carboxylate complexes; tertiary amines; imidazoles; N-heterocyclic carbenes; tetraalkylammonium (pseudo)halides; phosphines; and combinations thereof.

[0392] Typically, the catalyst may be used in an amount of 0.0001 to 0.1% by weight, based on the total weight of components a), b), c), and d).

[0393] This method may be carried out in the presence of a solvent. Alternatively, this method may not require the presence of a solvent. As used herein, the term “solvent” means a non-reactive organic solvent, i.e., a solvent that does not react with the other components used in the preparation of the self-crosslinkable urethane (meth)acrylate.

[0394] Examples of suitable solvents include aliphatic hydrocarbons, e.g., n-pentane, n-hexane, n-heptane, octanecyclohexane, or methylcyclohexane; aromatic hydrocarbons, e.g., benzene, toluene, or xylene; hydrogenated hydrocarbons, e.g., dichloromethane, chloroform, or trichloroethane; ketones, e.g., acetone, methyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclopentanone, or cyclohexanone; esters, e.g., methyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, or butyl acetate; ethers, e.g., diethyl ether, diisopropyl ether, dibutyl ether, ethylene glycol diethyl ether, tetrahydrofuran, or tetrahydropyran; carbonates, e.g., diethyl carbonate; and combinations thereof.

[0395] Preferably, this method does not involve the use of a solvent. When a solvent is used, the total amount of the solvent may be 5 to 150% by weight, based on the total weight of components a), b), c), and d).

[0396] This process can be carried out in the presence of stabilizers such as antioxidants, light-blocking / absorbing agents, or polymerization inhibitors. Alternatively, this method may not require the presence of stabilizers.

[0397] Introducing stabilizers during the preparation process of self-crosslinking urethane (meth)acrylates can prevent undesirable reactions during the manufacturing process and / or during storage of the resulting product. The stabilizer may be a compound or substance that delays or prevents the reaction or curing of chemically polymerizable functional groups present in the composition in the absence of electromagnetic radiation that induces the chemical reaction. However, it is advantageous to select the amount and type of stabilizer so that the self-crosslinking urethane (meth)acrylate maintains its curing ability when exposed to electromagnetic radiation that induces the chemical reaction (i.e., so that the stabilizer does not inhibit the radiation curing of the composition). The stabilizer may, in particular, be a free radical stabilizer (i.e., a stabilizer that functions by inhibiting free radical reactions).

[0398] In the present invention, any stabilizer known in the art related to (meth)acrylate functionalized compounds may be used. Quinone represents a particularly preferred type of stabilizer that can be used in relation to the present invention. As used herein, the term “quinone” includes both quinone and hydroquinone, as well as their ethers such as monoalkyl, monoaryl, monoaralkyl, and bis(hydroxyalkyl) ethers of hydroquinone. Hydroquinone monomethyl ether (MeHQ) is an example of a suitable stabilizer that can be used. Other stabilizers known in the art include hydroquinone (HQ), 4-tert-butylcatechol (TBC), 3,5-di-tert-butyl-4-hydroxytoluene (BHT), phenothiazine (PTZ), pyrogallol, phosphite compounds, triphenylantimony, and tin(II) salts.

[0399] Preferably, this method involves the use of a stabilizer such as MeHQ or BHT. When a stabilizer is used, the total amount of the stabilizer may be 0.01 to 1% by weight, based on the total weight of components a), b), c), and d).

[0400] The method for preparing self-crosslinkable urethane (meth)acrylate does not necessarily involve the use of any components other than components a), b), c), d), catalyst, solvent, and stabilizer.

[0401] In particular, the method for preparing self-crosslinking urethane (meth)acrylate does not necessarily involve the use of dye components. Therefore, components a), b), c), and d) do not necessarily have to contain dye portions.

[0402] The dye component contains or consists of at least one NCO-reactive dye. The dye component may contain or consist of a mixture of NCO-reactive dyes.

[0403] NCO-reactive dyes are dyes having at least one group that is reactive to isocyanate groups, such as a hydroxyl group, a thiol group, or an amino group. As used herein, the term “dye” means a compound that imparts a color different from the color of a self-crosslinking urethane (meth)acrylate that does not contain such a dye moiety, and the different color is detectable by the naked eye with a colorant having a solubility of 10 mg / L or more in a medium introduced at 25°C.

[0404] The NCO-reactive dye may be selected from portions derived from azo dyes, phthalocyanine dyes, anthraquinone dyes, dicyanovinyl dyes or tricyanovinyl dyes, methine dyes, aniline dyes, or indoaniline dyes, such as those described in U.S. Patent Publication No. 2014 / 0316060.

[0405] Polymerization process The self-crosslinkable urethane (meth)acrylate of the present invention can be used in polymerization steps, i.e., steps for polymerizing (e.g., curing) one or more ethylenically unsaturated compounds.

[0406] A step for polymerizing one or more ethylenically unsaturated compounds includes contacting one or more ethylenically unsaturated compounds with a self-crosslinkable urethane (meth)acrylate according to the present invention, and irradiating the mixture with ultraviolet light, near-ultraviolet light, visible light, infrared light, near-infrared light and / or electron beams.

[0407] In particular, the polymerization step does not require the use of any radical initiator or initiator system other than the self-crosslinkable urethane (meth)acrylate of the present invention.

[0408] In another embodiment, the polymerization step may use a radical initiator or initiator system other than the self-crosslinkable urethane (meth)acrylate of the present invention. When an initiator or initiator system other than the self-crosslinkable urethane (meth)acrylate of the present invention is used in the polymerization step of the present invention, the amount of the initiator or initiator system may be less than the amount conventionally used in the polymerization step system. For example, the amount of the initiator or initiator system may be 0.01 to 5%, particularly 0.1 to 2.5%, and more specifically 0.5 to 1.5%, based on the total weight of the ethylenically unsaturated compound to be cured.

[0409] Examples of radical initiators and initiation systems include photoinitiators, peroxides, redox systems, and azo compounds.

[0410] Photoinitiators are compounds that absorb light and generate reactive species useful for initiating polymerization reactions. Non-limited types of photoinitiators include, for example, benzoin, benzoin ethers, acetophenone, α-hydroxyacetophenone, benzyl, benzyl ketal, phosphine oxide, acylphosphine oxide, α-hydroxyketone, phenylglyoxylate, α-aminoketone, benzophenone, thioxanthone, xanthone, acridine derivatives, phenazine derivatives, quinoxaline derivatives, triazine compounds, benzoyl formates, aromatic oximes, metallocenes, acylsilyl or acylgermanyl compounds, camphorquinones, polymer derivatives thereof, and mixtures thereof. Examples of specific photoinitiators include, but are not limited to, benzoin ether, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, alpha-methylbenzoin, alpha-phenylbenzoin, Michler ketone, acetophenone, e.g., 2,2-dialkoxybenzophenone and 1-hydroxyphenyl ketone, benzophenone, 4,4'-bis-(diethylamino)benzophenone, acetophenone, 2,2-diethyloxyacetophenone, 2-isopropylthioxanthone, thioxanthone, diethylthioxanthone, 1,5-acenaphthylene, benzyl, α-hydroxyketone, 2,4,6-trimethylbenzoyldiphosphate Nylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 2-hydroxy-2-methyl-1-phenyl-propanone, oligomer α-hydroxyketone, benzoylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphineate, anisoin, (benzene)tricarbonylchromium, benzoin isobutyl ether, benzophenone / 1-hydroxycyclohexyl phenyl ketone 50 / 50 blend, 3,3',4,4'-Benzophenonetetracarboxylic dianhydride, 4-benzoylbiphenyl, 2-benzyl-2-(dimethylamino)-4'-morpholinobtyrophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, camphorquinone, 2-chloroxanthene-9-one, dibenzosverenone, 4,4'-dihydroxybenzophenone, 4-(dimethylamino)benzophenone, 4,4'-dimethylbenzyl, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone, diphenyl(2, This includes 4,6-trimethylbenzoyl)phosphine oxide / 2-hydroxy-2-methylpropiophenone 50 / 50 blend, 4'-ethoxyacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, methylbenzoyl formate, phenanthrenequinone, 4'-phenoxyacetophenone, (cumene)cyclopentadienyl iron(II) hexafluorophosphate, 9,10-diethoxy and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, and combinations thereof.

[0411] Peroxides can be defined as compounds containing an oxygen-oxygen single bond. Peroxides may be selected from persulfates, hydrogen peroxide (H2O2), organic hydroperoxides, peracids, or mixtures thereof. Non-limiting examples of peroxides include ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, cumene hydroperoxide, t-butyl hydroperoxide, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, peracetic acid, and perbenzoic acid.

[0412] A redox system can be defined as a mixture of a peroxide and a reducing agent that promotes the decomposition of the peroxide. Examples of suitable reducing agents include ferrous compounds, carboxylic acids, and / or sodium metabisulfite.

[0413] Azo compounds can be defined as compounds containing a nitrogen-nitrogen double bond. Examples of suitable azo compounds include 2,2'-azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), or 2,2'-azobis(2-methylbutyronitrile).

[0414] The ethylenically unsaturated compound polymerized in the polymerization process may be one of the following:

[0415] curable composition The self-crosslinking urethane (meth)acrylates disclosed herein are particularly useful in applications requiring very low extractability and fast curing time upon chemical irradiation. In particular, self-crosslinking urethane (meth)acrylates can be used in curable compositions to obtain coatings (especially scratch-resistant wood coatings, concrete coatings, or plastic coatings), inks, varnishes, encapsulation or embedding materials, 3D printed articles, molded articles, sealants, adhesives, nail polish, or dental materials. Self-crosslinking urethane (meth)acrylates are particularly useful for obtaining thick parts or thick coatings.

[0416] The curable composition of the present invention comprises a self-crosslinkable urethane (meth)acrylate (referred to as component A) according to the present invention, and optionally a polymerizable component other than component A (referred to as component B).

[0417] The curable composition of the present invention may contain component A) in amounts of 1-100% by weight, 5-95% by weight, 10-90% by weight, 15-85% by weight, 20-80% by weight, 25-75% by weight, 30-70% by weight, 35-65% by weight, or 40-60% by weight, based on the total weight of components A) and B).

[0418] The curable composition of the present invention may contain component B) in amounts of 0-99% by weight, 0-95% by weight, 10-90% by weight, 15-85% by weight, 20-80% by weight, 25-75% by weight, 30-70% by weight, 35-65% by weight, or 40-60% by weight, based on the total weight of components A) and B).

[0419] The curable composition of the present invention may contain component A) in amounts of 1-100% by weight, 5-95% by weight, 5-90% by weight, 10-85% by weight, 10-80% by weight, 15-75% by weight, 15-70% by weight, 20-65% by weight, and 20-60% by weight, based on the weight of the curable composition.

[0420] The curable composition of the present invention may contain component B) in amounts of 0-99% by weight, 0-95% by weight, 10-95% by weight, 15-90% by weight, 20-90% by weight, 25-85% by weight, 30-85% by weight, 35-80% by weight, and 40-80% by weight, based on the weight of the curable composition.

[0421] Polymerizable components The curable composition of the present invention may optionally contain polymerizable component B).

[0422] The polymerizable component contains or consists of one or more ethylenically unsaturated compounds. The polymerizable component may contain or consist of one or more ethylenically unsaturated compounds.

[0423] Component B) is different from component A). Therefore, one or more ethylenically unsaturated compounds in component B) do not contain a chromophore moiety.

[0424] Component B) may comprise one or more ethylenically unsaturated compounds selected from (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, and mixtures thereof. In particular, component B) may comprise one or more (meth)acrylate-functionalized monomers.

[0425] As used herein, “(meth)acrylate-functionalized monomer” means a monomer containing a (meth)acrylate group, in particular an acrylate group. The term “(meth)acrylate-functionalized oligomer” means an oligomer containing a (meth)acrylate group, in particular an acrylate group.

[0426] Component B) may contain at least one (meth)acrylate-functionalized monomer. Component B) may contain a mixture of (meth)acrylate-functionalized monomers.

[0427] (Meth)acrylate-functionalized monomers may have a molecular weight of less than 600 g / mol, particularly 100-550 g / mol, and more specifically 200-500 g / mol.

[0428] (Meth)acrylate-functionalized monomers may have 1 to 6 (meth)acrylate groups, particularly 1 to 3 (meth)acrylate groups.

[0429] Component B) may comprise a mixture of (meth)acrylate-functionalized monomers having different functionalities. For example, component B) may comprise a mixture of (meth)acrylate-functionalized monomers containing a single acrylate or methacrylate group per molecule (referred to herein as "mono(meth)acrylate-functionalized compounds") and (meth)acrylate-functionalized monomers containing two or more, preferably two or three acrylate and / or methacrylate groups per molecule (referred to herein as "poly(meth)acrylate-functionalized compounds").

[0430] In particular, component B) may contain a mono(meth)acrylate-functionalized monomer. The mono(meth)acrylate-functionalized monomer may advantageously function as a reactive diluent and reduce the viscosity of the composition.

[0431] Examples of suitable mono(meth)acrylate functionalizations include, but are not limited to, mono(meth)acrylate esters of aliphatic alcohols (the aliphatic alcohol may be linear, branched, or alicyclic, and may 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 containing alkylated phenols); mono(meth)acrylate esters of alkylated alcohols (such as benzyl alcohol); and mono(meth)acrylates of oligomers and polymer glycols, e.g., diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, por This includes: ethylene glycol and polypropylene glycol; mono(meth)acrylates of monoalkyl ethers of glycols and oligoglycols; mono(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aliphatic alcohols (the aliphatic alcohol may be linear, branched or alicyclic, and may 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, etc.

[0432] The following compounds are specific examples of mono(meth)acrylate functionalized monomers suitable for use in component B): 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 )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; Tricyclodecane methanol (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; methoxy polyethylene glycol (meth)acrylate; hydroxyl-ethyl-butyl urethane (meth)acrylate; 3-(2-hydroxyalkyl) oxazolidinone (meth)acrylate; and combinations thereof.

[0433] Component B) may contain poly(meth)acrylate-functionalized monomers.

[0434] Poly(meth)acrylate-functionalized monomers may have 2 to 6 (meth)acrylate groups, particularly 2 to 6 acrylate groups.

[0435] Examples of suitable poly(meth)acrylate-functionalized monomers include acrylate esters and methacrylate esters of polyols. Examples of suitable polyols are listed above for any polyol component d) used to prepare the self-crosslinkable urethane (meth)acrylate of the present invention. Such polyols may be fully or partially esterified (by (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.) as long as they contain at least two (meth)acrylate functional groups per molecule.

[0436] Exemplary poly(meth)acrylate functionalized monomers include: bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; 1,2-butanediol di(meth)acrylate; 2,3-butanediol di(meth)acrylate; 1,3-butanediol di(meth)acrylate; 1,4-butanediol Di(meth)acrylate; 1,5-pentanediol; Di(meth)acrylate; 1,6-hexanediol; Di(meth)acrylate; 1,8-octanediol; Di(meth)acrylate; 1,9-nonanediol; Di(meth)acrylate; 1,10-nonanediol; Di(meth)acrylate; 1,12-dodecanediol; Di(meth)acrylate; neopentyl glycol; Di(meth)acrylate; 2-methyl-2,4-pentanediol; Di(meth)acrylate; polybutadiene; Di(meth)acrylate; cyclohexane-1,4-dimethanol; Di(meth)acrylate; tricyclodecanedimethanol; 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;This may include 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.

[0437] In a preferred embodiment, component B) comprises at least one poly(meth)acrylate-functionalized monomer selected from glycerol tri(meth)acrylate; diglycerol tetra(meth)acrylate, triglycerol penta(meth)acrylate, tetraglycerol hexa(meth)acrylate, trimethylolethane tri(meth)acrylate; trimethylolpropane tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, di(trimethylolpropane)tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol) hexa(meth)acrylate; tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives, and combinations thereof.

[0438] Component B) may contain urethane (meth)acrylate monomer.

[0439] The urethane (meth)acrylate monomer has 2 to 10 (meth)acrylate groups and at least 2 urethane bonds.

[0440] In particular, component B) is given by the following formula (XXXXVII) TIFF2026518308000071.tif32170[In the formula, R4, R5, and w' are as defined above for the (meth)acrylate functionalization moiety ACR; R1 is as defined above for the polyisocyanate moiety UU. It may contain urethane (meth)acrylate monomers.

[0441] Component B) may contain 0 to 100% by weight, particularly 5 to 90% by weight, more specifically 10 to 80% by weight, even more specifically 15 to 75% by weight, and even more specifically 20 to 70% by weight, based on the total weight of component B). In particular, component B) may contain 50 to 100% by weight, or 55 to 100% by weight, or 60 to 100% by weight, or 65 to 100% by weight, or 70 to 100% by weight, based on the total weight of component B).

[0442] Component B) may contain (meth)acrylate-functionalized oligomers. Component B) may contain a mixture of (meth)acrylate-functionalized oligomers.

[0443] (Meth)acrylate-functionalized oligomers may be selected, in particular, to improve the flexibility, strength, and / or modulus of the cured polymer prepared by curing the curable composition of the present invention, among other properties.

[0444] (Meth)acrylate-functionalized oligomers may have 1 to 18 (meth)acrylate groups, particularly 2 to 6 (meth)acrylate groups, and more specifically 2 to 6 acrylate groups.

[0445] (Meth)acrylate-functionalized oligomers may have a number-average molecular weight of 600 g / mol or less, particularly 800 to 15,000 g / mol, and more specifically 1,000 to 5,000 g / mol.

[0446] In particular, component B) 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)acrylic poly(meth)acrylate, and mixtures thereof.

[0447] Non-limiting examples of epoxy (meth)acrylates are reaction products of epoxides (such as glycidyl ethers, glycidyl esters, alicyclic epoxides, or epoxides obtained by epoxideization of mono- and / or polyunsaturated compounds) and (meth)acrylicating agents (such as (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or combinations thereof). Epoxides include 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, vinylcyclohexane oxide, 4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl l-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl) ether, 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, trimethylol methane triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, di(trimethylolpropane) tetraglycidyl ether, pentaerythritol Tetraglycidyl ether, diglycidyl cyclohexane dicarboxylate, cyclohexane diglycidyl ether, cyclohexane-1,4-Dimethanol diglycidyl ether, tricyclodecanedimethanol 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 The following can be selected: polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as triglycidyl ethers, diglycidyl phthalate, diglycidyl terephthalate, diglycidyl isophthalate, ethylene glycol, propylene glycol, and glycerol; diglycidyl esters of aliphatic long-chain (C6-C22) dibasic acids; monoglycidyl ethers of aliphatic higher alcohols; phenols, cresols, butylphenols, or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these compounds; glycidyl esters of higher fatty acids; epoxide-modified vegetable oils (such as epoxide-modified soybean oil and epoxide-modified linseed oil); epoxybutyl stearic acid; epoxyoctyl stearic acid; epoxide-modified polybutadiene; triglycidyl isocyanurate, etc.

[0448] Non-limiting examples of polyester (meth)acrylates are reaction products of hydroxyl-terminated polyester polyols with (meth)acrylicating 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 so that all or substantially all of the hydroxyl groups of the polyester polyol are (meth)acrylelated. Polyester polyols can be prepared by polycondensation reactions of polyhydroxyl-functional components (particularly diols) and polycarboxylic acid-functional compounds (particularly dicarboxylic acids or anhydrides). To prepare polyester (meth)acrylates, the hydroxyl groups of the polyester polyol are partially or completely esterified by reaction with a (meth)acrylicating agent. Polyester (meth)acrylates can also be synthesized by reacting hydroxyl-containing (meth)acrylates, such as hydroxyalkyl (meth)acrylates (e.g., hydroxyethyl acrylate), with polycarboxylic acids. The polyhydroxyl functional components and polycarboxylic acid functional components may each have linear, branched, alicyclic, or aromatic structures, and can be used individually or in mixtures.

[0449] Non-limiting examples of polyether (meth)acrylates are condensation reaction products of polyether polyols, which are polyetherols, with (meth)acrylicating agents (such as (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or combinations thereof). Suitable polyetherols can be linear or branched substances containing ether links 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) using starting molecules. Suitable starting molecules include water, hydroxyl-functional materials, polyester polyols, and amines. Polyetherols can also be obtained by condensation of diols such as glycols.

[0450] Non-limiting examples of urethane (meth)acrylates are condensation reaction products of at least one polyisocyanate (e.g., diisocyanate, triisocyanate), at least one polyol (such as a polyether polyol or polyester polyol), and a hydroxyl-functionalized (meth)acrylate (such as 2-hydroxyethyl (meth)acrylate or 3-hydroxypropyl (meth)acrylate), providing terminal (meth)acrylate groups. For example, urethane (meth)acrylate may contain two, three, four or more (meth)acrylate groups per molecule. The order of adding components for preparing urethane (meth)acrylate is well known in the art. For example, a hydroxyl-functionalized (meth)acrylate may first react with a polyisocyanate to obtain an isocyanate-functionalized (meth)acrylate, which may then react with a polyol. In yet another embodiment, the polyisocyanate may first react with a polyol to obtain an isocyanate-functionalized polyol, which may then react with a hydroxyl-functionalized (meth)acrylate. Alternatively, all components may be combined and reacted simultaneously.

[0451] Non-limiting examples of (meth)acrylated poly(meth)acrylates are substances having an oligomeric (meth)acrylic skeleton functionalized with one or more (meth)acrylate groups (which may be at the ends of the oligomer or pendants of the acrylic skeleton). The (meth)acrylic skeleton may be a homopolymer, random copolymer, or block copolymer composed of repeating units of (meth)acrylic monomers. The (meth)acrylic monomers may be any monomer (meth)acrylate, such as C1-C6 alkyl (meth)acrylates, as well as functionalized (meth)acrylates, such as (meth)acrylates having hydroxyl groups, carboxylic acid groups, and / or epoxy groups. (Meth)acrylated poly(meth)acrylates can be prepared by 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) functionalized with at least a portion of a hydroxyl group, a carboxylic acid group and / or an epoxy group to obtain a functionalized poly(meth)acrylate, and then reacting this with one or more (meth)acrylate-containing reaction products to introduce a desired (meth)acrylate functional group.

[0452] Component B) may contain 0 to 100% by weight, particularly 10 to 95% by weight, more specifically 20 to 90% by weight, even more specifically 25 to 85% by weight, and even more specifically 30 to 80% by weight of (meth)acrylate-functionalized oligomers, based on the total weight of component B). In particular, component B) may contain 0 to 50% by weight, or 0 to 45% by weight, or 0 to 40% by weight, or 0 to 35% by weight, or 0 to 30% by weight of (meth)acrylate-functionalized oligomers, based on the total weight of component B).

[0453] Component B) may contain one or more ethylenically unsaturated compounds other than (meth)acrylate-functionalized monomers or oligomers. Examples of such ethylenically unsaturated compounds include: - Polyvinyl and / or polyallyl monomers (especially divinylbenzene, 1,4-butanediol divinyl ether, tri(ethylene glycol) divinyl ether, diallyl ether, glycerol diallyl ether, glycerol triallyl ether, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, diallyl phthalate, triallyl isocyanurate, 2,4,6-triallyloxy-1,3,5-triazine, glyoxal bis(diallyl acetal) and combinations thereof); - Vinyl esters of carboxylic acids (especially vinyl acetate, vinyl propionate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl octanoate, vinyl pelargonate, vinyl laurate, vinyl stearate, vinyl versatinate, and mixtures thereof); - Vinyl ethers (especially vinyl methyl ether, vinyl ether ether, vinyl n-butyl ether, vinyl isobutyl ether and mixtures thereof, ethylene glycol divinyl ether, triethylene glycol divinyl ether and trimethylolpropane trivinyl ether); - Alicyclic vinyl monomers (especially vinylcyclohexane); - Olefins (especially ethylene, propene, 1-butene, isobutylene, diisobutylene, 1-nonene, 1-decene, and mixtures thereof); - Conjugated dienes (especially butadiene, isoprene, pentadiene, chlorodiene, and mixtures thereof); - Vinyl aromatic monomers (especially styrene, alpha-methylstyrene, tert-butylstyrene, ortho-, meta- and para-methylstyrene, ortho-, meta- and para-ethylstyrene, o-methyl-p-isopropylstyrene, p-chlorostyrene, p-bromostyrene, o,p-dichlorostyrene, o,p-dibromostyrene, ortho-, meta- and para-methoxystyrene, optionally substituted indene, optionally substituted vinylnaphthalene, acenaphthylene, diphenylethylene, vinylanthracene, and mixtures thereof); - Mono- or dicarboxylic acid monomers, cyclic anhydride monomers and salts thereof (in particular, 3-butenic acid, crotonic acid, vinyl acetic acid, fumaric acid, maleic acid, maleic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, itaconic acid, mesaconic acid, citraconic acid, glutaconic acid, muconic acid and mixtures thereof); - Unsaturated polymers such as polybutadiene; - and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives - and mixtures thereof.

[0454] Other ingredients The curable composition of the present invention may further comprise one or more additives and / or one or more solvents, as detailed below.

[0455] additives The curable composition of the present invention may further contain additives. The curable composition may contain a mixture of additives.

[0456] In particular, additives may be selected from initiators or initiators, sensitizers, amine synergies, stabilizers (such as antioxidants, light-shielding / absorbing agents or polymerization inhibitors), anti-foaming agents, flowing agents or leveling agents, colorants, pigments, dispersants (wetting agents, surfactants), lubrication additives, fillers, thixotropic agents, matting agents, impact modifiers, waxes and mixtures thereof; as well as any other additives conventionally used in coatings, sealants, adhesives, molding, 3D printing or ink art.

[0457] The curable composition may contain radical initiators or initiator systems other than the self-crosslinkable urethane (meth)acrylate of the present invention. The initiators or initiator systems may be as defined above in the polymerization step of the present invention.

[0458] Preferably, the curable composition does not substantially contain initiators or initiator systems other than the self-crosslinkable urethane (meth)acrylate of the present invention.

[0459] When an initiator is added to the curable composition, the initiator may be selected from photoinitiators having Norrish type I activity and / or Norrish type II activity, more specifically from radical photoinitiators having Norrish type I activity. Such photoinitiators may be as defined above in the polymerization step of the present invention.

[0460] In particular, photoinitiators include benzophenones, such as SpeedCure® BP (benzophenone), SpeedCure® 7005 (polymer benzophenone), SpeedCure® 7006 (polymer benzophenone), SpeedCure® EMK (4,4'-bis(diethylamino)benzophenone), or SpeedCure® BMS (4-benzoyl-4'-methyldiphenyl sulfide); and thioxanthones, such as SpeedCure® 70 10 (polymer thioxanthone), SpeedCure® ITX (isopropyl thioxanthone), SpeedCure® DETX (2,4-diethyl thioxanthone), or SpeedCure® CPTX (1-chloro-4-propoxythioxanthone); α-hydroxyacetophenone, e.g., SpeedCure® 73 (2-hydroxy-2-methyl-1-phenylpropanone); acylphosphine oxide, e.g., SpeedCure® BPO (phenyl The following may be selected: bis(2,4,6-trimethylbenzoyl)-phosphine oxide), SpeedCure® TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide), or SpeedCure® TPO-L (ethyl(2,4,6-trimethylbenzoyl)phenylphosphine); phenyl glyoxylates, such as SpeedCure® MBF (methylbenzoyl formate); and mixtures thereof.

[0461] When an initiator or initiator system other than the self-crosslinkable urethane (meth)acrylate of the present invention is added to the curable composition of the present invention, the amount of the initiator or initiator system may be less than the amount conventionally used in photocurable systems. For example, the amount of the initiator or initiator system may be 0.01 to 5%, particularly 0.1 to 2.5%, and more specifically 0.5 to 1.5%, based on the total weight of the curable composition.

[0462] The curable composition may contain stabilizers such as antioxidants, light-blocking / absorbing agents, or polymerization inhibitors. Suitable stabilizers are as defined above for any components used in the preparation process of self-crosslinking urethane (meth)acrylates.

[0463] The concentration of stabilizers in a curable composition varies depending on the specific stabilizer or combination of stabilizers selected for use, the desired degree of stabilization, and whether the components in the curable composition are prone to degradation in the absence of stabilizers. However, typically, curable compositions are formulated to contain 5 to 5000 ppm of stabilizer.

[0464] The curable composition may contain an amine synergist, or it may not contain an amine synergist substantially. As used herein, the term “amine synergist” refers to an amine synergist other than the self-crosslinkable urethane (meth)acrylate of the present invention. The amine synergist may be a compound having a hydrogen atom at the alpha position relative to a heteroatom such as N or S. The amine synergist may be added to the curable composition to increase the curing rate as needed. The amine synergist may, in particular, act as a hydrogen donor for Norrish type II chromophores. Non-limiting examples of amine synergs include tertiary amines and polythiols, such as ethylhexyl-dimethylaminobenzoate (SpeedCure® EHA), triethanolamine, pentaerythritol tetrakis-3-mercaptopropionate, or aminoacrylates obtained by the reaction of primary or secondary amines with acrylate-functionalized monomers or oligomers (such as CN174 (Sartomer) and CN186 (Sartomer)).

[0465] The curable composition may be substantially free of dyes. For example, the curable composition may contain less than 1% by weight, particularly less than 0.5% by weight, or even 0% by weight of dyes, based on the weight of the curable composition.

[0466] The curable composition may contain a colorant. As used herein, the term “colorant” means a substance other than a dye that imparts color to the curable composition. The colorant may also be a pigment. The term “pigment” is defined in DIN 55943 as a colorant that is substantially insoluble in the application medium under the relevant ambient conditions and therefore has a solubility of less than 10 mg / L at 25°C. The term “CI” is used as an abbreviation for Colour Index.

[0467] In particular, the composition may contain a pigment selected from organic and / or inorganic pigments. If the pigment is not a self-dispersing pigment, the curable composition preferably also contains a dispersant, more preferably a polymer dispersant. The pigment may be black, cyan, magenta, yellow, red, orange, purple, blue, green, brown, and mixtures thereof. The pigment may be selected from those disclosed in HERBST, Willy, et al. Industrial Organic Pigments, Production, Properties, Applications. 3rd edition. Wiley-VCH, 2004. ISBN 3527305769.

[0468] The curable composition of the present invention may contain a dispersant. The dispersant may be used to disperse insoluble materials such as pigments or fillers in the curable composition.

[0469] solvent The curable composition of the present invention may contain a solvent. The solvent may be as defined above for the preparation of the self-crosslinkable urethane (meth)acrylate.

[0470] Advantageously, the curable composition of the present invention can be formulated to be substantially solvent-free. For example, the curable composition may contain little to no solvent based on the total weight of the curable composition, for example, the weight of the solvent may be less than 10%, less than 5%, less than 1%, or 0%.

[0471] According to some embodiments, the curable composition is liquid at 25°C. In various embodiments of the present invention, the curable compositions described herein are formulated to have a viscosity of less than 10,000 mPa.s, or less than 5,000 mPa.s, or less than 1,000 mPa.s, or less than 5000 mPa.s, or less than 200 mPa.s, or less than 100 mPa.s, or less than 250 mPa.s, or even less than 100 mPa.s, when measured at 25°C using a Brookfield viscometer, Model DV-II, 27 spindle (spindle speed typically varies between 20 rpm and 200 rpm depending on viscosity). In advantageous embodiments of the present invention, the viscosity of the curable composition is 10 to 10,000 mPa.s, or 10 to 5,000 mPa.s, or 10 to 1,000 mPa.s, or 10 to 500 mPa.s, or 10 to 250 mPa.s, or 10 to 100 mPa.s, at 25°C.

[0472] composition The curable compositions described herein may be compositions subjected to curing by free radical polymerization. In certain embodiments, the curable compositions may be cured by exposure to chemical rays, particularly ultraviolet light, near-ultraviolet light, visible light, infrared light, near-infrared light, and / or electron beams.

[0473] The curable composition of the present invention may be a coating composition, an ink composition, a varnish composition, an encapsulation or potting composition, a 3D printing composition, a molding composition, a sealant composition, an adhesive composition, a nail polish composition, or a dental composition.

[0474] The end uses of the curable compositions include, but are not limited to, inks, coatings, adhesives, additive manufacturing resins (such as 3D printing resins), molding resins, sealants, composite materials, antistatic layers, electronic applications, recyclable materials, smart materials that can detect and react to irritants, packaging materials, personal care products, manicures, articles for use in agriculture, water or food processing, or livestock farming, and biomedical materials. Therefore, the curable compositions of the present invention are useful in the manufacture of biocompatible articles. Such articles may, for example, exhibit high biocompatibility, low cytotoxicity, and / or low extractability.

[0475] The composition according to the present invention can be used, in particular, to obtain a cured product according to the following steps.

[0476] Process for preparing a cured product A step for preparing a cured product according to the present invention includes curing the curable composition of the present invention. In particular, the curable composition can be cured by exposing the composition to electromagnetic radiation that causes a chemical reaction. More specifically, the curable composition can be cured by exposing the composition to ultraviolet light, near-ultraviolet light, visible light, infrared light, near-infrared light, and / or electron beams. The curable composition can be advantageously cured by exposing the composition to an LED light source.

[0477] Curing can be accelerated and facilitated by supplying energy to the curable composition, such as by heating it. Therefore, the cured product can be considered a reaction product of the curable composition formed by curing. The curable composition can be partially cured by exposure to electromagnetic radiation that induces a chemical reaction, and further curing can be achieved by heating the partially cured article. For example, the product formed from the curable composition can be heated at a temperature of 40°C to 120°C for a period of 5 minutes to 12 hours.

[0478] Before curing, the curable composition can be applied to the substrate surface by known conventional methods such as spraying, jetting, knife coating, roller coating, casting, drum coating, dipping, and combinations thereof. Indirect application using a transfer process may also be used.

[0479] The substrate to which the curable composition is applied and cured may be of any type. Suitable substrates are detailed below. When used as an adhesive, the curable composition is placed between two substrates and then cured, and the cured composition can thereby bond the substrates to provide an adhesive article. Curable compositions according to the present invention can also be formed or cured in bulk (for example, the curable composition can be cast into a suitable mold and then cured).

[0480] The substrate may be a ceramic, metal, mineral, cellulose, animal-based, or polymer substrate. The substrate may also be a part of the human body, such as a tooth or nail.

[0481] The substrate may be porous or substantially non-porous. The substrate may be transparent, translucent, or opaque.

[0482] Examples of ceramic substrates include alumina-based ceramics and zirconia-based ceramics. Examples of metal substrates include titanium, gold, silver, copper, brass, steel, and bronze. Examples of mineral substrates include glass, asbestos, and basalt. Examples of cellulose substrates include plain paper or resin-coated paper (e.g., paper coated with polyethylene or polypropylene). There are no particular restrictions on the type of paper, and it includes not only newsprint, magazine paper, office paper, and wallpaper, but also higher-gram papers commonly called boards, such as white cardboard, corrugated cardboard, and packaging board. Further examples of cellulose substrates include bamboo, cotton, flax, hemp, jute, lyocell, modal, rayon, raffia, ramie, and sisal. Examples of cellulosic substrates include wool, fur, silk, and leather. Examples of polymer substrates include polyethylene, polypropylene, polycarbonate, polyvinyl chloride, polyethylene terephthalate, polyethylene naphthalate, polylactide, polyimide, polyacrylonitrile, polyurethane, and acrylonitrile butadiene styrene.

[0483] There are no restrictions on the shape of the substrate. The substrate may be a sheet, film, nonwoven or woven fiber mat, or a three-dimensional object.

[0484] In particular, the base material may be selected from food and beverage packaging, pharmaceutical packaging, textiles, nails, teeth, medical devices, food and beverage processing equipment, water pipes, or toys.

[0485] The cured product obtained by the method of the present invention may be a coating (particularly a scratch-resistant wood coating, concrete coating, or plastic coating), an ink, a varnish, a material for encapsulation or embedding, a 3D printed article, a molded article, a sealant, an adhesive, a nail polish, or a dental material.

[0486] 3D printing process 3D printed articles can be obtained in particular by a 3D printing process that includes printing a 3D article with the composition of the present invention. In particular, this process may include printing the 3D article layer by layer or continuously.

[0487] Three-dimensional (3D) printing (also known as additive manufacturing) is the process of creating 3D digital models by stacking building materials. 3D printed objects are created by using computer-aided design (CAD) data of the object to sequentially construct two-dimensional (2D) layers or slices corresponding to the cross-sections of the 3D object. Radiation can take the form of electromagnetic waves or electron beams. The most commonly applied energy sources are ultraviolet, near-ultraviolet, visible light, infrared, and / or near-infrared.

[0488] Multiple layers of the curable composition according to the present invention can be applied to the surface of a substrate. The multiple layers can be cured simultaneously (for example, by exposure to a single dose of radiation), or each layer can be cured sequentially before applying additional layers of the curable composition.

[0489] Non-limiting examples of suitable 3D printing processes include stereolithography (SLA), digital light-emitting diode (DLP), liquid crystal displays (LCD), inkjet head (or multi-jet) printing, continuous liquid interface fabrication (CLIP), extrusion processes such as continuous fiber 3D printing or cast-in-motion 3D printing, and volumetric 3D printing. The construction method may be "layer-by-layer" or continuous. The liquid may be in a vat or deposited, for example, by inkjet or gel deposition.

[0490] Stereolithography and other photocurable 3D printing methods typically involve applying a low-intensity light source to irradiate each layer of a photocurable resin to form the desired article. Consequently, the polymerization rate of the photocurable resin and the raw strength of the printed article are important criteria for determining whether a particular photocurable resin has sufficient raw strength to polymerize (cure) sufficiently upon irradiation and maintain integrity throughout the 3D printing process and post-processing.

[0491] The curable compositions of the present invention can be used as 3D printing resin formulations, i.e., compositions for use in manufacturing three-dimensional articles using 3D printing technology. Such three-dimensional articles may be self-supporting / self-supporting and may consist essentially of or derived from the cured compositions of the present invention. The three-dimensional articles may be composite materials comprising at least one component consisting essentially of or derived from the aforementioned cured compositions and at least one additional component consisting of one or more materials other than such cured compositions (e.g., metallic components, thermoplastic components, inorganic fillers, or fiber reinforcements). While the curable compositions of the present invention are particularly useful in digital optical printing (DLP), other types of three-dimensional (3D) printing methods (e.g., SLA, inkjet, multijet printing, piezoelectric printing, chemical beam curing extrusion, and gel deposition printing) can also be carried out using the curable compositions of the present invention. The curable compositions of the present invention may be used in three-dimensional printing operations together with other materials that function as scaffolds or supports for articles formed from the curable compositions of the present invention.

[0492] Therefore, the curable compositions of the present invention are useful in implementing various types of three-dimensional manufacturing or printing techniques, including methods for constructing three-dimensional objects stepwise or layer by layer. In such methods, layer formation can be carried out by solidification (curing) of the curable composition under the action of exposure to radiation such as visible light, ultraviolet light, or other chemical rays. For example, a new layer may be formed on the top or bottom surface of a growing object. The curable compositions of the present invention can also be advantageously used in methods for manufacturing three-dimensional objects by additive manufacturing carried out continuously. For example, an object may be manufactured from a liquid interface. Suitable methods of this kind are sometimes referred to in the art as "continuous liquid interface (or interface) manufacturing (or printing) ("CLIP") methods." Such methods are described, for example, in International Publication Nos. 2014 / 126830; 2014 / 126834; 2014 / 126837; and Tumbleston et al., “Continuous Liquid Interface Production of 3D Objects”, Science Vol. 347, Issue 6228, pp. 1349-1352 (March 20, 2015).

[0493] The curable composition may be supplied by ejection from the printhead rather than from a vat. This type of process is commonly called inkjet or multi-jet 3D printing. One or more UV curing sources mounted immediately behind the inkjet printhead cure the curable composition immediately after it is applied to the build surface substrate or a previously coated layer. This process allows the use of two or more printheads, enabling the application of different compositions to different areas of each layer. For example, compositions with different colors or different physical properties can be applied simultaneously to create 3D printed parts with various compositions. In typical use, support material, which is later removed during post-processing, is deposited simultaneously with the composition used to create the desired 3D printed part. The printhead can operate at temperatures ranging from approximately 25°C to approximately 100°C. The viscosity of the curable composition is less than 30 mPa·s at the printhead's operating temperature.

[0494] The process for preparing 3D printed articles is as follows: a) a step of providing a first layer of the curable composition according to the present invention onto a surface (e.g., coating); b) a step of curing the first layer at least partially to provide a cured first layer; c) the step of providing (e.g., coating) a second layer of the curable composition onto the first cured layer; d) A step of curing the second layer at least partially to provide a cured second layer bonded to the cured first layer; e) A process of constructing a three-dimensional object by repeating steps c) and d) a desired number of times; It may include.

[0495] Alternatively, the process for preparing a 3D printed item is as follows: a) A step of providing a carrier and an optically transparent member having a build surface, wherein the carrier and the build surface define a build region between them; b) The step of filling the build area with the composition defined above; c) A step of curing a portion of the composition in the build region continuously or intermittently according to the method defined above to form a cured composition; d) A step of moving the carrier away from the build surface and advancing it continuously or intermittently to form a 3D printed article from the cured composition; It may include.

[0496] After a 3D article is printed, one or more post-processing steps may be performed. These post-processing steps may be selected simultaneously or sequentially from one or more of the following: removal of printed support structures; washing with water and / or organic solvents to remove residual resin; and post-curing using heat treatment and / or electromagnetic radiation to induce chemical reactions. The post-processing steps may be used to transform the freshly printed article into a finished, functional article ready for use in its intended application.

[0497] Inkjet printing process The inkjet printing process according to the present invention includes spraying the curable composition of the present invention onto a substrate.

[0498] Any type of substrate can be used to spray the curable composition. Suitable substrates are detailed above.

[0499] The curable composition can be ejected by one or more print heads, and small droplets can be sprayed in a controlled manner through a nozzle onto a substrate moving relative to the print head.

[0500] The print head can be either a piezoelectric head or a continuous print head.

[0501] The inkjet printing process can be carried out in single-pass or multi-pass printing mode.

[0502] The inkjet printing process may further include a UV curing process. In inkjet printing, a UV curing device can be positioned in conjunction with the print head of the inkjet printer and move with it so that the liquid UV-curable inkjet ink is exposed to curing radiation immediately after it is ejected.

[0503] In a particularly preferred embodiment, the UV curing process is performed using a UV LED light source.

[0504] To accelerate curing, an inkjet printer may include one or more oxygen-deficient units. The oxygen-deficient units position a blanket of nitrogen or another relatively inert gas (e.g., CO2) while adjusting its position and inert gas concentration to reduce the oxygen concentration in the curing environment.

[0505] Nail coating process The process of coating a nail according to the present invention includes the steps of applying the curable composition of the present invention to the nail and curing the composition on the nail.

[0506] use The self-crosslinking urethane (meth)acrylate of the present invention can be used to obtain cured products with reduced extractant content. In particular, the cured products may be coatings (especially scratch-resistant wood coatings, concrete coatings, or plastic coatings), inks, varnishes, encapsulation or embedding materials, 3D printed articles, molded articles, sealants, adhesives, nail polish, or dental materials.

[0507] The reduction in the amount of extract can be evaluated in comparison to cured products obtained with conventional photopolymerization initiators.

[0508] The extract can be any component that migrates from the cured product. In particular, the extract may be a photopolymerization initiator or its residue.

[0509] Inkjet ink migration can occur in various ways: - Penetration migration - Transfer of print to the back side through the substrate. - Set-off transition - The transition from the printed side to the reverse side of the substrate while it is stacked or stored in a roll. - Gas phase transfer - Evaporation of volatile compounds during heating. - Concentration Extraction - Concentration of important compounds during cooking or sterilization.

[0510] The amount of extract can be quantitatively measured using appropriate analytical methods such as liquid chromatography-mass spectrometry (LC-MS). For example, the curable composition can be coated onto a glass substrate to a thickness of 12 μm and crosslinked using a UV Hg lamp. The resulting cured film is removed from the glass plate, weighed, and then immersed in a solvent such as acetonitrile or dichloromethane. Finally, the liquid is evaporated, and the residue corresponding to the extract is weighed to determine the amount of uncured (not trapped within the photocuring network) product.

[0511] Subsequently, analytical methods such as nuclear magnetic resonance (NMR), liquid chromatography-mass spectrometry (LC-MS), and gas chromatography-mass spectrometry (GC-MS) can be used to identify the properties of the extract and purify the corresponding content.

[0512] In particular, the cured product may contain extracts of less than 5% by weight, less than 2% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.25% by weight, or less than 0.1% by weight, based on the weight of the cured product.

[0513] The curable compositions of the present invention can be used to obtain coatings, inks, varnishes, encapsulation or embedding materials, 3D printed articles, molded articles, sealants, adhesives, nail polish, or dental materials.

[0514] Within this specification, embodiments are described in a manner that enables a clear and concise description; however, embodiments are intended and understood to be combined and separated in various ways without departing from the present invention. For example, it will be understood that all preferred features described herein are applicable to all embodiments of the present invention described herein.

[0515] Although the present invention is illustrated and described herein with reference to specific embodiments, the present invention is not intended to be limited to the illustrated details. Rather, various modifications can be made in detail without departing from the present invention, within the scope of the claims and equivalents.

[0516] The present invention will be described in more detail with reference to the following examples, but it should be understood that the present invention is not limited thereto. [Examples]

[0517] method: Optical DSC: Optical DSC was performed using a TA Instruments Q800 DSC equipped with photo accessories. The sample was illuminated with Hg arc-based light output via a liquid silica glass optical light guide. The light intensity at the sample was approximately 290 mW / cm² as measured by EIT Power Puck II. 2 The samples were typically irradiated for 3–4 minutes until polymerization exothermic reaction was complete. The time from initial irradiance to peak exothermic reaction rate was measured and reported as the time from start to peak. Polymerization enthalpy was measured as the area under the total polymerization curve. To observe the effect of atmosphere on polymerization behavior, samples were UV-cured under a nitrogen stream and under atmospheric pressure.

[0518] NCO titration: Isocyanate titration was performed colorimetrically by reacting the resin with an excess amine in the form of a 0.2N toluene solution of dibutylamine. Next, isopropyl alcohol and bromocresol green indicator were added, and the excess amine was back-titrated with 0.1N HCl until the yellow endpoint was reached.

[0519] Example 1: Self-crosslinking urethane (meth)acrylate according to the present invention The self-crosslinking urethane (meth)acrylate of Example 1 was prepared as follows using the reagents in the amounts shown in Table 1 below. In a 500 mL brown bottle, caprolactone acrylate (SR495B, Sartomer Americas) was combined with a hydroxyl-functionalized photoinitiator of formula (XXe12) shown below (available from Arkema as SpeedCure® 9001) and placed in an 80°C oven until all of the photoinitiator was dissolved. To this solution, butylated hydroxytoluene (BHT) as an antioxidant, dibutyltin dilaurate catalyst (DBTDL), and isophorone diisocyanate (IPDI) were added in the amounts shown in Table 1. The reactants were thoroughly mixed, slightly exothermic, and then placed in an 80°C oven to complete the reaction. The isocyanate value (NCO wt%) was tested by titration until it stopped at approximately 3.6 wt%. SR495B was added to the reactor (part 2), and the reaction mixture was placed again in an 80°C oven for several hours, at which point the NCO value reached less than 0.1% by weight. Table 1: Example 1 Reagent addition amount TIFF2026518308000072.tif47170* The photoinitiator (XXe12) is given by the following formula: This corresponds to TIFF2026518308000073.tif32170.

[0520] Example 2: Self-crosslinking urethane (meth)acrylate according to the present invention The self-crosslinkable urethane (meth)acrylate of Example 2 was prepared in the same manner as in Example 1, except that dicyclohexylmethane-4,4'-diisocyanate (Desmodur W, Covestro) was used as the diisocyanate component and the amount of reagents was adjusted as shown below in Table 2. Table 2: Example 2 Reagent Loading TIFF2026518308000074.tif47170

[0521] Example 3: Self-crosslinking urethane (meth)acrylate according to the present invention The self-crosslinkable urethane (meth)acrylate of Example 3 was prepared in the same manner as in Example 1, except that dicyclohexylmethane-4,4'-diisocyanate (Desmodur W, Covestro) was used as the diisocyanate component and the amount of reagents was adjusted as shown below in Table 3. Table 3: Amount of reagent added in Example 3 The reaction scheme for Example 3 is shown below. (TIFF2026518308000075.tif47170) TIFF2026518308000076.tif59170

[0522] Example 4: Self-crosslinking urethane (meth)acrylate according to the present invention The self-crosslinkable urethane (meth)acrylate for Example 4 was prepared in the same manner as in Example 1, except that the amount of reagent was adjusted as shown below in Table 4. Table 4: Example 4 Amount of reagent added TIFF2026518308000077.tif46170

[0523] Example 5: Self-crosslinking urethane (meth)acrylate according to the present invention A hydroxyl-functionalized photoinitiator of formula (XXe1) was prepared by the reaction of 2-carboxymethylthioxanthone with 1,4-butanediol diglycidyl ether. Details of the preparation of this chromophore-supported component are disclosed in Japanese Patent Application EP23305849.4, filed on 30 May 2023, which is incorporated herein by reference for all purposes. TIFF2026518308000078.tif65170

[0524] First, a hydroxyl-functionalized photoinitiator of formula (XXe1) was prepared by mixing 2-carboxymethylthioxanthone (Arkema CMTX, 31.8 g, 0.1054 mol), 1,4-butanediol diglycidyl ether (CVC GE-21, 15 g, 0.1289 mol), benzyltriethylammonium chloride (Aldrich BTEAC, 0.14 g, 0.3 wt%) as a catalyst, and 50 wt% cyclopentanone as a process solvent in a three-necked flask equipped with a mechanical stirrer under a nitrogen atmosphere and heating to 125°C. The reaction was then carried out at 125°C until a stopping criterion was reached after approximately 3 hours: acid value (AV) < 2 mg KOH / gm and epoxy value (EV) < 2 mg KOH / gm. The AV or EV was adjusted as needed by adding 2-carboxymethylthioxanthone or 1,4-butanediol diglycidyl ether as the reaction progressed. The hydroxyl-functionalized photoinitiator of formula (XXe1) is a liquid and is acceptable for FT-IR and 1 The 1H NMR spectral characteristics are shown.

[0525] Subsequently, the self-crosslinkable urethane (meth)acrylate of Example 5 was prepared as follows using the amounts of reagents shown in Table 5 below. SR495B (Part 1), the photoinitiator of formula (XXe1) pre-dissolved in cyclopentanone, BHT, and dicyclohexylmethane-4,4'-diisocyanate (Desmodur® W, Covestro) were mixed in a 1 / 2 liter resin kettle equipped with an air sparge, stirrer, thermocouple, temperature control device, heating mantle, side arms, and condenser. After stirring the mixture for 10 minutes, DBTDL was added. Heat was added as needed to allow the exothermic reaction to reach 75°C. The reaction mixture was held at 75°C for 1 hour. The intermediate isocyanate (NCO) level was checked until it reached 4.5% by weight (4.4-4.8% by weight) or stopped. SR495B (Part 2) was added. The mixture was stirred at 85°C until the NCO% by weight was below 0.1% by weight. SR495B (Part 3) and / or (Part 4) were added as needed to achieve the desired NCO value of less than 0.1% by weight. Table 5: Example 5 Reagent Loading TIFF2026518308000079.tif61170* The photoinitiator (XXe1) contains 50% by weight of cyclopentanone, and its titration hydroxyl value is 69.1 mg KOH / gm.

[0526] The reaction scheme for Example 5 is shown below. TIFF2026518308000080.tif59170

[0527] Example 6: Self-crosslinking urethane (meth)acrylate according to the present invention The self-crosslinkable urethane (meth)acrylate of Example 6 was prepared according to the procedure of Example 5, except that the diisocyanate was isophorone diisocyanate (IPDI, Wanhua) and the amount of reagent was adjusted as shown below in Table 6. Table 6: Amount of reagent added in Example 6 TIFF2026518308000081.tif56170* The photoinitiator (XXe1) contains 50% by weight of cyclopentanone, and its titration hydroxyl value is 69.1 mg KOH / gm.

[0528] Example 7: Self-crosslinking urethane (meth)acrylate according to the present invention The self-crosslinkable urethane (meth)acrylate of Example 7 was prepared as follows using the amounts of reagents shown in Table 7 below. Irganox® 1035 antioxidant, BHT antioxidant, DBTDL catalyst, and IPDI were mixed in a 0.5-liter resin kettle equipped with an air sparge, stirrer, thermocouple, temperature control device, heating mantle, side arms, and condenser. 2-Hydroxyethyl acrylate (HEA) was added to the resin kettle through an addition funnel over 2 hours. The reaction mixture was heated to 60°C. After holding the mixture at 60°C for 30 minutes, the NCO% by weight was measured and confirmed to be approximately 8.5-8.9% by weight (8.7% by weight). Next, the hydroxyl-functionalized photoinitiator (XXe1) and molten poly(neopentyl glycol adipate) (Chemtura's Fomrez® 55-225-polyesterdiol) with an MW of 500 g / mol were pre-mixed in a weight ratio of 1:1. The premixture was added to the reactor over several minutes, and the mixture was heated to 80°C. The reaction temperature was maintained at approximately 80°C, with heating as needed. The remaining molten Fomrez® 55-225 was added in three portions at 15-minute intervals. The reaction mixture was brought to 90°C, with heating as needed. The reaction mixture was held until the NCO% by weight was less than 0.06. Table 7: Example 7 Reagent addition amount TIFF2026518308000082.tif51170* The photoinitiator (XXe1) contains 50% by weight of cyclopentanone, and its titration hydroxyl value is 69.1 mg KOH / gm.

[0529] Example 8: Self-crosslinking urethane (meth)acrylate according to the present invention The self-crosslinkable urethane (meth)acrylate of Example 8 was prepared as follows using the amounts of reagents shown in Table 8 below. Triphenyl antimony (TPA), methylhydroquinone (MeHQ), DBTDL (catalyst), and IPDI were mixed in a 1 / 2 liter resin kettle equipped with an air sparge, stirrer, thermocouple, temperature control device, heating mantle, side arms, and condenser. 2-Hydroxyethyl acrylate (HEA) was added to the reaction mixture over 2 hours through an addition funnel. The reaction mixture was heated to 60°C. The reaction mixture was held at 60°C for 30 minutes. The weight percentage of NCO was confirmed by titration to be approximately 12.4% (desirable range is 12.0-12.8%). Next, a hydroxyl-functionalized photoinitiator (XXe1) and pre-molten poly(tetrahydrofuran) (PolyTHF 650-polyetherdiol from BASF) were pre-mixed in a weight ratio of 1:2 and added to the reactor. The reaction mixture was heated to 75°C, and then further heat was added as needed. The remaining PolyTHF 650 was added in three portions at 15-minute intervals. The mixture was heated to 80°C, and further heat was added as needed. The reaction mixture was maintained at 80°C until it was confirmed that the NCO% by weight was less than 0.06% by weight. Table 8: Example 8 Reagent Loading TIFF2026518308000083.tif66170* The photoinitiator (XXe1) contains 50% by weight of cyclopentanone, and its titration hydroxyl value is 69.1 mg KOH / gm.

[0530] Example 9: Investigation of UV-curing gel content of self-crosslinking urethane (meth)acrylates from Examples 5-8 The self-crosslinkable urethane (meth)acrylates of Examples 5-8 were coated onto an aluminum substrate using a drawdown bar to produce films with a nominal thickness of 50 μm. No individual photopolymerization initiators were added to the coated film material. The films were exposed to a Fusion H bulb (300 W / in, irradiation dose approximately 1 JUVA / cm²). 2 ) or 8W / cm 2The film was UV-cured using a 395nm LED. The film was removed from the substrate, weighed, and immersed in THF for >24 hours. The remaining solid was separated, dried at 65°C for 4 hours, weighed again, and the gel content was calculated.

[0531] All self-crosslinkable urethane (meth)acrylates exhibited high inherent reactivity, as evidenced by the high gel content shown in Table 9 below. The high gel content observed using a 395 nm LED exemplifies the excellent activity of the resin at long wavelengths typical of general industrial LED light sources. This study exemplifies that the self-crosslinkable urethane (meth)acrylates of the present invention can efficiently perform both the roles of photoinitiator and curable oligomer. Furthermore, this example demonstrates that the hydrogen donor functionality required for type II photoinitiation can be supplied from the resin backbone itself, and that it is not necessary to add amine synergies or other H donors to obtain efficient curing. Table 9: Gel content of self-crosslinking urethane (meth)acrylate in Examples 5-8 TIFF2026518308000084.tif31170

[0532] Example 10: Curable composition containing the self-crosslinking urethane (meth)acrylate of Examples 5-8 The self-crosslinkable urethane (meth)acrylates of Examples 5-8 were blended with SR355 (di(trimethylolpropane)tetraacrylate, Arkema) in a 1:1 weight ratio. No photoinitiators were added. These 100% solid-liquid formulations containing the self-crosslinkable urethane (meth)acrylates of Examples 5-8 were coated onto an aluminum substrate using a drawdown bar to produce a film with a nominal thickness of 50 μm. The film was exposed to a Fusion H bulb (300 W / in, UVA / cm² irradiation dose of approximately 1 J). 2 ) or 8W / cm 2 The film was UV-cured using a 395nm LED. After removing the cured film from the substrate and weighing it, the uncrosslinked material was dissolved by immersion in THF for at least 24 hours. The remaining solid was isolated, dried at 65°C for 4 hours, and then weighed again to calculate the gel content.

[0533] All curable compositions, including the self-crosslinkable urethane (meth)acrylate of the present invention, exhibited high intrinsic reactivity, as indicated by the high gel content shown in Table 10 below. The high gel content observed using a 395 nm LED exemplifies the excellent activity of the resin at long wavelengths typical of common industrial LED light sources. This investigation of gel content demonstrated that the self-crosslinkable urethane (meth)acrylate of the present invention, in addition to being inherently curable, can efficiently function as a photoinitiator for other radical-curable materials. As described in Example 9, the efficient curing obtained indicates that, when using the self-crosslinkable urethane (meth)acrylate of the present invention, no additional hydrogen donors or synergists are required to obtain excellent UV curability. Table 10: Gel content when self-crosslinkable urethane (meth)acrylate and SR355 are combined in a 1:1 weight ratio in Examples 5-8. TIFF2026518308000085.tif31170

[0534] Example 11: Curing speed of self-crosslinking urethane (meth)acrylates from Examples 5-8 as investigated by photoDSC The resins and compositions used in the gel content investigations of Examples 9 and 10 were analyzed by differential scanning calorimetry (optical DSC) to investigate the basic curing rate, indicated by the exothermic time from start to peak. This value of time from start to peak corresponds to the time it takes for polymerization to reach its peak reaction rate after the sample is irradiated with the selected light source.

[0535] Samples of the self-crosslinkable urethane (meth)acrylates from Examples 5-8, and samples of curable compositions containing the self-crosslinkable urethane (meth)acrylates from Examples 5-8 and SR355 (di(trimethylolpropane)tetraacrylate) in a 1:1 weight ratio, were investigated in the same manner as in Examples 9 and 10. The samples were examined under an Hg-arc light source (UVA intensity approximately 280 mW / cm²). 2 ) or 405nm LED light source (intensity approximately 280mW / cm²) 2The material was irradiated with SR355. For the blend with SR355, curing was investigated in both air and nitrogen environments. The results are summarized in Table 11 and plotted in Figure 1 below. Table 11: Photo-DSC results for the self-crosslinking urethane (meth)acrylates of Examples 5-8, both as themselves and as a 1:1 weight ratio blend with SR355. TIFF2026518308000086.tif198170

[0536] The results above demonstrate that the self-crosslinking urethane (meth)acrylate of the present invention exhibits excellent curing rates, both alone and when diluted with other photocurable compounds, without the addition of any other photoinitiator. Notably, no auxiliary curing agents, such as amine synergies, were required. This offers the advantage of reduced or zero extractability by adding another low molecular weight photoinitiator or another small molecule extractable hydrogen source.

[0537] Example 12: Self-crosslinking urethane (meth)acrylate according to the present invention A hydroxyl-functionalized photoinitiator of formula (XXe9) was prepared by reaction of 2-carboxymethylthioxanthone with trimethylolpropane triglycidyl ether. Details of the preparation of this hydroxyl-functionalized photoinitiator are disclosed in patent application EP23305849.4, filed on 30 May 2023, which is incorporated herein by reference for all purposes. TIFF2026518308000087.tif77170

[0538] First, a hydroxyl-functionalized photoinitiator of formula (XXe9) was prepared by mixing 2-carboxymethylthioxanthone (Arkema CMTX, 35.2 g, 0.1167 mol), trimethylolpropane triglycidyl ether (CVC GE-30, 18.7 g, 0.136 mol), benzyltriethylammonium chloride (Aldrich BTEAC, 0.14 g, 0.26 wt%) as a catalyst, and cyclopentanone (54 g) as a process solvent in a three-necked flask equipped with a mechanical stirrer under a nitrogen atmosphere and heating to 130°C. The reaction was then carried out at 130°C until the stopping criteria of acid value (AV) < 2 mg KOH / gm and epoxy value (EV) < 2 mg KOH / gm (after 3 hours) were reached. AV or EV was adjusted as needed by adding 2-carboxymethylthioxanthone or trimethylolpropane triglycidyl ether depending on the progress of the reaction. The final product is expected to be FT-IR and 1 The liquid exhibited 1H NMR spectral characteristics.

[0539] Subsequently, the self-crosslinkable urethane (meth)acrylate of Example 12 was prepared as follows: SR495B (106.65 g, 0.3161 mol), photoinitiator of formula (XXe9) (50% solids solution in cyclopentanone, 19.6 g solution, 0.026 mol), BHT (0.19 g), and dicyclohexylmethane-4,4'-diisocyanate (Desmodur® W, Covestro) (66.7 g, 0.51 mol NCO) were packed into a 1-liter lidded plastic kettle equipped with an air sparge, stirrer, thermocouple, internal temperature control device, and condenser. After stirring the mixture for 10 minutes, dibutyltin dilaurate (DBTDL) was added to the reactor (0.16 g). Stirring was continued, and the reaction was exothermic, reaching an internal temperature of 75°C. The reaction was heated to maintain an internal temperature of 75°C for 1 hour. Titration of NCO revealed 3.6% NCO. The SR495B was refilled (50.61g, 0.15mol) and heated to 85°C until the NCO content of the reactant was less than 0.1 wt.%. The reaction contents were discharged, and FT-IR and GPC (M) were performed. n Approximately 1080, M wApproximately 1458) showed properties consistent with the expected product.

[0540] Example 13: Self-crosslinking urethane (meth)acrylate according to the present invention Amino-functionalized self-crosslinkable urethane (meth)acrylate was prepared as follows using the reagents shown in Table 12 below. SR495B (Part 1), a photoinitiator of formula (XXe1) pre-dissolved in cyclopentanone, N-methyldiethanolamine, BHT, and dicyclohexylmethane-4,4'-diisocyanate (Desmodur® W, Covestro) were mixed in a 1 / 2 liter resin kettle equipped with an air sparge, stirrer, thermocouple, temperature control device, heating mantle, side arms, and condenser. After stirring the mixture for 10 minutes, DBTDL was added. Heat was added as needed to allow the exothermic reaction to reach 75°C. The reaction mixture was held at 75°C for 1 hour. The mixture was stirred at 75°C until the NCO% by weight was less than 0.1% by weight, as determined by FT-IR analysis. The NCO% by weight was measured at 2260 cm⁻¹ based on an external standard calibration curve. -1 The NCO peak height was calculated. SR495B was added as needed to reach the NCO cessation criterion of <0.1 wt%NCO. Table 12: Example 13 Reagent addition amount: TIFF2026518308000088.tif62170* The photoinitiator (XXe1) contains 50% by weight of cyclopentanone, and its titration hydroxyl value is 69.1 mg KOH / gm.

[0541] Example 14: Investigation of UV-curing gel content of the self-crosslinking urethane (meth)acrylate from Example 13 Using gel content analysis, the reactivity of the amino-functionalized self-crosslinkable urethane (meth)acrylate of Example 13 was compared to that of the analogue of Example 5, which lacks a tertiary amine functional group. Samples of the self-crosslinkable urethane (meth)acrylates themselves from Examples 5 and 13, and samples of curable compositions containing the self-crosslinkable urethane (meth)acrylates from Examples 5 and 13 combined with SR355 (di(trimethylolpropane)tetraacrylate) in a 1:1 weight ratio, were investigated in the same manner as in Examples 9 and 10. The gel content results are shown in Table 13 below. While the amine synergistic agent bonded to the polymer is not necessarily required to induce the intrinsic reactivity, in such cases, the presence of the amine synergistic functional group on the oligomer skeleton promotes faster and broader UV curing. Table 13. Comparison of gel content illustrating the use of polymer-bonded tertiary amine synergistic effects on reactivity. TIFF2026518308000089.tif31170

[0542] Example 15: Self-crosslinking urethane (meth)acrylate according to the present invention A hydroxyl-functionalized photoinitiator of formula (XXe15) was prepared by esterifying 2-carboxymethylthioxanthone and then reacting the resulting methyl ester with diethanolamine. TIFF2026518308000090.tif79170

[0543] First, 2-carboxymethylthioxanthone (130.4 g; 455.5 mmol) was suspended in methanol (1250 mL), and a hydroxyl-functionalized photoinitiator of formula (XXe15) was prepared by dropwise addition of 98 wt% sulfuric acid (20 g). The mixture was heated to reflux with stirring for 8 hours. The reaction product was cooled to 20°C and analyzed by TLC (petroleum ether-AcOEt 1:1) to confirm almost complete conversion to the methyl ester. Sodium acetate (30.0 g) was added, and the mixture was stirred for 30 minutes. The resulting suspension was then partially evaporated until a concentrated mass (459.6 g) was obtained. Water (1250 mL) was added, the suspension was stirred, and then filtered. The crude solid product was then suspended in water (750 mL), and saturated NaHCO3 solution (105 mL) was added. The mixture was stirred for 20 minutes, the solid was filtered, and washed with water (400 mL). The solid product was dried in a vacuum at 50°C. This yielded methyl[(9-oxo-9H-thioxanthene-2-yl)oxy]acetate (131.8 g; 96% of the theoretical value) as a powder.

[0544] Methyl [(9-oxo-9H-thioxanthene-2-yl)oxy]acetate (131.2 g; 436.9 mmol), diethanolamine (161.5 g; 1.53 mol), and methanol (50 mL) were combined in a reaction flask purged with nitrogen. The reaction mixture was homogenized and heated under reflux (105-110°C) for 3 hours. The resulting dark orange mass was analyzed by TLC (dichloromethane-methanol 10:1) to confirm that the methyl ester had been completely converted. The reaction mass was poured into water (1000 mL), the resulting suspension was vigorously stirred for 30 minutes, and then filtered. The resulting crystalline product was suspended in water (150 mL), vigorously stirred for 1 hour, and then filtered. The isolated crystalline product was washed with water (100 mL) and dried under vacuum at 50°C. This yielded a hydroxyl-functionalized photoinitiator of formula (XXe15) (146.5 g; 90% of the theoretical value) as a crystalline solid with a melting point of 152-154°C and a purity (HPLC area) of 98.5%.

[0545] Subsequently, the self-crosslinkable urethane (meth)acrylate of Example 15 was prepared as follows using the amounts of reagents detailed in Table 14. SR495B (Part 1), the hydroxyl-functionalized photoinitiator of formula (XXe15), BHT, and dicyclohexylmethane-4,4'-diisocyanate (Desmodur® W, Covestro) were mixed in a 500 mL resin kettle equipped with an air sparge, stirrer, thermocouple, temperature control device, heating mantle, side arms, and condenser. After stirring the mixture for 10 minutes, DBTDL was added. The reaction was exothermic, reaching 110°C, and the internal temperature was maintained at approximately 110°C, with heating as needed. After all of the hydroxyl-functionalized photoinitiator of formula (XXe15) had disappeared, the reaction mixture was held at 110°C for 1 hour. The intermediate isocyanate (NCO) level was checked until it fell below 3.2% by weight or stopped. SR495B (Part 2) was added. The mixture was stirred at 110°C until the NCO% by weight was less than 0.1% by weight. Table 14: Example 15 Amount of reagent added TIFF2026518308000091.tif47170

[0546] Example 16: Self-crosslinking urethane (meth)acrylate according to the present invention The self-crosslinkable urethane (meth)acrylate of Example 16 was prepared in the same manner as in Example 15, except that isophorone diisocyanate (IPDI, Wanhua) was used as the diisocyanate component and the amount of reagent was adjusted as shown below in Table 15. Table 15: Amount of reagent added in Example 16. TIFF2026518308000092.tif47170

[0547] Example 17: Self-crosslinking urethane (meth)acrylate according to the present invention The self-crosslinkable urethane (meth)acrylate of Example 17 was prepared as follows using the amounts of reagents shown in Table 16 below. Pre-molten Fomrez® 55-225 (Chemtura polyester diol), the hydroxyl-functionalized photoinitiator of formula (XXe15) synthesized in Example 15, and IPDI were mixed in a 500 mL resin kettle equipped with a nitrogen sparge, stirrer, thermocouple, temperature control device, heating mantle, side arms, and condenser. After stirring the mixture for 10 minutes, Reaxis® C716 (bismuth neodecanoate) catalyst was added. The reaction was heated to 130°C, with additional heat added as needed. After all the photoinitiator had disappeared, the reaction mixture was held at 130°C for 1 hour. The level of intermediate isocyanate (NCO) was checked until it fell below 12.8% by weight or remained unchanged for 30 minutes. The mixture was cooled to 90°C. Irganox® 1035 antioxidant was added, and the nitrogen sparge was switched to an air sparge. 2-Hydroxyethyl acrylate (HEA) was supplied to the resin kettle over 1 hour through an addition funnel. The reaction mixture was heated to 95°C and maintained at 95°C until the NCO% by weight was less than 0.1%. Table 16: Example 17 Reagent addition amount TIFF2026518308000093.tif42170

[0548] Example 18: Self-crosslinking urethane (meth)acrylate according to the present invention The self-crosslinkable urethane (meth)acrylate of Example 18 was prepared as follows using the amounts of reagents shown in Table 17 below. Pre-molten poly(tetrahydrofuran) (PolyTHF 650, BASF, polyetherdiol), the hydroxyl-functionalized photoinitiator of formula (XXe15) synthesized in Example 15, and IPDI were mixed in a 500 mL resin kettle equipped with a nitrogen sparge, stirrer, thermocouple, temperature control device, heating mantle, side arms, and condenser. After stirring the mixture for 10 minutes, the Reaxis® C716 (bismuth neodecanoate) catalyst was added. The exothermic temperature was increased to 130°C, and heat was added as needed. After all the photoinitiator had disappeared, the reaction mixture was held at 130°C for 1 hour. The level of intermediate isocyanate (NCO) was monitored until it fell to less than 8.1% by weight or remained constant for 30 minutes. The mixture was cooled to 90°C. Irganox® 1035 antioxidant was added, and the nitrogen sparge was switched to an air sparge. 2-Hydroxyethyl acrylate (HEA) was supplied to the resin kettle over 1 hour through an addition funnel. The reaction mixture was heated to 95°C and maintained at 95°C until the NCO% by weight was less than 0.1%. Table 17: Example 18 Reagent Loading TIFF2026518308000094.tif47170

[0549] Example 19: Investigation of UV-curing gel content of self-crosslinking urethane (meth)acrylates from Examples 15-16 The self-crosslinkable urethane (meth)acrylates of Examples 15-16 were coated onto an aluminum substrate using a drawdown bar to produce a film with a nominal thickness of 50 μm. No individual photopolymerization initiators were added to the coated film material. The film was exposed to a Fusion H bulb (300 W / in, irradiation dose approximately 1 JUVA / cm²). 2 ) or 8W / cm 2 The film was UV-cured using a 395nm LED. The film was removed from the substrate, weighed, and immersed in THF for >24 hours. The remaining solid was separated, dried at 65°C for 4 hours, weighed again, and the gel content was calculated.

[0550] Both self-crosslinkable urethane (meth)acrylates exhibited unique reactivity, as judged from the gel content shown in Table 18 below. This study illustrates that the self-crosslinkable urethane (meth)acrylates of the present invention can efficiently perform both the roles of photoinitiator and curable oligomer. The examples also demonstrate that the hydrogen donor functionality required for type II photoinitiation can be supplied from the resin backbone itself. Table 18: Gel content of self-crosslinking urethane (meth)acrylate in Examples 15-16 TIFF2026518308000095.tif21170

[0551] Example 20: Curable composition containing the self-crosslinking urethane (meth)acrylate of Examples 15-16 The self-crosslinkable urethane (meth)acrylates of Examples 15-16 were blended with SR355 (di(trimethylolpropane)tetraacrylate, Sartomer) in a 1:1 weight ratio. No photoinitiator was added. These 100% solid-liquid formulations containing the self-crosslinkable urethane (meth)acrylates of Examples 15-16 were coated onto an aluminum substrate using a drawdown bar to produce a film with a nominal thickness of 50 μm. The film was exposed to a Fusion H bulb (300 W / in, UVA / cm² irradiation dose of approximately 1 J). 2 ) or 8W / cm 2 The film was UV-cured using a 395nm LED. After removing the cured film from the substrate and weighing it, the uncrosslinked material was dissolved by immersion in THF for at least 24 hours. The remaining solid was isolated, dried at 65°C for 4 hours, and then weighed again to calculate the gel content.

[0552] All curable formulations of the present invention, including the self-crosslinkable urethane (meth)acrylate, exhibited high intrinsic reactivity, as indicated by the high gel content shown in Table 19 below. The high gel content observed using a 395 nm LED exemplifies the excellent activity of the resin at long wavelengths typical of common industrial LED light sources. This investigation of gel content demonstrated that the self-crosslinkable urethane (meth)acrylate of the present invention, in addition to being inherently curable, can efficiently function as a photoinitiator for other radical-curable materials. As described in Example 19, the efficient curing obtained indicates that, when using the self-crosslinkable urethane (meth)acrylate of the present invention, no additional hydrogen donors or synergists are required to obtain excellent UV curability. Table 19: Gel content when self-crosslinkable urethane (meth)acrylate and SR355 are combined in a 1:1 weight ratio in Examples 15-16. TIFF2026518308000096.tif21170

[0553] Example 21: Self-crosslinking urethane (meth)acrylate according to the present invention The self-crosslinkable urethane (meth)acrylate of Example 21 was prepared as follows using the amounts of reagents shown in Table 20 below. SR495B (Part 1), a hydroxyl-functionalized photoinitiator of formula (XXf5) shown below (available from Aldrich), BHT, and isophorone diisocyanate (IPDI) were mixed in a 1 / 2 liter resin kettle equipped with an air sparge, stirrer, thermocouple, temperature control device, and heating mantle. After stirring the mixture for 10 minutes, DBTDL was added. Heat was added as needed to allow the exothermic reaction to reach 100°C. The reaction mixture was held at 100°C for 4 hours. The intermediate isocyanate (NCO) level was checked until it reached 2.8% by weight or stopped. SR495B (Part 2) was added. The mixture was stirred at 100°C until the NCO% by weight was below 0.1% by weight. Table 20: Example 21 Amount of reagent added TIFF2026518308000097.tif47170* The photoinitiator (XXf5) is given by the following formula: This corresponds to TIFF2026518308000098.tif23170.

[0554] Example 22: Self-crosslinking urethane (meth)acrylate according to the present invention The self-crosslinkable urethane (meth)acrylate of Example 22 was prepared as follows using the amounts of reagents shown in Table 21 below. Pre-molten poly(tetrahydrofuran) (PolyTHF 650, BASF, polyetherdiol), the hydroxyl-functionalized photoinitiator of formula (XXf5), and IPDI were mixed in a 500 mL resin kettle equipped with a stirrer, thermocouple, temperature control device, and heating mantle. After stirring the mixture for 10 minutes, the Reaxis C716 (bismuth neodecanoate) catalyst was added. The exothermic temperature was increased to 95°C, and heat was added as needed. The reaction mixture was held at 95°C for 1 hour. The level of intermediate isocyanate (NCO) was monitored until it fell below 8.2% by weight or remained constant for 30 minutes. The mixture was cooled to 80°C. The Irganox 1035 antioxidant was added, and an air sparge was applied. 2-hydroxyethyl acrylate (HEA) was supplied into the resin kettle through an addition funnel over 30 minutes. The reaction mixture was heated to 95°C and maintained at 95°C until the NCO weight percentage was less than 0.1%. Table 21: Example 22 Amount of reagent added TIFF2026518308000099.tif42170

[0555] Example 23: Self-crosslinking urethane (meth)acrylate according to the present invention The self-crosslinkable urethane (meth)acrylate of Example 23 was prepared as follows using the amounts of reagents shown in Table 22 below. SR495B (Part 1), the hydroxyl-functionalized photoinitiator of formula (XXf5), Irganox 1035 (BASF), and isophorone diisocyanate (IPDI) were mixed in a 1 / 2 liter resin kettle equipped with an air sparge, stirrer, thermocouple, temperature control device, and heating mantle. After stirring the mixture for 10 minutes, Reaxis C716 (bismuth catalyst, Reaxis) was added. Heat was added as needed to ensure that the exothermic reaction reached 70°C. The reaction mixture was held at 70°C for 4 hours, after which residual hydroxyl-functionalized photoinitiator <10 ppm was sampled by HPLC. The intermediate isocyanate (NCO) level was also checked until it reached 3.5% by weight or stopped. Methyldiethanolamine (Aldrich) was added, and the mixture was stirred at 70°C for 30 minutes. The mixture was cooled to 50°C. SR495B (Part 2) was added to the mixture to induce a reaction at 70°C. The mixture was stirred at 70°C until the NCO content fell below 0.1% by weight. Table 22: Amount of reagent added in Example 23 TIFF2026518308000100.tif52170

[0556] Example 24: Self-crosslinking urethane (meth)acrylate according to the present invention The self-crosslinkable urethane (meth)acrylate of Example 24 was prepared as follows using the amounts of reagents shown in Table 23 below. Pre-molten poly(tetrahydrofuran) (PolyTHF 650, BASF, polyetherdiol), the hydroxyl-functionalized photoinitiator of formula (XXf5), and IPDI were mixed in a 500 mL resin kettle equipped with a stirrer, thermocouple, temperature control device, and heating mantle. After stirring the mixture for 10 minutes, the Reaxis C716 (bismuth neodecanoate) catalyst was added. The exothermic temperature was increased to 70°C, and heat was added as needed. The reaction mixture was held at 70°C for 2 hours, and then the residual hydroxyl-functionalized photoinitiator of formula (XXf5) was sampled by HPLC for <10 ppm. The level of intermediate isocyanate (NCO) was also monitored until it reached 8.7% by weight or remained constant for 30 minutes. Methyldiethanolamine (Aldrich) was added, and the mixture was stirred at 70°C for 30 minutes. The mixture was cooled to 50°C. Irganox 1035 antioxidant was added, and air sparging was applied. 2-hydroxyethyl acrylate (HEA, manufactured by Nippon Shokubai) was added to the resin kettle through an addition funnel over a period of 30 minutes. The reaction mixture was heated to 70°C and maintained at 70°C while stirring until the NCO% by weight was less than 0.1%. Table 23: Example 24 Amount of reagent added TIFF2026518308000101.tif47170

[0557] Example 25: Self-crosslinking urethane (meth)acrylate according to the present invention Example 25 was prepared as follows, using the reagent addition amounts shown in Table 24. First, 2-carboxymethylthioxanthone (CMTX, Arkema), 1,4-butanediol diglycidyl ether (GE-21, CVC), benzyltriethylammonium chloride (BTEAC, Aldrich) as a catalyst, and pre-molten poly(tetrahydrofuran) (PolyTHF 650, BASF) were mixed in a 500 mL resin kettle equipped with a nitrogen sparge, stirrer, thermocouple, temperature control device, and heating mantle, and heated to 130°C to prepare the hydroxyl-functionalized photoinitiator of formula (XXe1). The reaction was carried out at 130°C until residual CMTX <0.1 wt%, acid value (AV) <0.5 mg KOH / gm, and epoxy value (EV) <2 mg KOH / gm were achieved by HPLC after approximately 8 hours. To keep residual CMTX levels low, 1,4-butanediol diglycidyl ether can be added. The mixture was cooled to 25°C. The hydroxyl-functionalized photoinitiator of formula (XXf5) and IPDI were added with stirring over 10 minutes, followed by the addition of the Reaxis C716 catalyst. The exothermic temperature was increased to 70°C, with additional heat added as needed. The reaction mixture was stirred at 70°C for 2 hours, after which residual hydroxyl-functionalized photoinitiator of formula (XXf5) was sampled by HPLC for <10 ppm. The level of intermediate isocyanate (NCO) was also monitored until it reached 9% by weight or remained constant for 30 minutes. Methyldiethanolamine (Aldrich) was added, and the mixture was stirred at 70°C for 30 minutes. The mixture was cooled to 50°C. The antioxidant Irganox 1035 was added, and the sparge was switched from nitrogen to air. 2-hydroxyethyl acrylate (HEA, manufactured by Nippon Shokubai) was supplied to the resin kettle through an addition funnel over 1 hour. The reaction mixture was heated to 70°C and maintained at 70°C while stirring until the NCO weight percentage was less than 0.1%. Table 24: Example 25 Amount of reagent added TIFF2026518308000102.tif67170

[0558] Example 26: Curing investigation of self-crosslinking urethane (meth)acrylate from Examples 23-25 The self-crosslinkable urethane (meth)acrylates of Examples 23-25 ​​were characterized using the methodologies described in Example 9 (gel content) and Example 11 (photoDSC curing analysis). In these analyses, all oligomers were mixed with SR355 (ditrimethylolpropanetetraacrylate) in a 1:1 weight ratio without the addition of any small molecule photoinitiators. The resins exhibited excellent UV reactivity, as exemplified by their high gel content and good curing rate (short time from initiation to peak). Table 25: Gel content and rate when self-crosslinking urethane (meth)acrylate and SR355 are combined in a 1:1 weight ratio in Examples 23-25 TIFF2026518308000103.tif26170

[0559] Example 27: Self-crosslinking urethane (meth)acrylate according to the present invention Example 27 was prepared as follows, using the reagent addition amounts shown in Table 26. First, SR495B (Part 1), 2-carboxymethylthioxanthone (CMTX, Arkema), 1,4-butanediol diglycidyl ether (GE-21, CVC), benzyltriethylammonium chloride (BTEAC, Aldrich) as a catalyst, Irganox 1035 (BASF), Irgafos 168 (BASF), and 4-methoxyphenol (MeHQ, Aldrich) as an inhibitor were mixed in a 500 mL resin kettle equipped with an air sparge, stirrer, thermocouple, temperature control device, and heating mantle, and heated to 130°C to prepare a hydroxyl-functionalized photoinitiator of formula (XXe1). The reaction was carried out at 130°C until residual CMTX <0.1 wt%, acid value (AV) <0.5 mg KOH / gm, and epoxy value (EV) <3 mg KOH / gm were achieved by HPLC after approximately 8 hours. Further addition of 1,4-butanediol diglycidyl ether may be used to keep residual CMTX levels low. The mixture was cooled to 25°C. The hydroxyl-functionalized photoinitiator of formula (XXf5) and IPDI were added with stirring over 10 minutes, followed by the addition of the Reaxis C716 catalyst. The exothermic temperature was increased to 70°C, with additional heat added as needed. The reaction mixture was stirred at 70°C for 2 hours, after which residual hydroxyl-functionalized photoinitiator of formula (XXf5) was sampled by HPLC for <10 ppm. The level of intermediate isocyanate (NCO) was also monitored until it reached 3 wt% or remained constant for 30 minutes. Methyldiethanolamine (Aldrich) was added, and the mixture was stirred at 70°C for 30 minutes. The mixture was cooled to 50°C. SR495B Part 2 was added to the resin kettle. The reaction mixture was heated to 70°C and maintained at 70°C with stirring until the NCO% by weight was less than 0.1%. If the mixture stopped at NCO% >0.1%, additional SR495B was added. Table 26: Amount of reagent added in Example 27 TIFF2026518308000104.tif82170

[0560] Example 28: Self-crosslinking urethane (meth)acrylate according to the present invention Example 28 was prepared as follows, using the reagent addition amounts shown in Table 27. SR495B (Part 1), the hydroxyl-functionalized photoinitiator of formula (XXf5), Irganox 1035 (BASF), and dicyclohexylmethane 4,4'-diisocyanate (Desmodur® W, Covestro) were mixed in a 1 / 2 liter plastic kettle equipped with an air sparge, stirrer, thermocouple, temperature control device, and heating mantle. After stirring the mixture for 10 minutes, Reaxis C716 (bismuth catalyst, Reaxis) was added. Heat was added as needed to ensure that the exothermic reaction reached 60°C. The reaction mixture was held at 60°C for 11 hours, after which residual hydroxyl-functionalized photoinitiator of formula (XXf5) <10 ppm was sampled by HPLC. Methyldiethanolamine (Aldrich) was added, and the mixture was stirred at 60°C for 1 hour. The intermediate isocyanate (NCO) level was checked until it reached less than 4.9% by weight or stopped. The mixture was cooled to 50°C. SR495B (Part 2) was added to the mixture over 15 minutes, maintaining the temperature at 50°C. The mixture was stirred at 50°C until the NCO% by weight was below 0.2% by weight. Table 27: Amount of reagent added in Example 28 TIFF2026518308000105.tif52170

[0561] Example 29: FT-IR comparison of surface curing and through-curing of compositions containing self-crosslinkable urethane (meth)acrylate according to the present invention The self-crosslinkable urethane (meth)acrylates of Examples 23 and 27 were blended with SR355 (di(trimethylolpropane)tetraacrylate) in a 1:1 weight ratio for investigation. A control formulation was prepared by combining a standard urethane acrylate (UA) oligomer with a similar structure but without a photoinitiator moiety with SR355 in a 1:1 weight ratio, and adding 2 wt% benzophenone as a photoinitiator and 0.5 wt% ethylhexyl-dimethylaminobenzoate (EHA) as an amine synergist. A 2 mil thick blend film was cast onto a metal substrate and cured with a Heraeus LC-6 microwave Hg lamp equipped with a 300 W / inch H bulb. The dose received by the film was 200-1000 mJ / cm². 2 This range varied depending on the line speed of the curing apparatus. After conditioning at 75°F and 55% relative humidity for 24 hours, the film was peeled from the metal substrate and analyzed by placing it directly on the CdSe ATR window of the FT-IR apparatus. Both sides of the cured film were analyzed. The upper side (closest to the H valve) represents surface curing, and the lower side (farthest from the H valve) represents through-curing. 812cm -1 The chemical conversion rate was calculated using the following formula, based on the peak height of the acrylate absorption band. Here, H0 represents the initial peak height, and H represents the peak height after UV irradiation.

[0562] Equation 1. Calculation of chemical transformations using FT-IR: Conversion = 100(H0-H) / H0 Surface and through-curing of three related resin systems were analyzed by FT-IR acrylate conversion. The curing efficiency of the bulk film is shown in Figure 2. As the irradiation dose decreases (line speed increases), the acrylate conversion rate measured by FT-IR also decreases. Compared to a control UA system blended with a small molecule photoinitiator, the self-crosslinkable urethane (meth)acrylate (SC-UA) system according to the present invention exhibits equivalent or superior acrylate conversion rates across the entire dose range. The SC-UA system performed better than the control at 1000 mJ / cm². 2 and 800 mJ / cm 2 The acrylate conversion rate drops significantly between these points, but at 1000 mJ / cm²2 Irradiation improves curing efficiency on both the front and back surfaces. Therefore, synthesizing SC-UA resins in which the photoinitiator is covalently bonded to the oligomer skeleton does not sacrifice the curing efficiency of the bulk film on either the front or bottom surface of the film. Furthermore, no significant differences in acrylate conversion are observed among the various urethane skeletons of SC-UA. In all systems, the acrylate conversion rate on the surface is similar to that on the back surface of a 2-mil thick film. Overall, the self-crosslinkable urethane (meth)acrylate systems of the present invention showed comparable or better curing than standard structure-related benchmark systems with added small molecule type II photoinitiators and amine synergistic systems.

[0563] Comparison of mechanical properties between the self-crosslinking resin of Example 30 and standard urethane acrylate of Example 23. A basic comparison was made between a comparative standard UA cured with the addition of a small molecule photoinitiator and a similar self-reactive urethane acrylate resin (SC-UA) from Example 23 without the addition of a small molecule photoinitiator, using dynamic mechanical analysis (DMA). The only compositional difference between these two oligomers is that the SC-UA of Example 23 contains a polymer-bound benzophenone chromophore, while the comparative standard UA does not. Both resins were cast as self-supporting films approximately 5 mil thick and cured for dynamic mechanical analysis (tensile DMA, frequency 1 Hz) against temperature. The resin of Example 23 was coated and cured without the addition of a small molecule photoinitiator, while 3 wt% TPO was added to the comparative standard UA for UV curing. Thin film tensile DMA plots are shown in Figure 3. The DMA plot for the comparative standard UA is at the top of Figure 3, and the DMA plot for the SC-UA of Example 23 is at the bottom of Figure 3.

[0564] Although there are slight differences in the DMA of the cured films, the basic mechanical properties of the comparative standard UA and the SC-UA of Example 23 are found to be very similar. The presence of polymer-bonded chromophores at the level used in Example 23 has minimal effect on the basic mechanical properties of the oligomer. Both cured materials have a glass storage modulus (E') of 1500-2000 MPa and a rubber modulus of 3-4 MPa. The comparative standard UA has a primary glass transition temperature (T g The Tg (measured by the peak value of the tandelta curve) is approximately 30°C, with the shoulder region at around 50°C, while the self-crosslinking analog of Example 23 has a main Tg of 54°C and the shoulder region at around 40°C. Analysis revealed that although some physical differences in the cured film were expected due to the incorporation of a benzophenone chromophore into the oligomer skeleton of the resin in Example 23, the overall mechanical properties were remarkably similar.

[0565] Within this specification, embodiments are described in a manner that enables a clear and concise description, but the embodiments are intended and understood to be combined and separated in various ways without departing from the invention. For example, it will be understood that all preferred features described herein are applicable to all embodiments of the invention described herein. The foregoing description of various forms of the invention is presented for illustrative and explanatory purposes only and is not intended to exhaustively describe the invention or limit it to the exact forms disclosed. Numerous modifications or variations are possible in light of the above teachings. All such modifications and variations are within the scope of the invention as determined by the appended claims and shall be interpreted in accordance with the breadth that is justly, legally, and equitably granted.

Claims

1. At least one (meth)acrylate functionalized moiety ACR; At least two polyurethane parts UU; At least one chromophore portion Q; Optionally, at least one chain extension portion EXT Self-crosslinking urethane (meth)acrylate, including.

2. The self-crosslinkable urethane (meth)acrylate according to claim 1, wherein each (meth)acrylate-functionalized moiety ACR independently has 1 to 5 (meth)acrylate groups, particularly 1 to 3 (meth)acrylate groups, and more specifically 1 (meth)acrylate group.

3. Each (meth)acrylate functionalization moiety ACR is independently expressed by the following formula (I): [In the formula, R ４ is a (w'+1) valence linker; R ５ is H or methyl; w' is 1 to 5, especially 1 to 3, and more specifically 1. A self-crosslinkable urethane (meth)acrylate according to claim 1 or 2.

4. R ４ The self-crosslinkable urethane (meth)acrylate according to claim 3, wherein the linker is a (w'+1) valence selected from aliphatic or aromatic hydrocarbon linkers, polyether linkers, polyester linkers, polycarbonate linkers, polyorganosiloxane linkers, polydiene linkers, isocyanurate linkers and combinations thereof; in particular, aliphatic or aromatic hydrocarbon linkers, polyether linkers, polyester linkers and combinations thereof; more specifically, alkylene, alkoxylated alkylene, polycaprolactone linkers and combinations thereof.

5. R ４ However, equations (IIa) to (VIa): -(CR ２２ R' ２２ ) ｍ - (--a) -[(CR ２３ R’ ２３ ) ｎ -O] ｏ -(CR ２３ R’ ２３ ) ｎ - (IIIa) -[(CR ２４ R’ ２４ ) ｐ -O] ｑ -(CR ２５ R’ ２５ ) ｒ -[O-(CR ２６ R’ ２６ )p’] ｑ’ - (IVa) -[(CR ２７ R’ ２７ ) ｓ -C(=O)O] ｔ -(CR ２８ R’ ２８ ) ｕ -* (Va) -[(CR ２９ R’ ２９ ) ｖ -O-C(=O)-(CR ３０ R’ ３０ )w-C(=O)-O] ｘ -(CR ２９ R’ ２９ ) ｖ - (VIa) [In the formula, R ２２ , R' ２２ , R ２５ , R' ２５ , R ２９ , R' ２９ , R ３０ and R' ３０ is 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 These are independently H or methyl; m is between 2 and 50; n, p, and p' are independently 2 to 4; o is between 1 and 20; q and q' are independently between 0 and 20, provided that at least one of q and q' is not 0; r is between 2 and 20; s is between 3 and 12; t is between 1 and 20; u is between 2 and 8; v is between 2 and 20; w is between 2 and 30; x is between 1 and 20; The symbol * represents a bond point to the (meth)acrylate group. A divalent linker selected from one of the following, in particular, R ４ These include alkylenes such as 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,12-dodecylene, 1,18-octadecylene, 2-methyl-1,3-propanediyl, 2,2-diethyl-1,3-propanediyl, 3-methyl-1,5-pentanediyl, 3,3-dimethyl-1,5-pentanediyl, 2,2-dimethyl-1,3-propanediyl, and 2,4-diethyl-1,5-pentanediyl; and alkoxylated derivatives of the aforementioned alkylenes. The self-crosslinkable urethane (meth)acrylate according to claim 3 or 4, which is a divalent linker selected from: esterified derivatives of the aforementioned alkylenes; residues of di, tri, tetra, or polyoxyalkylene (without OH groups), such as di, tri, or tetraethylene glycol, di, tri, or tetrapropylene glycol, di, tri, or tetrabutylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, and poly(ethylene glycol-co-propylene glycol); and residues of polyester polyol (without OH groups).

6. The self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 5, wherein the total amount of (meth)acrylate functionalized portion ACR in the self-crosslinkable urethane (meth)acrylate accounts for 5 to 85%, particularly 10 to 80%, and more specifically 15 to 75%, of the total weight of the self-crosslinkable urethane (meth)acrylate.

7. The self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 6, wherein each polyurethane portion UU independently has 2 to 3 urethane bonds.

8. Each polyurethane portion UU is independently defined by the following formula (VIIa) or (VIIb): [In the formula, R １ and R １ [It is independently either an aliphatic linker or an aromatic linker.] A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 7.

9. R １ However, the following formula: [In the formula: Alk is linear or branched alkylene, particularly methylene, 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 2,2,4- or 2,4-,4-trimethylhexylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,12-dodecylene, and 1,18-octadecylene; Ar is an optionally substituted arylene, in particular an optionally substituted arylene selected from phenylene, trilene, biphenylene, naphthylene, and anthracenylene; Cy is an optionally substituted cycloalkylene, in particular an optionally substituted cyclohexylene. A self-crosslinkable urethane (meth)acrylate according to claim 8, selected from one of the following.

10. R １ 'However, the following formula: [In the formula, Alk ＊ These are linear or branched alkylenes, particularly methylene, methanetriyl, and undecane-1,6,11-triyl; Ar ＊ is an optionally substituted arylene, in particular an optionally substituted arylene selected from phenylene, trilene, and biphenylene; R １ The formula (VIIa) is as described above, and in particular, it is 1,6-hexamethylene. A self-crosslinkable urethane (meth)acrylate according to claim 8 or 9, which may be selected from one of the following.

11. Each polyurethane portion UU is independent, - Part of equation (VIIa) [In the formula, R １ The formula is as follows: (In the formula, Alk is linear or branched alkylene, particularly methylene, 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 2,2,4- or 2,4,4-trimethylhexylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,12-dodecylene, and 1,18-octadecylene; Cy is selected from one of the optionally substituted cycloalkylenes, in particular optionally substituted cyclohexylenes; - Part of equation (VIIb) [In the formula, R' １ The formula is as follows: This corresponds to R １ [These are linear or branched alkylenes, particularly 1,6-hexylene]; - and mixtures thereof A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 10, selected from the above.

12. The self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 11, wherein the total amount of polyurethane portion UU in the self-crosslinkable urethane (meth)acrylate accounts for 10 to 65%, particularly 15 to 60%, and more specifically 20 to 55% of the total weight of the self-crosslinkable urethane (meth)acrylate.

13. Each chromophore portion Q independently comprises at least one monovalent or divalent photoinitiator portion PI selected from benzophenone portions, thioxanthone portions, xanthone portions, acridone portions, camphorquinone portions, benzyl portions, coumarin portions, ketocoumarin portions, derivatives thereof, and combinations thereof, preferably at least one monovalent or divalent photoinitiator portion PI selected from benzophenone portions or thioxanthone portions, according to any one of claims 1 to 12.

14. Each chromophore portion Q independently comprises at least one monovalent photoinitiator portion PI corresponding to one of the following formulas (VIII), (XI), (XIV), (XVII), (XVIII), or (XIX), or at least one divalent photoinitiator portion PI corresponding to one of the following formulas (IX), (X), (XII), (XIII), (XV), or (XVI): [In the formula, Each E is independently S, O, or NR, especially S; R is H, an optionally substituted alkyl, or an optionally substituted aryl; Each R ａ These are independently H, F, Cl, Br, I, -OR ｂ ,-SR ｂ , -N(R ｂ ) ２ , -NO ２ , -CN, -C(=O)R ｂ , -OC(=O)R ｂ , -C (=O) OR ｂ , -C(=O)N(R ｂ ) ２ , -NR ｂ -C(=O)-R ｂ , -SO ２ -N(R) ｂ ) ２ or a optionally substituted group selected from the group consisting of alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl and heteroaryl; or two adjacent R ａ The groups may form a 5- to 8-membered ring with the carbon atoms to which they are bonded; Each R ｂ Each R is independently H, or an optionally substituted group selected from alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl and heteroaryl, preferably each R ｂ [These are independently substituted groups selected from alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl, and heteroaryl.] A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 13, comprising:

15. Each chromophore portion Q includes at least one monovalent photoinitiator portion PI corresponding to one of formulas (VIII) or (XI) (wherein E is S), or at least one divalent photoinitiator portion PI corresponding to one of formulas (IX), (X), (XII), or (XIII) (wherein E is S), preferably each chromophore portion Q includes at least one monovalent photoinitiator portion PI corresponding to one of the following formulas (VIIIa) or (XIa), or at least one divalent photoinitiator portion PI corresponding to one of the following formulas (IXa), (Xa), (XIIa), or (XIIIa). [In the formula, R' ａ and R' ｄ are each independently alkyl, Ar, -S-Ar or -O-Ar, where Ar is aryl, particularly methyl, Ph, -S-Ph or -O-Ph, and Ph is phenyl; R' ｂ These are alkyl, especially methyl; R' ｃ , R' ｅ and R' ｆ is independently a halogen, alkoxy, alkyl or -C(=O)-Ar, where Ar is an aryl, in particular F, Cl, methyl, ethyl, isopropyl or -C(=O)-Ph, and Ph is phenyl; x １ and x ４ independently, is 0, 1, 2, or 3, in particular 0 or 1; x ２ , x ３ and x ５ are, independently, 0, 1 or 2, particularly 0 or 1; x ６ [is 0 or 1] A self-crosslinkable urethane (meth)acrylate according to claim 14, comprising:

16. Each chromophore portion Q independently corresponds to the following equations: (XXa), (XXb), or (XXc): [In the formula, L ０ is a (s' + t' + 2) valence linker; Each L １ It is an independently divalent linker; Each L ２ It is an independent (u'+2) valence linker; Each PI １ independently is a monovalent photoinitiator partial PI according to any one of claims 13 to 15; Each PI ２ independently is a divalent photoinitiator partial PI according to any one of claims 13 to 15; s' is 0, 1, or 2; in particular, 0 or 1; t' is 1, 2, 3, or 4; in particular, 2 or 3; Each u' is independently 0 or 1, especially 0. A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 15.

17. Each L １ and L ２ However, independently, directly bonded, or selected from linkers containing 1 to 20, preferably 1 to 10, carbon atoms, the linker optionally containing one or more heteroatoms, for example, O, N, or S; in particular, each L １ and L ２ However, independently, directly bonded, or -O-, -S-, -NR ｌ -, -C(=O)-, -O-C(=O)-, -C(=O)-O-, -NR ｌ -C(=O)-, -C(=O)-NR ｌ -, -O-C(=O)-O-, and combinations thereof (where R ｌ The self-crosslinkable urethane (meth)acrylate according to claim 16, which is selected from a hydrocarbon linker that may contain one or more bonds selected from H, alkyl, or aryl.

18. L ０ However, the linker contains 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and the linker may contain one or more heteroatoms, for example, O, N, or S; in particular, L ０ However, -O-, -S-, -NR ｌ -, -C(=O)-, -O-C(=O)-, -C(=O)-O-, -NR ｌ -C(=O)-, -C(=O)-NR ｌ -, -O-C(=O)-O-, and combinations thereof (where R ｌ The self-crosslinkable urethane (meth)acrylate according to claim 16 or 17, wherein the hydrocarbon linker may contain one or more bonds selected from H, alkyl, or aryl.

19. The self-crosslinkable urethane (meth)acrylate comprises at least one chromophore portion Q according to formula (XXa) as described in claim 16, L １ Preferably, direct bonding, alkylene of formula (C-1), oxyalkylene of formula (C-2), thioalkylene of formula (C-3), ketoalkylene of formula (C-4), aminoalkylene of formula (C-5), carboxyalkylene of formula (C-6), amidealkylene of formula (C-7), alkylene-aminoalkylene of formula (C-8), oxyalkylene-aminoalkylene of formula (C-9), oxyalkylene-amidealkylene of formula (C-10): [In the formula, Each R ｍ , R' ｍ , R ｏ , R' ｏ , R ｐ , R' ｐ , R ｑ , R' ｑ , R ｒ , R' ｒ , R ｓ , R' ｓ , R ｔ and R' ｔ is independently H or an optionally substituted alkyl, particularly H; R'' ｒ and R* ｒ is independently H or an optionally substituted alkyl; f, g, h, j, and j' are independently 1, 2, 3, 4, 5, or 6, especially 1 or 2; i and i' are independently 1, 2, 3, 4, or 5, especially 1; The symbol ● represents a connection point to the PI portion; PI １ Preferably, according to formula (VIII) or (XI) described in claim 14, where E in formula (XI) is S; more preferably, PI １ [This conforms to formula (VIIIa) or (XIa) as described in claim 15] Selected from, A self-crosslinking urethane (meth)acrylate according to any one of claims 1 to 18.

20. Self-crosslinking urethane (meth)acrylate is defined by the following formula (XXa1) or (XXa2) [In the formula, R' ａ is alkyl, Ar, -S-Ar or -O-Ar, where Ar is aryl, especially methyl, Ph, -S-Ph or -O-Ph, and Ph is phenyl; R' ｂ These are alkyl, especially methyl; R' ｃ is a halogen, alkoxy, alkyl or -C(=O)-Ar, where Ar is an aryl, in particular F, Cl, methyl, ethyl, isopropyl or -C(=O)-Ph, and Ph is phenyl; x1 is 0, 1, 2, or 3, especially 0 or 1; x2 is 0, 1, or 2, especially 0 or 1; x3 is 0, 1, or 2, especially 0 or 1; L １ [Selected from direct bonding, alkylene of formula (C-1), oxyalkylene of formula (C-2), aminoalkylene of formula (C-5), amidealkylene of formula (C-7), alkylene-aminoalkylene of formula (C-8), oxyalkylene-aminoalkylene of formula (C-9), or oxyalkylene-amidealkylene of formula (C-10)] A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 19, comprising at least one chromophore portion Q corresponding to the above.

21. Self-crosslinking urethane (meth)acrylate is expressed in the following formulas (XXa3) to (XXa17) A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 20, comprising at least one chromophore portion Q corresponding to one of the above.

22. The self-crosslinking urethane (meth)acrylate comprises at least one chromophore portion Q according to formula (XXc) as described in claim 16, Each L ２ Preferably, the directly bonded alkylene of formula (C-1) as described in claim 19, the oxyalkylene of formula (C-2) as described in claim 19, the thioalkylene of formula (C-3) as described in claim 19, the ketoalkylene of formula (C-4) as described in claim 19, the aminoalkylene of formula (C-5) as described in claim 19, the carboxyalkylene of formula (C-6) as described in claim 19, the amidealkylene of formula (C-7) as described in claim 19, the alkylene-aminoalkylene of formula (C-8) as described in claim 19, the oxyalkylene-aminoalkylene of formula (C-9) as described in claim 19, or the oxyalkylene-amidealkylene of formula (C-10) as described in claim 19; Each u' is preferably 0; PI ２ However, preferably, according to formula (IX), (X), (XII), or (XIII) described in claim 14, where E in formula (XII) and (XIII) is S; more preferably, PI ２ This is according to the formula (IXa), (Xa), (XIIIa), or (XIIIa) described in claim 15. A self-crosslinking urethane (meth)acrylate according to any one of claims 1 to 21.

23. Self-crosslinking urethane (meth)acrylate is expressed by the following formulas (XXc1) to (XXc4) [In the formula, R' ｄ is alkyl, Ar, -S-Ar or -O-Ar, where Ar is aryl, especially methyl, Ph, -S-Ph or -O-Ph, and Ph is phenyl; R' ｅ and R' ｆ is independently a halogen, alkoxy, alkyl or -C(=O)-Ar, where Ar is an aryl, in particular F, Cl, methyl, ethyl, isopropyl or -C(=O)-Ph, and Ph is phenyl; x4 is 0, 1, 2, or 3, especially 0 or 1; x5 is 0, 1, or 2, especially 0 or 1; x6 is either 0 or 1; Each L ２ [These are independently selected from the directly bonded amide alkylene of formula (C-7) described in claim 19 or the oxyalkylene-amide alkylene of formula (C-10) described in claim 19.] A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 22, comprising at least one chromophore portion Q of one of the following.

24. Self-crosslinking urethane (meth)acrylate is expressed by the following formulas (XXc5) to (XXc13) A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 23, comprising at least one chromophore portion Q of one of the following.

25. Self-crosslinking urethane (meth)acrylate is given by the following formula (XXI) [In the formula, n １ is 0, 1, 2, 3, or 4; n ２ is 0, 1, 2, 3, or 4; Total n １ +n ２ is equal to 1, 2, 3, or 4; Each PI １ independently is a monovalent photoinitiator partial PI according to any one of claims 13 to 15; Each X is independently -NR １ -, -O-, -S-, *-C(=O)-O- or *-C(=O)-NR １ - and; Each V is independently directly bonded, #-O-CH ２ -, #-C(=O)-O-CH ２ -, #-NR ５ -CH ２ - or # - C (= O) - NR ５ -CH ２ - and; Each W is independently directly bonded, -CH ２ -O-C(=O))-# or -C(=O)-O-#; Each R １ These are independently H, alkyl, or aryl; R ２ This is a direct link or linker; Each R ３ They are independently, directly coupled, or linkers; Each R ４ independently, H, an optionally substituted alkyl, or an optionally substituted alkenyl; Each R ５ These are independently H, alkyl, aryl, or the following formulas: (In the formula, X, R ３ and PI １ It is a group as described above, and the symbol} represents a bond point to the nitrogen atom; The symbol * is R ３ Represents the connection point to; The symbol # is R ２ [Represents a connection point to] A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 24, comprising at least one chromophore portion Q.

26. Self-crosslinking urethane (meth)acrylate is expressed in the following formulas (XXII) to (XXXV) [In the formula, PI １ X, R ２ , R ３ , R ４ and R ５ The same applies as described in claim 25; n ３ , n ４ , n ７ , n １４ and n １５ These are independently 2, 3, or 4, preferably 2 or 3; n ５ and n ６ Each is independently 1 or 2, preferably 2; n ８ is 1, 2, or 3, preferably 2; n ９ is 1, 2, or 3, preferably 1; n １０ , n １１ , n １６ , n １７ , n １８ , n １９ , n ２０ , n ２１ , n ２２ and n ２３ Each is independently 1 or 2, preferably 1; n １２ and n １３ [Independently, 1, 2, or 3, preferably 1] A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 25, comprising at least one chromophore portion Q of one of the following.

27. Each R ３ However, independently, directly bonded, C1-C6 alkylene, C1-C6 oxyalkylene, C1-C6 alkenylene, C1-C6 thioalkylene, C1-C6 ketoalkylene or C1-C6 aminoalkylene are selected; in particular, each R ３ However, independently, directly bonded, alkylene of formula (C-11), oxyalkylene of formula (C-12), thioalkylene of formula (C-13), ketoalkylene of formula (C-14), or aminoalkylene of formula (C-15): [In the formula, Each R ｍ , R' ｍ , R ｏ , R' ｏ , R ｐ , R' ｐ , R ｑ , R' ｑ , R ｒ and R' ｒ is independently H or an optionally substituted alkyl, particularly H; R'' ｒ is H or an optionally substituted alkyl group; f, g, h, and j are independently 1, 2, 3, 4, 5, or 6, especially 1 or 2; i is 1, 2, 3, 4, or 5, especially 1; The symbol ● is PI １ Represents the connection point to a part; The symbol § represents a connection point to the X portion. A self-crosslinkable urethane (meth)acrylate according to claim 26, selected from the above.

28. Each X independently, -NR １ -, -O- or *-C(=O)-O-; in particular, each X independently, -NR １ A self-crosslinkable urethane (meth)acrylate according to claim 26 or 27, wherein it is - or *-C(=O)-O-.

29. R ２ However, the linker is either directly bonded or selected from the group consisting of alkylene, heteroatom-containing alkylene, alkenylene, heteroatom-containing alkenylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, and combinations thereof; In particular, R ２ However, the linker is either directly bonded or selected from the group consisting of alkylene, heteroatom-containing alkylene, cycloalkylene, arylene, heteroarylene, and combinations thereof. The self-crosslinkable urethane (meth)acrylate according to any one of claims 26 to 28.

30. Self-crosslinkable urethane (meth)acrylates are defined by the following formulas: (XXII), (XXIII), (XXIV), or (XXVI): [In the formula, n ３ , n ４ , n ５ and n ７ These are independently 2, 3, or 4, preferably 2 or 3; Each PI １ Each is independently a monovalent photoinitiator moiety PI according to formula (VIII) or (XI) as described in claim 14, preferably each PI １ is a monovalent photoinitiator molar PI according to formula (VIIIa) or (XIa) as described in claim 15; Each X is independently -NR １ -, -O- or *-C(=O)-O-, preferably -NR １ - or * - C (= O) - O -; Each R １ is independently H or alkyl; Each R ２ These are, independently, alkylenes or heteroatom-containing alkylenes; Each R ３ These are independently, directly bonded, alkylene of formula (C-11) as described in claim 27, oxyalkylene of formula (C-12) as described in claim 27, or aminoalkylene of formula (C-15) as described in claim 27, preferably directly bonded, alkylene of formula (C-11) or oxyalkylene of formula (C-12); Each R ４ is H; Each R ５ These are independently H, alkyl, or the following formula: (In the formula, X, R ３ and PI １ It is a group as described above, and the symbol} represents a bond point to the nitrogen atom; The symbol * is R ３ [Represents a connection point to] A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 29, comprising at least one chromophore portion Q of one of the following.

31. Self-crosslinking urethane (meth)acrylate is defined by the following formulas (XXb1) to (XXb9): A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 30, comprising at least one chromophore portion Q comprising one of the above.

32. Self-crosslinking urethane (meth)acrylate is defined by the following formulas (XXXVI) to (XXXXI): [In the formula, Each PI is independently a monovalent or divalent photoinitiator partial PI according to any one of claims 13 to 15; Each PI １ independently is a monovalent photoinitiator partial PI according to any one of claims 13 to 15; Each L ３ These are independently selected from direct bonds or linkers containing 1 to 20 carbon atoms; Each Y is independently either H or alkyl; Each Z and Z' is independently a linker containing 1 to 20 carbon atoms; each n ２４ , n ２６ , n ２８ and n ３１ independently, is 0 or 1, especially 1; each n ２９ , n ３２ , n ３４ and n ３６ It is independently 1, 2, or 3, especially 1; each n ２７ and n ３３ It is independently 1, 2, or 3; in particular 1 or 2; each n ２５ and n ３０ It is independently 1 or 2, especially 1; n ３５ is 1, 2, or 3, especially 2; n ３７ is either 1 or 2, especially 2. A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 31, comprising at least one chromophore portion Q of one of the following.

33. Each L ３ However, these are independently selected from direct bonding, C1-C6 alkylene, C1-C6 oxyalkylene, C1-C6 alkenylene, C1-C6 thioalkylene, C1-C6 ketoalkylene, C1-C6 ketoalkenylene, C7-C13 ketoarylene, and C6-C13 ketocycloalkylene; More specifically, each L ３ However, independently, directly bonded, alkylene of formula (C-16), oxyalkylene of formula (C-17), thioalkylene of formula (C-18), ketoalkylene of formula (C-19), aminoalkylene of formula (C-20), or alkylene of formula (C-21): [In the formula, Each R ｍ , R' ｍ , R ｎ , R' ｎ , R ｏ , R' ｏ , R ｐ , R' ｐ , R ｑ , R' ｑ , R ｒ and R' ｒ is independently H or an optionally substituted alkyl, particularly H; R'' ｒ and R'' ｎ is independently H or an optionally substituted alkyl; f, g, h, and j are independently 1, 2, 3, 4, 5, or 6, especially 1 or 2; i and k are independently 1, 2, 3, 4, or 5, especially 1; The symbol ● is PI or PI １ Represents the connection point to a part; The symbol § is PI or PI １ [Represents connection points to parts other than the main body] A self-crosslinkable urethane (meth)acrylate according to claim 32, selected from the above.

34. The self-crosslinkable urethane (meth)acrylate according to claim 32 or 33, wherein each Y is independently alkyl, particularly methyl or ethyl.

35. Each Z is independently an alkylene; in particular, each Z is independently an alkylene according to one of the following formulas (C-22), (C-23), or (C-24), and more specifically, each Z is independently an alkylene of formula (C-22): [In the formula, each R ｖ , R' ｖ , R ｗ , R' ｗ , R ｘ , R' ｘ is independently H or alkyl, especially H; R'' ｗ is H or alkyl, especially alkyl; h' is 1, 2, 3, 4, 5, or 6, especially 2; Each i'' is independently 1, 2, or 3, especially 1; Each j'' is independently 1, 2, or 3, especially 1; symbol [This represents a bond point to a nitrogen atom or an oxygen atom.] The self-crosslinkable urethane (meth)acrylate according to any one of claims 32 to 34.

36. Each Z' is independently selected from aliphatic or aromatic hydrocarbon linkers, polyether linkers, polyester linkers, polycarbonate linkers, polyorganosiloxane linkers, polydiene linkers, isocyanurate linkers and combinations thereof; in particular, each Z' is independently selected from aliphatic or aromatic hydrocarbon linkers, polyether linkers, polyester linkers and combinations thereof; more specifically, each Z' is independently selected from alkylene, alkoxylated alkylene and polycaprolactone linkers, according to any one of claims 32 to 35.

37. The self-crosslinking urethane (meth)acrylate of the present invention is defined by the following formulas (XXXXXII) to (XXXXXIV): [In the formula, Each PI １ Each is independently a monovalent photoinitiator moiety PI according to formula (VIII) or (XI) as described in claim 14, preferably each PI １ is a monovalent photoinitiator molar PI according to formula (VIIIa) or (XIa) as described in claim 15; Each L ３ These are independently, directly bonded, alkylene of formula (C-16) as described in claim 33, oxyalkylene of formula (C-17) as described in claim 33, thioalkylene of formula (C-18) as described in claim 33, or alkylene of formula (C-21) as described in claim 33; Each Z is independently an alkylene of formula (C-22) as described in claim 35; Each Z' is independently an alkylene or polyether linker. A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 36, comprising at least one chromophore portion Q of one of the following.

38. Self-crosslinking urethane (meth)acrylate is defined by the following formulas (XXb10) to (XXb26): A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 37, comprising at least one chromophore portion Q of one of the following.

39. The self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 38, wherein the total amount of chromophore portion Q in the self-crosslinkable urethane (meth)acrylate accounts for 0.5 to 20%, particularly 1 to 15%, and more specifically 1.5 to 10%, of the total weight of the self-crosslinkable urethane (meth)acrylate.

40. The self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 39, wherein the self-crosslinkable urethane (meth)acrylate comprises at least one chain extension portion EXT which is a polyol residue selected from a polymer polyol residue, a nonpolymer polyol residue, or an amino-functional polyol residue.

41. The self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 40, comprising at least one chain extension portion EXT which is a polymer diol residue, particularly a polyether diol or polyester diol residue, more specifically, a polyether diol residue selected from polyethylene glycol, poly(1,2-propylene glycol), poly(1,3-propylene glycol), poly(1,4-butylene glycol) and combinations thereof, or a polyester diol residue selected from poly(caprolactone), poly(lactide), poly(alkylene glycol adipate) and poly(alkylene glycol succinate).

42. Self-crosslinkable urethane (meth)acrylates contain residues of nonpolymeric diols, particularly nonpolymeric aliphatic diols, more specifically, ethylene glycol, di, tri, or tetraethylene glycol, 1,2- or 1,3-propylene glycol, di, tri, or tetra(1,2-propylene glycol), di, tri, or tetra(1,3-propylene glycol), 1,2-, 1,3- or 1,4-butylene glycol, di, tri, or tetra(1,4-butylene glycol), 1,5-pentanediol, 1,6-hexanediol, 1, 7-Heptanediol, 1,8-Octanediol, 1,9-Nonanediol, 1,10-Decanediol, 1,12-Dodecanediol, 2-Methyl-1,3-Propanediol, 2,2-Dimethyl-1,3-Propanediol, 2,2-Diethyl-1,3-Propanediol, 2-Methyl-2-Ethyl-1,3-Propanediol, 3-Methyl-1,5-Pentanediol, 3,3-Dimethyl-1,5-Pentanediol, 2,4-Diethyl-1,5-Pentanediol, 3-Butyl-3-Ethyl-1,5-Pentanediol, 2,2,4-Trimethyl A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 41, comprising at least one chain extension portion EXT, which is a residue of a nonpolymer aliphatic diol selected from 1,5-pentanediol, cyclohexanediol, cyclohexane-1,4-dimethanol, norbornenedimethanol, norbornanedimethanol, tricyclodecanediol, tricyclodecanedimethanol, hydrogenated bisphenol A, B, F or S, dianhydrohexitol (i.e., isosorbide, isomannide, isoidide), hydrogenated dimeric fatty acids (i.e., diols obtained by dimerizing one or more unsaturated fatty acids such as oleic acid or linoleic acid, and then hydrogenating the resulting product to convert the carboxylic acid group to a hydroxyl group, e.g., Pripol® 2033 of Croda), and its alkoxylated (i.e., ethoxylated and / or propoxylated) derivatives having up to four oxyalkylene units.

43. Self-crosslinkable urethane (meth)acrylate has at least one chain extension portion EXT containing a tertiary amine group, particularly triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-t-butyldiethanolamine, trimethanolamine, N-methyldimethanolamine, 3-(dimethylamino)-1,2-propanediol, 3-(diethylamino)-1,2-propanediol, 3-(dipropyl Ropyramino)-1,2-propanediol, 2-(dimethylamino)propane-1,3-diol, bis(2-hydroxyethyl)dodecylamine, bis(2-hydroxyethyl)octadecylamine, N,N-dioctadecyl-N',N'-bis(2-hydroxyethyl)-1,3-diaminopropane, 3-morpholino-1,2-propanediol, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1-yl-1,2-propanediol, and the following formula (XXXXXVI): [In the formula, R ｙ and R' ｙ This is independently a substituted group selected from alkyl, alkenyl, alkynyl, aryl, aralkyl, alkalyl, and heteroaryl groups; Each R ｚ These are independently H, F, Cl, Br, I, -OR*, -SR*, -N(R*) ２ , -NO ２ , -CN, -C(=O)R*, -OC(=O)R*, -C(=O)OR*, -C(=O)N(R*) ２ , -NR*-C(=O)-R*, -SO ２ -N(R*) ２ , or a optionally substituted group selected from the group consisting of alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkalyl, and heteroaryl; Each R* is independently H, or an optionally substituted group selected from alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkalyl, and heteroaryl; L' ３ L in claim 32 or 33 ３ As described below; Each Z'' is independently as described for Z in claim 32 or 35; n ３８ [is 0 or 1] A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 42, comprising at least one chain extension portion EXT which is a residue of an amino-functional polyol selected from aminobenzamide diols.

44. The self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 43, wherein the total amount of chain extension portions EXT in the self-crosslinkable urethane (meth)acrylate accounts for 0 to 84.5%, particularly 0.1 to 75%, and more specifically 1 to 65% of the total weight of the self-crosslinkable urethane (meth)acrylate.

45. The self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 44, wherein each (meth)acrylate functionalized portion ACR is a terminal portion bonded to a single polyurethane portion UU.

46. The self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 45, comprising a chromophore portion Q bonded to at least two different polyurethane portions UU.

47. Self-crosslinking urethane (meth)acrylate has the following structure (A): [wherein ACR, UU, Q, and EXT are as described in any one of claims 1 to 44; a is an integer between 1 and 100; b is an integer between 0 and 100; c is an integer equal to 0, 1, or 2, preferably 0 or 1. A self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 46, which corresponds to the above.

48. The self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 45, comprising at least one chromophore portion Q bonded to a single polyurethane portion UU.

49. Self-crosslinking urethane (meth)acrylate has the following structure (B): [In the formula, Each D is independently either Q or EXT; Each T is independently ACR or Q; ACR, UU, Q, and EXT are as described in any one of claims 1 to 44; a' is an integer between 0 and 100; b' is an integer between 0 and 100; Here, at least one of a' and b' is not 0; At least one of D and T is Q. A self-crosslinking urethane (meth)acrylate according to any one of claims 1 to 45 and 48, which corresponds to the above.

50. The self-crosslinkable urethane (meth)acrylate according to any one of claims 1 to 49, wherein the self-crosslinkable urethane (meth)acrylate does not contain an effective amount of dye portion, and preferably the self-crosslinkable urethane (meth)acrylate does not contain any dye portion.

51. A method for preparing a self-crosslinking urethane (meth)acrylate, a) With hydroxyl-functionalized (meth)acrylate components; b) Polyisocyanate components; c) With a hydroxyl-functionalized photoinitiator component; d) Optionally, the polyol component and A method that includes reacting [something].

52. The method according to claim 51, wherein component a) comprises at least one hydroxyl-functionalized (meth)acrylate compound having 1 to 5 (meth)acrylate groups, particularly 1 to 3 (meth)acrylate groups, and more specifically 1 (meth)acrylate group.

53. Component a) is given by the following formula (Ia): [In the formula, R ４ , R ５ And w' is as described in any one of claims 3 to 5. The method according to claim 51 or 52, comprising at least one hydroxyl-functionalized (meth)acrylate compound.

54. Component a) is hydroxyalkyl (meth)acrylate (e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, neopentyl glycol mono(meth)acrylate or 1,6-hexanediol mono(meth)acrylate), 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, tris(2-hydroxyethyl) isocyanurate mono- and di(meth)acrylate, di-, tri-, tetra- or polyethylene glycol Mono(meth)acrylate, di, tri, tetra, or poly(1,2-propylene glycol) mono(meth)acrylate, di, tri, tetra, or poly(1,3-propylene glycol) mono(meth)acrylate, di, tri, tetra, or poly(1,4-butylene glycol) mono(meth)acrylate, glycerin mono and di(meth)acrylate, 2-hydroxy-1-acrylooxy-3-(meth)acrylooxypropane, trimethylolpropane mono and di(meth)acrylate, di(trimethylolpropane) mono, di and tri(meth)acrylate, trimethylolethane mono and di(meth)acrylate, pentaerythritol mono, di and tri(meth)acrylate, dipentaerythritol Mono-, di-, tri-, tetra-, and penta(meth)acrylates, and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives, and the above hydroxyl-functionalized (meth)acrylate compounds (i.e., (poly)caprolactone (meth)acrylate, e.g., the following formula: CH ２ =CR ５ -C(=O)-O-CH ２ -CH ２ -[O-(C=O)-(CH ２ ) ５ ] ｎ -OH [wherein, R ５ The method according to any one of claims 51 to 53, comprising at least one hydroxyl-functionalized (meth)acrylate compound selected from a combination thereof, obtained by ring-opening polymerization of ε-caprolactone initiated by one of (poly)caprolactone (2-hydroxyethyl (meth)acrylate) by [where is H or methyl and t is 1 to 20].

55. The method according to any one of claims 51 to 54, wherein the total amount of component a) used to prepare a self-crosslinking urethane (meth)acrylate is 5 to 85%, particularly 10 to 80%, more specifically 15 to 75%, of the total amount of components a), b), c) and d) by weight.

56. The method according to any one of claims 51 to 55, wherein component b) comprises at least one polyisocyanate compound having two to three isocyanate groups.

57. Component b) is at least one diisocyanate compound according to the following formula (VIIa) and / or at least one triisocyanate compound according to the following formula (VIIb): [In the formula, R １ and R １ ' is as described in any one of claims 8 to 10.' The method according to any one of claims 51 to 56, including the method described in any one of claims 51 to 56.

58. Component b) is, - 2,4- and 2,6-toluene diisocyanate (TDI), isophorone diisocyanate (IPDI, equivalent to 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate), methylene diisocyanate, ethylene diisocyanate, 1,2- or 1,3-propylene diisocyanate, 1,2-, 1,3- or 1,4-butylene diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,2,4- and 2,4,4-trimethylhexamethylene Diisocyanates (TMDI), 1,10-decylene diisocyanate, 1,12-dodecylene diisocyanate, 1,18-octadecylene diisocyanate, 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 2,2'-, 2,4'- and 4,4'-dicyclohexylmethane diisocyanate (H12MDI), benzidine diisocyanate, 3,3'-dimethyl 4,4'-biphenyl diisocyanate, dianisidine diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylenediisocyanate, 1,4- and 1,5-naphthalenediisocyanate (NDI), 1,4- and 9,10-anthracene diisocyanate, 1,3- and 1,4-cyclohexane diisocyanate, 1-methyl-2,4 -Diisocyanatocyclohexane, 1-methyl-2,6-diisocyanatocyclohexane, 1,3 and 1,4-bis(isocyanatomethyl)cyclohexane, m-tetramethylxylenediisocyanate, m-xylenediisocyanate, 4-methoxy-1,3-phenylenediisocyanate, 4-ethoxy-1,3-phenylenediisocyanate, 5,6-dimethyl-1,3-phenylenediisocyanate, 2,4'- or 4,4'-diisocyanate diphenyl ether, lysine diisocyanate, dimeric acid diisocyanate, dimers of the above diisocyanates (especially uretdione or allophanate dimers), and polyureas or polyurethane prepolymers functionalized with isocyanate functional groups, and at least one diisocyanate selected from combinations thereof; and / or - At least one triisocyanate selected from 1,6,11-undecane triisocyanate, triphenylmethane triisocyanate, 2,4,6-tolurene triisocyanate, 2,4,4'-triisocyanate diphenyl ether, trimers of the above diisocyanates (especially isocyanurate or biuret trimers), polymer derivatives of the above diisocyanates, and combinations thereof. The method according to any one of claims 51 to 57, including the method described in any one of claims 51 to 57.

59. The method according to any one of claims 51 to 58, wherein the total amount of component b) used to prepare the self-crosslinkable urethane (meth)acrylate is 10 to 65%, particularly 15 to 60%, more specifically 20 to 55%, of the total amount of components a), b), c) and d) by weight.

60. The method according to any one of claims 51 to 59, wherein component c) comprises at least one hydroxyl-functionalized photoinitiator comprising at least one monovalent or divalent photoinitiator partial PI as described in any one of claims 13 to 15.

61. The method according to any one of claims 51 to 60, comprising at least one hydroxyl-functionalized photoinitiator, wherein component c) is a monool, diol, triol, or tetraol.

62. Component c) is given by the following formulas (XXd), (XXe), or (XXf): [In the formula, L ０ , L １ and L ２ This is as described in any one of claims 16 to 19, 22, and 23; Each PI １ independently is a monovalent photoinitiator partial PI according to any one of claims 13 to 15; Each PI ２ independently is a divalent photoinitiator partial PI according to any one of claims 13 to 15; s', t', and u' are as described in claim 16. The method according to any one of claims 51 to 61, comprising at least one hydroxyl-functionalized photoinitiator, one of the following.

63. Component c) comprises at least one hydroxyl-functionalized photoinitiator according to formula (XXd) described in claim 62, L １ and PI １ However, the method according to any one of claims 51 to 62, preferably as described in claim 19.

64. Component c) is given by the following formula (XXd1) or (XXd2): [In the formula, R' ａ , R' ｂ , R' ｃ x1, x2, x3 and L １ This is as described in claim 20. The method according to any one of claims 51 to 63, comprising at least one hydroxyl-functionalized photoinitiator.

65. Component c) is given by the following equations (XXd3) to (XXd17): The method according to any one of claims 51 to 64, comprising at least one hydroxyl-functionalized photoinitiator corresponding to one of the following.

66. Component c) comprises a hydroxyl-functionalized photoinitiator according to formula (XXf) as described in claim 62, and each L ２ u' and PI ２ The method according to any one of claims 51 to 65, as described in claim 22.

67. Component c) is given by the following equations (XXf1) to (XXf4): [In the formula, R' ｄ , R' ｅ , R' ｆ , x4, x5, x6 and L ２ This is as described in claim 23. The method according to any one of claims 51 to 66, comprising at least one hydroxyl-functionalized photoinitiator corresponding to one of the following.

68. Component c) is given by the following equations (XXf5) to (XXf13): The method according to any one of claims 51 to 67, comprising at least one hydroxyl-functionalized photoinitiator, one of the following.

69. Component c) comprises at least one hydroxyl-functionalized photoinitiator according to formula (XXe) described in claim 62, wherein the hydroxyl-functionalized photoinitiator preferably has a number of photoinitiator moieties equal to the number of OH groups. １ The method according to any one of claims 51 to 68, comprising:

70. Component c) is given by the following formula (XXIa): [In the formula, n １ , n ２ PI １ V, W, X, R ２ , R ３ and R ４ This is as described in claim 25. The method according to any one of claims 51 to 69, comprising at least one hydroxyl-functionalized photoinitiator.

71. Component c) is given by the following equations (XXIIa) to (XXXVa): [In the formula, n ３ , n ４ , n ５ , n ６ , n ７ , n ８ , n ９ , n １０ , n １１ , n １２ , n １３ , n １４ , n １５ , n １６ , n １７ , n １８ , n １９ , n ２０ , n ２１ , n ２２ , n ２３ PI １ X, R ２ , R ３ and R ４ The same applies as described in any one of claims 26 to 29; Each R ５ These are independently H, alkyl, aryl, or the following formulas: (In the formula, X, R ３ and PI １ As described above, the symbol} represents a bond point to the nitrogen atom. The method according to any one of claims 51 to 70, comprising at least one hydroxyl-functionalized photoinitiator, one of the following.

72. Component c) is one of the following formulas: (XXIIa), (XXIIIa), (XXIVa), or (XXVIa): [In the formula, n ３ , n ４ , n ５ , n ７ PI １ X, R ２ , R ３ , R ４ The same applies as described in claim 30; Each R ５ These are independently H, alkyl, or the following formula: (In the formula, X, R ３ and PI １ As described above, the symbol} represents a bond point to the nitrogen atom. The method according to any one of claims 51 to 71, comprising at least one hydroxyl-functionalized photoinitiator, one of the following.

73. Component c) is given by the following equations (XXe1) to (XXe9): The method according to any one of claims 51 to 72, comprising at least one hydroxyl-functionalized photoinitiator, one of the following.

74. Component c) is given by the following equation (XXXVIa) to (XXXXXIa): [In the formula, PI, PI １ , L ３ , Y, Z, Z', n ２４ , n ２５ , n ２６ , n ２７ , n ２８ , n ２９ , n ３０ , n ３１ , n ３２ , n ３３ , n ３４ , n ３５ , n ３６ and n ３７ This is as described in any one of claims 32 to 36. The method according to any one of claims 51 to 73, comprising at least one hydroxyl-functionalized photoinitiator, one of the following.

75. Component c) is given by the following equations (XXXXXIIa) to (XXXXXIVa): [In the formula, PI １ , L ３ , Z and Z' are as described in claim 37. The method according to any one of claims 51 to 74, comprising at least one hydroxyl-functionalized photoinitiator, one of the following.

76. Component c) is given by the following equations (XXe10) to (XXe26): The method according to any one of claims 51 to 75, comprising at least one hydroxyl-functionalized photoinitiator, one of the following.

77. The method according to any one of claims 51 to 76, wherein the total amount of component c) used to prepare the self-crosslinkable urethane (meth)acrylate is 0.5 to 20%, particularly 1 to 15%, more specifically 1.5 to 10%, of the total amount of components a), b), c) and d) by weight.

78. The method according to any one of claims 51 to 77, wherein component d) comprises at least one polyol selected from polymer polyols, nonpolymer polyols, or amino-functional polyols.

79. The method according to any one of claims 51 to 78, wherein component d) comprises at least one polymer diol, particularly at least one polyether diol or at least one polyester diol, more specifically, at least one polyether diol selected from polyethylene glycol, poly(1,2-propylene glycol), poly(1,3-propylene glycol), poly(1,4-butylene glycol) and combinations thereof, or at least one polyester diol selected from poly(caprolactone)diol, poly(lactide)diol, poly(alkylene glycol adipate)diol and poly(alkylene glycol succinate)diol.

80. Component d) is at least one nonpolymeric diol, particularly at least one nonpolymeric aliphatic diol, more specifically, ethylene glycol, di, tri, or tetraethylene glycol, 1,2- or 1,3-propylene glycol, di, tri, or tetra(1,2-propylene glycol), di, tri, or tetra(1,3-propylene glycol), 1,2-, 1,3- or 1,4-butylene glycol, di, tri, or tetra(1,4-butylene glycol), 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol The method according to any one of claims 51 to 79, comprising at least one nonpolymer aliphatic diol selected from pandiol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 3,3-butylethyl-1,5-pentanediol, cyclohexanediol, cyclohexane-1,4-dimethanol, norbornenedimethanol, norbornanedimethanol, tricyclodecanediol, tricyclodecanedimethanol, hydrogenated bisphenol A, B, F or S, dianhydrohexitol (i.e., isosorbide, isomannide, isoidide), hydrogenated dimeric fatty acids, and alkoxylated (i.e., ethoxylated and / or propoxylated) derivatives thereof.

81. Component d) is at least one amino-functional polyol, particularly triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-t-butyldiethanolamine, trimethanolamine, N-methyldimethanolamine, 3-(dimethylamino)-1,2-propanediol, 3-(diethylamino)-1,2-propanediol, 3-(dipropylamino)-1,2 -Propanediol, 2-(dimethylamino)propane-1,3-diol, bis(2-hydroxyethyl)dodecylamine, bis(2-hydroxyethyl)octadecylamine, N,N-dioctadecyl-N',N'-bis(2-hydroxyethyl)-1,3-diaminopropane, 3-morpholino-1,2-propanediol, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1-yl-1,2-propanediol, and the following formula (XXXXVI): [In the formula, R ｙ , R' ｙ , R ｚ , L' ３ , Z'' and n ３８ This is as described in claim 43. The method according to any one of claims 51 to 80, comprising at least one amino-functional polyol selected from aminobenzamide diols.

82. The method according to any one of claims 51 to 81, wherein the total amount of component d) used to prepare the self-crosslinkable urethane (meth)acrylate is 0 to 84.5%, particularly 0.1 to 75%, and more specifically 1 to 65%, of the total amount of components a), b), c) and d) by weight.

83. The method according to any one of claims 51 to 82, wherein components a), b), c), and d) do not contain a dye portion.

84. A method for polymerizing one or more ethylenically unsaturated compounds, comprising contacting one or more ethylenically unsaturated compounds with a self-crosslinkable urethane (meth)acrylate prepared by any one of claims 1 to 50 or by any one of claims 51 to 83, and irradiating the mixture with ultraviolet light, near-ultraviolet light, visible light, infrared light, near-infrared light and / or electron beams.

85. The method according to claim 84, wherein the polymerization step does not involve the use of a radical initiator or initiator system other than a self-crosslinkable urethane (meth)acrylate prepared by any one of claims 1 to 50 or by the method according to any one of claims 51 to 83.

86. A curable composition, A) A self-crosslinkable urethane (meth)acrylate prepared by any one of claims 1 to 50 or by the method described in any one of claims 51 to 83, B) Selectively combine polymerizable components other than those in A) A curable composition containing the following:

87. The curable composition according to claim 86, comprising component A) in amounts of 1 to 100% by weight, 5 to 95% by weight, 5 to 90% by weight, 10 to 85% by weight, 10 to 80% by weight, 15 to 75% by weight, 15 to 70% by weight, 20 to 65% by weight, and 20 to 60% by weight, based on the weight of the curable composition.

88. The curable composition according to claim 86 or 87, comprising component B) in amounts of 0-99% by weight, 5-95% by weight, 10-95% by weight, 15-90% by weight, 20-90% by weight, 25-85% by weight, 30-85% by weight, 35-80% by weight, and 40-80% by weight, based on the weight of the curable composition.

89. The curable composition according to any one of claims 86 to 88, wherein component B) comprises at least one (meth)acrylate-functionalized monomer, more preferably at least one poly(meth)acrylate-functionalized monomer.

90. The curable composition according to any one of claims 86 to 89, wherein component B) comprises glycerol tri(meth)acrylate; diglycerol tetra(meth)acrylate, triglycerol penta(meth)acrylate, tetraglycerol hexa(meth)acrylate, trimethylolethane tri(meth)acrylate; trimethylolpropane tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, di(trimethylolpropane)tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol) hexa(meth)acrylate; tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof, and combinations thereof.

91. Component B) is a urethane (meth)acrylate monomer, in particular, the following formula (XXXXXVII): [In the formula, R ４ , R ５ And w' are as described in any one of claims 3 to 5; R １ This is as described in claim 8 or 9. A curable composition according to any one of claims 86 to 90, comprising a urethane (meth)acrylate monomer.

92. The curable composition according to any one of claims 86 to 91, wherein component B) comprises 0 to 100% by weight, particularly 5 to 90% by weight, more specifically 10 to 80% by weight, even more specifically 15 to 75% by weight, and even more specifically 20 to 70% by weight, of (meth)acrylate functionalized monomer, based on the total weight of component B).

93. A curable composition according to any one of claims 86 to 92, which substantially does not contain initiators or initiator systems other than component A).

94. A curable composition according to any one of claims 86 to 73, which is substantially free of dyes.

95. Preferably, a method for preparing a cured product comprising curing the curable composition according to any one of claims 86 to 94 by exposing the curable composition to electromagnetic radiation and / or electron beam radiation that induces chemical reactions, such as ultraviolet light, near-ultraviolet light, visible light, infrared light, and near-infrared light.

96. A substrate to which a curable composition according to any one of claims 86 to 94 has been applied and cured, the substrate being, in particular, food and beverage packaging, pharmaceutical packaging, textiles, nails, teeth, medical devices, food and beverage processing equipment, water pipes, or toys.

97. Use of a self-crosslinking urethane (meth)acrylate prepared by any one of claims 1 to 50 or by any one of claims 51 to 83 to obtain a cured product with a reduced amount of extract.

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