Chromophore-functionalized polyols

Abstract

A polyol having at least one chromophore moiety is provided. This polyol is useful for preparing photocurable compositions that do not require an additional separate chromophore.

Description

[Technical Field]

[0001] A polyol having at least one chromophore moiety is provided. The polyol is useful for preparing photocurable compositions that do not require an additional separate chromophore. [Background technology]

[0002] In photocuring systems or other chemical radiation curing systems, including those containing urethane (meth)acrylates, the radicals that initiate curing are generated by the photodegradation of photoinitiator molecules. A wide variety of such small molecule photoinitiators are commercially available and well known to those skilled in the art. A disadvantage of using small molecule photoinitiators is the inevitable residue of small molecule photofragments in the cured composition. This is true whether using fragmentation-type photoinitiators (Nourish type I) or hydrogen abstraction-type bimolecular photoinitiators (Nourish type II). These small molecule fragments often contribute to undesirable odors, volatile organic compounds, and extractable / leaching molecules.

[0003] Polymeric thioxanthones are disclosed in International Publication No. 2010 / 124950 and Japanese Patent Publication No. 2017-125033.

[0004] The use of oligomeric / polymer-type photoinitiators is not an ideal solution, as it typically involves trade-offs including reduced curing speed, limited compatibility with resins, and increased compounding costs due to reduced active ingredient content in polymer-type photoinitiator systems. In some cases, polymer-type photoinitiators may adversely affect the properties of the cured material because the initiator polymer backbone is not optimized for a given application. Therefore, having available monomer photoinitiators that can react with the backbone during the photoinitiation reaction that forms the polymer would be useful.

[0005] The inventors have prepared unique photoinitiators having at least two hydroxyl groups that can react with other monomers, such as polyisocyanates, to form polymers having a photoinitiator moiety in their backbone. Therefore, photopolymerizable compositions containing these photoinitiators may not require additional photoinitiators. Since the chromophore-containing material is included in the final polymer, there is no risk of the photoinitiator leaching or evaporating from the final polymer and contributing to undesirable volatile organic compound content. Another advantage is that in photopolymerizable compositions containing these monomers and related oligomers containing these monomers, the chromophore / photoinitiator is, by definition, bound to and compatible with the oligomers, and therefore the risk of phase separation or changes in the mechanical properties of the cured material due to the oligomer photoinitiator component is minimized. [Overview of the project]

[0006] The present invention relates to a photoinitiator according to the following formula (I): TIFF2026520472000001.tif37170[where n1, n2, Q, X, Y, Z, R 1 , R 2 , R 3 , and R 4 [This is defined as herein.]

[0007] The present invention also relates to a method for preparing a photoinitiator by reacting a chromophore-containing component a) with a polyepoxide component b), wherein component a) comprises at least one compound having at least one chromophore moiety and at least one epoxide-reactive group; and component b) comprises at least one compound having at least two epoxide rings.

[0008] The present invention also relates to the use of a photoinitiator according to the present invention as a photoinitiation system in a radiation-curable composition.

[0009] The present invention further relates to the use of the photoinitiator according to the present invention in a photopolymerization reaction.

[0010] The present invention also relates to the use of the photoinitiator according to the present invention for obtaining a photoreactive oligomer, particularly a photoreactive urethane oligomer, more specifically a photoreactive urethane (meth)acrylate oligomer.

Mode for Carrying Out the Invention

[0011] definition In the present application, the term "comprising one (a / an)~" means "comprising one or more~".

[0012] Unless otherwise specified, the weight percentages in the compounds or compositions are represented based on the weight of the compounds and the weight of the compositions, respectively.

[0013] In the present specification, the molecular weight is the number average molecular weight measured using gel permeation chromatography with polystyrene standards, unless otherwise specified.

[0014] As used herein, the term "independently selected" with respect to the selection of groups in a structure means that when there are multiple groups in the structure, they do not all have to be the same as long as they are selected from the listed options. For example, the description "R 3 can be independently selected from a direct bond or a linker" means that, for example, one R 3 in the structure can be a direct bond and another R 3 can be a linker.

[0015] According to some embodiments, all of the R a groups in the structure may be the same. According to some embodiments, all of the R' a groups in the structure may be the same. According to some embodiments, all of the R 3 groups in the structure may be the same. According to some embodiments, all of the R 4The groups may all be the same. According to some embodiments, all X groups in the structure may be the same. According to some embodiments, all Y groups in the structure may be the same. According to some embodiments, all Z groups in the structure may be the same. According to some embodiments, all Q groups in the structure may be the same.

[0016] The term "chromophore" refers to the portion containing groups that absorb light and can generate reactive species useful for initiating polymerization reactions. In particular, the chromophore may be a Norrish type II chromophore, i.e., a chromophore that does not cleave upon exposure to radiation and therefore would not normally initiate radical chain polymerization unless a co-initiator such as an amine synergist is present. Upon exposure to radiation, the interaction between the type II chromophore and the co-initiator leads to the generation of radical species that can initiate polymerization of UV-curable resins.

[0017] As used herein, "equivalent" refers to the number of moles of a particular reactant required to react with the total moles of another reactant, which may have a different number of reactive groups. For example, when reacting the hydroxyl group of a monoalcohol with the epoxy group of a triepoxide, 3 moles, or 3 "equivalents," of the monoalcohol are required to completely react with 1 mole of triepoxide.

[0018] As used herein, the term "glycidyl ether group" means the group of formula (3): TIFF2026520472000002.tif18170

[0019] As used herein, the term “glycidyl ester group” means the group of formula (4): TIFF2026520472000003.tif25170

[0020] As used herein, the term “glycidylamine group” means the group of formula (5): TIFF2026520472000004.tif19170 Here, R 6 is H, alkyl, aryl, or a glycidyl group of the following formula: TIFF2026520472000005.tif9170

[0021] As used herein, the term “glycidylamide group” refers to the group of formula (6): This means TIFF2026520472000006.tif25170, and in the formula, R 7 is H, alkyl, aryl, or a glycidyl group of the following formula: TIFF2026520472000007.tif9170

[0022] As used herein, the term “alicyclic epoxide group” means the group of formula (7): TIFF2026520472000008.tif23170

[0023] As used herein, the term “epoxy group derived by epoxidation of an acyclic carbon-carbon double bond” means the group of formula (8): This means TIFF2026520472000009.tif18170, and in the formula, R 4 is H, an optionally substituted alkyl, or an optionally substituted alkenyl, and The epoxide rings are represented by the formulas *-CH2-O-, *-CH2-OC(=O)-, and *-CH2-NR 7 -, or *-CH2-NR 7 It does not directly bond to the -C(=O)- group, where the symbol * represents a bond to an epoxide ring (i.e., epoxide rings are not included in glycidyl ether groups, glycidyl ester groups, glycidylamine groups, glycidylamide groups, or alicyclic epoxides).

[0024] 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.

[0025] The term "alkyl" is derived from formula C n H 2n+1 This refers to a monovalent saturated acyclic hydrocarbon group, where n is between 1 and 20. The alkyl group may 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.

[0026] The term "heteroatom-containing alkyl" means an alkyl group containing one or more heteroatoms independently selected from O, N, or S.

[0027] The term "cycloalkyl" refers to a monovalent saturated hydrocarbon group containing a ring. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and isobornyl.

[0028] The term "heterocycloalkyl" refers to a cycloalkyl group having at least one ring atom that is a heteroatom selected from O, N, or S.

[0029] The term "alkenyl" refers to a monovalent acyclic hydrocarbon group containing at least one carbon-carbon double bond. Alkenyls may be linear or branched in structure.

[0030] The term "alkynyl" refers to a monovalent acyclic hydrocarbon group containing at least one carbon-carbon triple bond. Alkynnyls may be linear or branched in structure.

[0031] The term "aryl" refers to a polyunsaturated aromatic group that may be substituted. An aryl can consist of a single ring (i.e., phenyl) or multiple rings, at least one of which is aromatic. If an aryl consists of multiple rings, those rings are fused and linked via covalent 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 above carbocyclic systems. Examples include phenyl, naphthyl, biphenyl, phenantrenyl, and naphthacenyl.

[0032] The term "heteroaryl" refers to an aryl compound having at least one ring atom that is a heteroatom selected from O, N, or S.

[0033] The term "aralkyl" refers to an aryl group substituted with an alkyl group. An example of an aralkyl group is a tolyl.

[0034] The term "alkaline" refers to alkyl groups substituted with an aryl group. An example of an alkaline group is benzyl(-CH2-phenyl).

[0035] The term "halogen" refers to an atom selected from Cl, Br, F, and I.

[0036] The term "alkoxy" refers to the -O-alkyl group, where alkyl is defined above.

[0037] The term "aryloxy" refers to the -O-aryl group of the formula, where aryl is as defined above.

[0038] The term "thioalkyl" refers to the group of the formula -S-alkyl, where alkyl is as defined above.

[0039] The term "thioaryl" refers to the -S-aryl group, where aryl is as defined above.

[0040] The term "aralkyloxy" refers to the base of the formula -O-aralkyl, where aralkyl is defined above.

[0041] The term "alkalyloxy" refers to the group of the formula -O-alkalyloxy, where alkalyl is as defined above.

[0042] The term "alkylene" is derived by removing one hydrogen atom from each bond point of the linker, as shown in formula C. m H 2m+2 This refers to a polyvalent linker derived from an alkane (where m is between 1 and 50). The alkylene may be divalent, trivalent, tetravalent, or have more than one valency.

[0043] The term "alkenylene" refers to a polyvalent aliphatic linker containing at least one carbon-carbon double bond.

[0044] The term "heteroatom-containing alkylene" means an alkylene containing one or more heteroatoms independently selected from O, N, or S.

[0045] The term "heteroatom-containing alkenylene" means an alkenylene containing one or more heteroatoms independently selected from O, N, or S.

[0046] The term "cycloalkylene" refers to 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).

[0047] 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.

[0048] The term "arirene" refers to a polyvalent linker containing at least one aromatic ring.

[0049] 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.

[0050] The term "alkylamino" refers to an alkyl group that is substituted with at least one amino group.

[0051] The term "alkylthiol" refers to an alkyl group that is substituted with at least one thiol group.

[0052] The term "hydroxyalkyl" refers to an alkyl group that is substituted with at least one hydroxyl group.

[0053] The term "haloalkyl" refers to an alkyl group that is substituted with at least one halogen.

[0054] The term "perfluoroalkyl" refers to an alkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[0055] 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, particularly two to four parts, to each other. For example, a linker that links two parts of a compound to each other is called a divalent linker, and a linker that links three parts of a compound to each other is called a trivalent linker, and so on.

[0056] The term “aliphatic compound, group, or linker” means non-aromatic compound, group, or linker. Compounds, groups, or linkers containing non-aromatic rings (i.e., alicyclic rings) are included in the term aliphatic compound, group, or linker. They can be linear or branched, saturated or unsaturated, cyclic or acyclic. They can be substituted with one or more groups selected from, for example, alkyl, hydroxyl, halogen (Br, Cl, I), isocyanate, carbonyl (=O), amine, carboxylic acid, -C(=O)-OR', -C(=O)-OC(=O)-R' (each R' is independently a C1-C6 alkyl). They can contain one or more bonds selected from ethers, esters, amides, urethanes, ureas, carbonates, organosiloxanes, and mixtures thereof.

[0057] The term “aromatic compound, group, or linker” means a compound, group, or linker containing at least one aromatic ring (i.e., a ring that satisfies Hückel’s law of aromaticity, such as phenyl), in particular one, two, or three aromatic rings, preferably one or two aromatic rings. Aroliphatic compounds, groups, or linkers, i.e., compounds, groups, or linkers containing both aromatic and non-aromatic parts, are encompassed within the term “aromatic compound, group, or linker.” It may be substituted with one or more groups as defined in the term “aliphatic compound, group, or linker.” It may contain one or more bonds as defined in the term “aliphatic compound, group, or linker.”

[0058] The term "acyclic compound, group, or linker" means a compound, group, or linker that does not contain a ring.

[0059] The term "cyclic compound, group, or linker" means a compound, group, or linker that contains at least one aromatic or non-aromatic ring.

[0060] The term "saturated compound, group, or linker" means a compound, group, or linker that does not contain double or triple carbon-carbon bonds.

[0061] 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.

[0062] The term "polyol" refers to a compound that contains at least two hydroxyl groups.

[0063] As used herein, the term “polyol residue” means the portion obtained by removing the hydroxyl group from a polyol.

[0064] As used herein, the term "polyacid" means a compound containing at least two carboxylic acid groups.

[0065] As used herein, the term “residue of polyacid” means the portion obtained by removing the carboxylic acid group from a polyacid.

[0066] As used herein, the term "polyamine" means a compound containing at least two primary and / or secondary amino groups.

[0067] As used herein, the term “polyamine residue” means the portion obtained by removing the primary and / or secondary amino groups of a polyamine.

[0068] As used herein, the term "hydroxy acid" means a compound containing at least one hydroxyl group and at least one carboxylic acid group.

[0069] 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.

[0070] As used herein, the term "hydroxyamine" means a compound containing at least one hydroxyl group and at least one primary and / or secondary amino group.

[0071] 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.

[0072] The term "hydroxyl group" refers to the -OH group.

[0073] 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. The "primary amino group" is -NR a1 R b1 It means base, and here, R a1 and R b1 is H. The "secondary amino group" is -NR a1 R b1 It means base, and here, R a1 H is R b1 is an alkyl group that may be substituted.

[0074] The term "carboxylic acid group" refers to the -COOH group.

[0075] The term "isocyanate group" refers to the -N=C=O group.

[0076] The term "direct bond" refers to a covalent bond.

[0077] The term "ester bond" refers to a -C(=O)-O- bond or an -OC(=O)- bond.

[0078] The term "ether bond" refers to an O-bond.

[0079] The term "organosiloxane bond" is a term that refers to -Si(R c1 ) means a 2-O bond, where R c1 This is an organic group, particularly an organic group selected from alkyl, alkoxy, and aryl groups.

[0080] The term "carbonate bond" refers to an -OC(=O)-O- bond.

[0081] The terms "urethane bond or carbamate bond" refer to -NH-C(=O)-O- bonds or -OC(=O)-NH- bonds.

[0082] The term "urethane oligomer" refers to an oligomer that contains at least two urethane bonds.

[0083] The term "polyisocyanate" refers to a compound containing at least two isocyanate groups.

[0084] The term "optionally substituted compound, group, or linker" 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, aralkyloxy, aralkyloxy, aralkyloxy, haloalkyl, -OH, -SH, hydroxyalkyl, thioalkyl, thioaryl, alkylthiol, amino, alkylamino, isocyanate, nitrile, oxo(=O), -C(=O)-R', -OC(=O)-R', -C(=O)-OR', -C(=O)-N(R')2, -NR'-C(=O)-R', -C(=O)-OC(=O)-R', and -SO2-N(R')2, where each R' is independently H, or an optionally substituted group selected from alkyl, aryl, and alkylaryl.

[0085] Photoinitiator of formula (I) The photoinitiator of the present invention corresponds to the following formula (I): TIFF2026520472000010.tif37170[In the formula, n1 is 0, 1, 2, 3, or 4; n2 is 0, 1, 2, 3, or 4; The sum of n1 + n2 is equal to 1, 2, 3, or 4; Each Q is an independent chromophore; Each X independently, -NR 1 -, -O-, -S-, *-C(=O)-O-, or *-C(=O)-NR 1 -and; Each Y is independently directly bonded, with #-O-CH2-, #-C(=O)-O-CH2-, and #-NR 5 -CH2-, or #-C(=O)-NR 5 -CH2-; Each Z 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 These are independently H, an optionally substituted alkyl, or an optionally substituted alkenyl; Each R 5 These are independently H, alkyl, aryl, or -CH2-CH(OH)-CH2-XR 3 -Q, where Q, X, and R 3 It is as defined above; The symbol * is R 3 Represents the connection point to; The symbol # is R 2 [Represents a connection point to].

[0086] In equation (I), the value of n1 is 0, 1, 2, 3, or 4. In particular, the value of n1 may be 0, 1, or 2, and more specifically, n1 may be 0.

[0087] In equation (I), the value of n² is 0, 1, 2, 3, or 4. In particular, the value of n² may be 2, 3, or 4, and more specifically, n² may be 2 or 3.

[0088] In equation (I), the sum of n1 + n2 is equal to 1, 2, 3, or 4. In particular, the sum of n1 + n2 may be equal to 2, 3, or 4, and more specifically, the sum of n1 + n2 may be equal to 2 or 3. When the sum of n1 + n2 is equal to 1, n1 is preferably 0, n2 is preferably 1, and Y is preferably #-NR 5 -CH2- or #-C(=O)-NR 5 -CH2- and R 5 Preferably -CH2-CH(OH)-CH2-XR 3 -Q is the answer.

[0089] 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.

[0090] In a preferred embodiment, n2 is non-zero, and R 2 This is given by the following equation (1): It has at least one part corresponding to TIFF2026520472000011.tif18170, where Q, X, Y, R 3 , and R 4 This is defined herein.

[0091] R 2 It can have at least one part of equation (1), where Y is #-O-CH2- and R 4 This is H. Such a part can be derived from ring-opening of the glycidyl ether group.

[0092] R 2 It can have at least one part of equation (1), where Y is #-(C=O)-O-CH2- and R 4 This is H. Such a part can be derived from ring-opening of the glycidyl ester group.

[0093] R 2 It can have at least one part of equation (1), where Y is #-NR 5 -CH2- and R 4 H is R 5 This is as defined above. Such a portion can be derived from ring-opening of the glycidylamine group.

[0094] R 2 It can have at least one part of equation (1), where Y 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.

[0095] R 2 It can have at least one part of equation (1), where Y is a direct bond and R 4 This 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.

[0096] R 2 R can have one, two, three, four, or four parts of equation (1). These parts may be identical or different from each other. For example, R 2 It can have two, three, or four parts of formula (1), where Y is #-O-CH2- and R 4 It is H. Or, R 2It can have two, three, or four parts of equation (1), where Y is #-(C=O)-O-CH2- and R 4 It is H. Or, R 2 This can have one or two parts of equation (1), where Y is #-NR 5 -CH2- and R 4 It is H. Or, R 2 This can have one or two parts of equation (1), where Y is #-(C=O)-NR 5 -CH2- and R 4 It is H. Or, R 2 It can have two or three parts of equation (1), where Y is a direct bond and R 4 is H or an optionally substituted alkyl group. Alternatively, R 2 It can have at least two parts of formula (1), where the parts are Y and / or R 4 They differ from one another due to their inherent properties.

[0097] In another embodiment, n1 is non-zero, R 2 The following equation (2): Having at least one part conforming to TIFF2026520472000012.tif27170, where Q, X, Z, and R 3 This is as defined herein.

[0098] Such parts can be derived from ring-opening of alicyclic epoxide groups.

[0099] R 2 It can have at least one part of equation (2), where Z is -CH2-OC(=O)-#.

[0100] R 2 It can have at least one part of equation (2), where Z is -C(=O)-O-#.

[0101] R 2can have at least one moiety of formula (2), where Z is a direct bond.

[0102] R 2 can have two, three, or four, or four moieties of formula (2). Such moieties may be identical to or different from each other. For example, R 2 can have two, three, or four moieties of formula (2), where Z is -CH2-O-C(=O))-. Alternatively, R 2 can have two, three, or four moieties of formula (2), where Z is -C(=O)-O-. Alternatively, R 2 can have at least two moieties of formula (2), where the moieties are different from each other due to the nature of Z.

[0103] In yet another embodiment, both n1 and n2 are other than 0, and R 2 has at least one moiety according to formula (1) and at least one moiety according to formula (2). In particular, R 2 can have one moiety according to formula (1), where Y is a direct bond, and R 4 is H and one moiety of formula (2), where Z is a direct bond. Alternatively, R 2 can have one moiety according to formula (1), where Y is #-O-CH2-, and R 4 is H and one moiety of formula (2), where Z is a direct bond. Alternatively, R 2 can have two moieties according to formula (1), where Y is #-(C=O)-O-CH2-, and R 4 is H and one moiety of formula (2), where Z is a direct bond.

[0104] The photoinitiator of formula (I) can correspond to one of the following formulas (I-a) to (I-n): TIFF2026520472000013.tif255170TIFF2026520472000014.tif250170[where Q, X, R2 , 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.]

[0105] Photoinitiators of formulas (Ia), (Ib), (Ic), (Ie), (If), (Ig), and (Ih) are preferred. Photoinitiators of formulas (Ia), (Ib), (Ic), and (Ie) are particularly preferred. More specifically, the photoinitiator of formula (Ia) is preferred.

[0106] The photoinitiators of formulas (I) and (Ia) through (In) contain at least one, preferably at least two, chromophore moieties Q. In particular, the photoinitiators of formulas (I) and (Ia) through (In) contain two, three, or four chromophore moieties Q.

[0107] Each chromophore portion Q may independently contain a benzophenone portion, a thioxanthone portion, an anthraquinone portion, a xanthone portion, or an acridone portion.

[0108] In particular, each chromophore portion Q may independently be a benzophenone portion according to formula (A), or a thioxanthone, anthraquinone, xanthone, or acridone portion according to formula (B): TIFF2026520472000015.tif29170[In the formula, E is S, O, C (=O), or NR, and in particular is S; R is H, an optionally substituted alkyl, or an optionally substituted aryl; Each R a and R' a These are independently H, F, Cl, Br, I, -OR b , -SR b , -N(R b )2, -NO2, -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 , -SO2-N(R b )2, or a optionally substituted group selected from alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl, and heteroaryl; Two adjacent R a or R' a The groups can form 5 to 8-membered rings together with the carbon atoms to which they are bonded; Each R b [These are independently H or a substituted group selected from alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl, and heteroaryl.]

[0109] More specifically, each chromophore portion Q can independently be a benzophenone portion according to formula (A1) or a thioxanthone portion according to formula (B1): TIFF2026520472000016.tif29170[In the formula, Each Rc independently of H, alkyl, Ar, -S-Ar, or -O-Ar, where Ar is aryl, in particular H, methyl, Ph, -S-Ph, or -O-Ph, where Ph is phenyl; Each R' c is independently H or alkyl, and in particular H or methyl; Each R d (i) is independently H, halogen, alkoxy, alkyl, or -C(=O)-Ar, where Ar is aryl, in particular H, F, Cl, methyl, ethyl, isopropyl, or -C(=O)-Ph (where Ph is phenyl).

[0110] In a preferred embodiment, all Q portions have the same structure. In particular, each chromophore portion Q may be a benzophenone portion according to formula (A1). Alternatively, each chromophore portion Q may be a thioxanthone portion according to formula (B1).

[0111] In the photoinitiators of formulas (I) and (Ia) to (In), each chromophore portion Q is R 3 It will be joined to

[0112] Each R 3 These are, independently, direct connections or linkers.

[0113] If Q follows equation (A), then R 3 It is preferable that the bond is direct.

[0114] If Q follows equation (B), then R 3 It is preferable that it be a linker.

[0115] Q follows equation (B), E is S, and R 3 If it is a direct bond, it is preferable that X is not -O-.

[0116] R 3 If it is a direct bond, X is -NR 1 -, *-C(=O)-O-, or *-C(=O)-NR 1 - is preferable.

[0117] R 3 If the linker is a divalent linker containing 1 to 15, preferably 1 to 10, carbon atoms, the linker may further optionally 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 a hydrocarbon linker which optionally comprises one or more bonds selected from combinations thereof, where R l is H, alkyl, or aryl.

[0118] R 3 If it is a linker, the linker may be: - 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 cyclic linkers, which may be monocyclic or polycyclic, in particular cyclic linkers having 6 to 10, 7 to 9, or 7 to 8 carbon atoms.

[0119] Preferred mounting method, each R 3 These are independently directly bonded, C1-C6 alkylene, C1-C6 oxyalkylene, C1-C6 alkenylene, C1-C6 thioalkylene, C1-C6 ketoalkylene, or C1-C6 aminoalkylene.

[0120] More specifically, each R 3 These can independently be a direct bond, an alkylene of formula (C-1), an oxyalkylene of formula (C-2), a thioalkylene of formula (C-3), a ketoalkylene of formula (C-4), or an aminoalkylene of formula (C-5): TIFF2026520472000017.tif41170[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, and in particular H; R" r is H or an optionally substituted alkyl group; f is 1, 2, 3, 4, 5, or 6, and in particular 1 or 2; g is 1, 2, 3, 4, 5, or 6, and especially 1 or 2; h is 1, 2, 3, 4, 5, or 6, and especially 1 or 2; i is 1, 2, 3, 4, or 5, and especially 1; j is 1, 2, 3, 4, 5, or 6, and especially 1 or 2; The symbol ● represents the connection point to the Q section; The symbol § represents a connection point to the X portion.

[0121] More specifically, each R 3 These can be independently selected from direct bonding, alkylene of formula (C-1), oxyalkylene of formula (C-2), and aminoalkylene of formula (C-5). More specifically, each R 3 These can be independently selected from direct bonds, alkylenes of formula (C-1), and oxyalkylenes of formula (C-2) as defined above. Further details are available for each R. 3 These are independently oxyalkylenes of formula (C-2), and in particular, each R 3 is the oxyalkylene of formula (C-2), where R o and R' o H is , and g is 1.

[0122] In the photoinitiators of formulas (I) and (Ia) (In), each R 3It is bonded to X. X can correspond to an epoxide-reactive group, i.e., a residue of a group that can open an epoxide ring. Examples of epoxide-reactive groups include alcohols, thiols, primary and secondary amines, carboxylic acids, and amides.

[0123] Each X independently, -NR 1 -, -O-, -S-, *-C(=O)-O-, or *-C(=O)-NR 1 -and; each R 1 These are independently H, alkyl, or aryl, and the symbol * is R 3 This represents a connection point to [a specific location].

[0124] 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-. More specifically, each X is *-C(=O)-O-.

[0125] In the photoinitiators of formulas (I) and (Ia) (In), each R 2 R is independently a direct link or a linker. 2 If it is a linker, the linker can be divalent, trivalent, or tetravalent. 2 If the linker is a linker, it may be aliphatic or aromatic, and may be particularly aliphatic.

[0126] In a preferred embodiment, R 2 This refers to a linker other than a direct bond or a polyether linker, and in particular, R 2This is a linker other than a polyether linker. As used herein, the term "linker other than a polyether linker" means a linker that does not contain a continuous repeating unit induced by ring-opening of a cyclic ether containing 2 to 4 carbon atoms. In particular, a linker other than a polyether does not have to contain a moiety containing multiple oxyalkylene units, and preferably a linker other than a polyether does not contain oxyalkylene units. More specifically, a linker other than a polyether is -[OA 1 ] z The part marked with a hyphen does not need to be included, and here, A 1 is a C2-C4 alkylene, z is greater than 1, and preferably the linker is not a polyether, -[OA 1 ]-Excluding the part, here, A 1 It is a C2-C4 alkylene. More specifically, linkers other than polyethers do not have to contain multiple acyclic ether bonds, and preferably, linkers other than polyethers do not contain acyclic ether bonds.

[0127] In a particularly preferred embodiment, R 2 This is a direct bond or a non-polymerizable linker, preferably R 2 It is a non-polymerizable linker. As used herein, the term "non-polymerizable linker" means a linker that does not contain consecutive repeating units other than consecutive carbon atoms.

[0128] R 2 It can contain 0 to 20 carbon atoms, particularly 0 to 15, and more specifically 0 to 10 carbon atoms. 2 It can contain 0 to 2 oxygen atoms, especially 0 to 1, and more specifically 0 oxygen atoms. 2 It may contain 0 to 2, especially 0 to 1, and more specifically 0, heteroatom atoms selected from O, N, or S.

[0129] R 2The molecular weight may be less than 500 g / mol, more specifically less than 400 g / mol, more specifically less than 300 g / mol, even more specifically less than 250 g / mol, and even more specifically less than 200 g / mol.

[0130] In particular, each R 2 R can be independently a linker selected from groups consisting of direct bonds, alkylene, heteroatom-containing alkylene, alkenylene, heteroatom-containing alkenylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, and combinations thereof. 2 The linker may be a direct bond or a group selected from alkylene, heteroatom-containing alkylene, cycloalkylene, arylene, and combinations thereof. More specifically, R 2 The linker may be selected from alkylenes, heteroatom-containing alkylenes, cycloalkylenes, arylenes, and combinations thereof.

[0131] In one embodiment, R 2 R can be an aromatic linker such as arylene, heteroarylene, or a combination thereof. In such cases, R 2 It is preferable that it be arylene.

[0132] For example, R 2 This can be expressed by one of the following equations (3) through (9): TIFF2026520472000018.tif115170[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 H or methyl; a, a', c, and c' are independently either 0 or 1; b is either 1 or 2.

[0133] In particular, R 2 R can be expressed by one of the above defined formulas (3) or (4), preferably by formula (4). 2 When expressed by formula (4), L can be selected from direct bonds, alkylene, -CR3R4-, -C(=O)-, -C(=O)-O-Alk-OC(=O)-, -SO-, -SO2-, -C(=CCl2)-, and -CR5R6-Ph-CR7R8-. During the ceremony, R3 and R4 may be independently selected from H, alkyl, cycloalkyl, aryl, haloalkyl, and perfluoroalkyl, or R3 and R4 may form a ring together with the carbon atoms to which they are bonded; R5, R6, R7, and R8 are independently selected from H, alkyl, cycloalkyl, aryl, haloalkyl, and perfluoroalkyl; Alk is an alkylene; Ph is phenylene substituted with one or more groups optionally selected from alkyl, cycloalkyl, aryl, and halogen atoms.

[0134] More specifically, R 2 This can correspond to residues (without OH, COOH, and / or amino groups) of an aromatic polyol, polyacid, polyamine, hydroxy acid, or hydroxyamine, which may be substituted.

[0135] For example, R 2This may be a residue of an optionally substituted aromatic polyol, polyacid, polyamine, hydroxy acid, or hydroxyamine, comprising one to three, preferably one or two 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 with formaldehyde (also called novolacs), phenylenediamine, toluylenediamine, xylylenediamine, diaminobiphenyl, diaminodiphenyl ether, diaminodiphenylmethane, diaminodiphenyl sulfone, aminophenol, (aminophenoxy)phenol, and the like.

[0136] More specifically, R 2 can be a bisphenol residue that may be substituted. Suitable examples of bisphenols include 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.

[0137] In another embodiment, R 2 R can be an aliphatic linker such as alkylene, heteroatom-containing alkylene, cycloalkylene, heterocycloalkylene, or a combination thereof. In such cases, R 2 The material is preferably an alkylene, a heteroatom-containing alkylene, a cycloalkylene, or a combination thereof.

[0138] More specifically, R 2This can be expressed by one of the following equations (10) to (20): TIFF2026520472000019.tif162170[In the formula, R' e And L are 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.

[0139] In particular, R 2 This can be expressed by one of the above-defined formulas (10), (11), (12), (13), (15), (16), (17), or (19), preferably by one of the formulas (10), (11), or (12).

[0140] Alternatively, R 2 This can be expressed by one of the above-defined formulas (10), (12), (13), or (14), where, Each R g , R' g and R h is independently H or alkyl, preferably H, methyl, or ethyl; d is between 1 and 12, preferably between 2 and 10.

[0141] R 2This can correspond to residues (without OH, COOH, and / or amino groups) of an aliphatic polyol, polyacid, polyamine, hydroxyacid, or hydroxyamine, which may be substituted.

[0142] 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, 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), pentaerythritol, glycerol, dianhydrohexitol (i.e., isosorbide, isomannide, iso) (Zide), hydrogenated 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, diaminocyclohexane, methylcyclohexanediamine, bis(aminomethyl)cyclohexane, diaminodecahydronaphthalene, dimethyldiaminodicyclohexylmethane, diaminodicyclohexylmeth The residues may be substituted aliphatic polyols, polyacids, polyamines, hydroxy acids, or hydroxyamines, selected from 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, dodecanediic acid, citric acid, 1,2-, 1,3-, or 1,4-cyclohexanedicarboxylic acid, glycolic acid, 12-hydroxystearic acid, ethanolamine, or diethanolamine.

[0143] Alternatively, R 2 This can correspond to residues of epoxidized polyunsaturated compounds, i.e., residues of compounds having at least two epoxidized non-aromatic carbon-carbon double bonds. As used herein, the term “residues of epoxidized polyunsaturated compounds” means residues obtained by removing terminal groups containing epoxide rings from a compound. For example, an epoxidized polyunsaturated compound may be given by the following formula: If TIFF2026520472000020.tif18170 is present, the residues of the epoxidized polyunsaturated compound correspond to the following formula: TIFF2026520472000021.tif11170

[0144] Alternatively, R 2 This can correspond to residues of an epoxidized oil. As used herein, the term “residues of an epoxidized oil” means residues obtained by removing epoxide-containing terminal groups from an oil. For example, an epoxidized oil may have the following formula: TIFF2026520472000022.tif41170[in the formula, Each R 4 These are 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 present, the residues of the epoxidized oil correspond to the following formula: TIFF2026520472000023.tif41170

[0145] If n1 is 0, R 2 Preferably, it is selected from one of formulas (3) to (19).

[0146] If n2 is 0, R 2 It is preferable that the bond is directly linked or alkylene.

[0147] If both n1 and n2 are non-zero, R 2 It is preferable that the bond is directly linked or alkylene.

[0148] In the photoinitiators of formulas (I) and (Ia) to (In), each R 4 R is independently H, an optionally substituted alkyl, or an optionally substituted alkenyl. In one embodiment, each R 4 is H. In another embodiment, each R 4 is an optionally substituted alkyl or optionally substituted alkenyl. In yet another embodiment, R 4 The base part 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.

[0149] R 2 However, R 4 If the part of formula (1) is an alkyl which may be substituted, then Y is preferably a direct bond.

[0150] In the photoinitiators of formulas (I), (Ic), (Id), and (Ig), each R 5 These are independently H, alkyl, aryl, or -CH2-CH(OH)-CH2-XR 3 -Q. In particular, each R 5 These are independently H, alkyl, or -CH2-CH(OH)-CH2-XR 3 -Q is the answer.

[0151] In a particularly preferred embodiment, the photoinitiator of formula (I) is according to one of the following formulas (Ia), (Ib), (Ic), or (Ie), preferably according to one of formulas (Ia) or (Ie), and more preferably according to formula (Ia): TIFF2026520472000024.tif126170[In the formula, n3, n4, n5, and n7 are independently 2, 3, or 4, preferably 2 or 3; Each chromophore portion Q conforms to the above-defined formula (A) or (B), preferably each chromophore portion Q conforms to the above-defined formula (A1) or (B1), and more preferably each chromophore portion Q conforms to the above-defined formula (B1); Each X independently, -NR 1 -, -O- or *-C(=O)-O-, preferably -NR 1 -or *-C(=O)-O-, more preferably *-C(=O)-O-; Each R 1 is independently H or alkyl; Each R 2 This is independently an alkylene or a heteroatom-containing alkylene, preferably an alkylene, and more preferably an alkylene represented by one of the formulas (10), (12), (13), or (14) defined above; Each R 3 These are independently, directly bonded, alkylene of formula (C-1) as defined above, oxyalkylene of formula (C-2) as defined above, or aminoalkylene of formula (C-5) as defined above, preferably directly bonded, alkylene of formula (C-1), or oxyalkylene of formula (C-2), more preferably oxyalkylene of formula (C-2); Each R 4 is H; Each R 5 These are independently H, alkyl, or -CH2-CH(OH)-CH2-XR 3 -Q, where X, R 3 , and Q are as defined above; The symbol * is R 3 [Represents a connection point to].

[0152] In a particularly preferred embodiment, the photoinitiator of formula (I) follows one of the following formulas (I-1) to (I-9): TIFF2026520472000025.tif220170TIFF2026520472000026.tif89170

[0153] Method for obtaining a photoinitiator The present invention also relates to a method for preparing a photoinitiator. The method can be used to prepare a photoinitiator according to the present invention. The method includes the step of reacting a polyepoxide component with a chromophore-containing component having at least one epoxide-reactive group, i.e., a group that can open an epoxide ring. The ring-opening of the epoxide ring of the polyepoxide component forms a free hydroxyl group, which may be useful for further reactions, such as obtaining a photoreactive urethane oligomer, a photoreactive polyester oligomer, or a polymerizable photoinitiator using a photoinitiator, as detailed below.

[0154] The photoinitiator of the present invention can be obtained using n equivalents of a chromophore-containing component per equivalent of a polyepoxide component. As used herein, n is the number of moles of epoxide rings present in the polyepoxide component. The value of n can be obtained by multiplying the number of moles of the polyepoxide component by its epoxide functional value (i.e., the number of epoxide rings on the polyepoxide compound). For example, if the photoinitiator of the present invention is obtained using 1 mole of a polyepoxide compound having 2 epoxide rings, then n is equal to 2. If the polyepoxide component contains a mixture of polyepoxide compounds, then n corresponds to the total number of moles of epoxide rings in the mixture.

[0155] The reaction between the polyepoxide component and the chromophore-containing component can be carried out in the presence of at least one catalyst. The catalyst can be any substance capable of catalyzing the ring-opening of the epoxide, particularly when the epoxide-reactive group of the chromophore-containing component is a carboxylic acid, alcohol, or thiol. In particular, the catalyst can be selected from the following: - Metal halides such as iron chloride, aluminum chloride, or boron trifluoride; - Quaternary ammonium salts such as benzyltriethylammonium chloride, tetrapropylammonium chloride, or tetrabutylammonium bromide; - Mineral acids such as sulfuric acid, - Organic acids such as acetic acid, trifluoromethanesulfonic anhydride ((CF3SO2)2O, Tf2O), methanesulfonic anhydride ((CH3SO2)2O), trifluoroacetic anhydride ((CF3CO)2O), and acetic anhydride ((CH3CO)2O), - Organometallic compounds, e.g., tin catalysts (e.g., dibutyltin dilaurate), bismuth carboxylate complexes (e.g., 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; - Quaternary phosphonium salts such as ethyltriphenylphosphonium bromide or tetrapropylphosphonium chloride, - Tertiary amines such as 2-phenylimidazoline, - Tertiary phosphines such as triphenylphosphine; And combinations of these.

[0156] The amount of catalyst may be less than 5% by weight, less than 2% by weight, less than 1% by weight, or even less than 0.5% by weight, based on the total weight of the polyepoxide component and the chromophore-containing component.

[0157] The reaction between the polyepoxide component and the chromophore-containing component can be carried out in the presence of a stabilizer, particularly one selected from hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ, 4-methoxyphenol), 4-tert-butylcatechol (TBC), and 3,5-di-tert-butyl-4-hydroxytoluene (BHT), phenothiazine (PTZ), and mixtures thereof.

[0158] The reaction between the polyepoxide component and the chromophore-containing component can be carried out in the presence of a solvent. Alternatively, this process 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 other components used in the preparation of the self-crosslinking urethane (meth)acrylate.

[0159] Examples of suitable solvents include aliphatic hydrocarbons, such as n-pentane, n-hexane, n-heptane, octane, cyclohexane, or methylcyclohexane; aromatic hydrocarbons, such as benzenetoluene or xylene; halogenated hydrocarbons, such as dichloromethane, chloroform, or trichloroethane; ketones, such as acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclopentanone, or cyclohexanone; esters, such as methyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, or butyl acetate; ethers, such as diethyl ether, diisopropyl ether, dibutyl ether, ethylene glycol diethyl ether, tetrahydrofuran, or tetrahydropyran; carbonates, such as diethyl carbonate; and combinations thereof.

[0160] The reaction between the polyepoxide component and the chromophore-containing component can be carried out at temperatures of 50 to 150°C, particularly 70 to 130°C.

[0161] The reaction between the polyepoxide component and the chromophore-containing component can be carried out until the epoxide reactive group value (ERV) and / or epoxy value (EV) is less than 10 mg KOH / g, particularly less than 5 mg KOH / g, and more specifically less than 2 mg KOH / g. The AV and / or EV can be adjusted as needed by adding further polyepoxide components or chromophore-containing components as the reaction progresses.

[0162] The reaction between the polyepoxide component and the chromophore-containing component can be carried out for 1 to 72 hours, particularly for 2 to 24 hours.

[0163] After completion of the reaction, the reaction medium can be washed one or more times with an aqueous solution, for example an aqueous solution of sodium chloride. The (one or more) solvents can be evaporated from the resulting organic phase.

[0164] Chromophore-containing component a) The photoinitiator of the present invention can be derived from the reaction of one or more chromophore-containing compounds. The one or more chromophore-containing compounds used to obtain the photoinitiator are referred to herein as component a).

[0165] As used herein, the term "chromophore-containing compound" means a compound containing at least one chromophore moiety as defined above. In particular, the chromophore moiety can correspond to the chromophore moiety Q as defined above for the photoinitiator of the present invention.

[0166] The chromophore-containing compound further has at least one epoxide-reactive group. In particular, the epoxide-reactive group can correspond to -X-H, where X is as defined above for the photoinitiator of the present invention. More specifically, the epoxide-reactive group -X-H can correspond to one of the groups -NHR 1 , -OH, -SH, *-C(=O)-OH, or *-C(=O)-NHR 1 where R 1 is independently H, alkyl, or aryl.

[0167] In particular, component a) comprises at least one compound according to the following formula (II): Q-R 3 -X-H (II) and may contain, consist of, or consist essentially of them, where Q, X, and R 3 are as defined above.

[0168] Q, X, and R as described above for the photoinitiator of the present invention3 All preferred embodiments of the same apply to component a).

[0169] More specifically, chromophore-containing component a) contains, consists of, or essentially consists of at least one compound according to formulas (II-a) to (II-f): TIFF2026520472000027.tif78170[In the formula, R 3 This is selected from directly bonded alkylenes of formula (C-1) as defined above, oxyalkylenes of formula (C-2) as defined above, and aminoalkylenes of formula (C-5) as defined above, preferably oxyalkylenes of formula (C-2); Each R c independently of H, alkyl, Ar, -S-Ar, or -O-Ar, where Ar is aryl, in particular H, methyl, Ph, -S-Ph, or -O-Ph, where Ph is phenyl; Each R' c is independently H or alkyl, and in particular H or methyl; Each R d (i) is independently H, halogen, alkoxy, alkyl, or -C(=O)-Ar, where Ar is aryl, in particular H, F, Cl, methyl, ethyl, isopropyl, or -C(=O)-Ph (where Ph is phenyl).

[0170] More specifically, the chromophore-containing component a) contains, consists of, or essentially consists of compounds according to formula (II-e).

[0171] Polyepoxide component b) The photoinitiator of the present invention is derived from the reaction of one or more polyepoxide compounds. The one or more polyepoxide compounds used to obtain the photoinitiator are referred to herein as component b).

[0172] As used herein, the term "polyepoxide compound" means a compound containing at least two epoxide rings.

[0173] An epoxide ring may consist of one or more of the following groups: glycidyl ether groups, glycidyl ester groups, glycidylamine groups, glycidylamide groups, alicyclic epoxide groups, epoxy groups derived from the epoxidation of acyclic carbon-carbon double bonds, and combinations thereof.

[0174] Polyepoxide compounds can have two epoxide rings. In particular, polyepoxide compounds can have two glycidyl ether groups, two glycidyl ester groups, or two epoxy groups derived from the epoxidation of an acyclic carbon-carbon double bond.

[0175] Polyepoxide compounds can have three epoxide rings. In particular, polyepoxide compounds can have three glycidyl ether groups.

[0176] Polyepoxide compounds can have four epoxide rings. In particular, polyepoxide compounds can have four glycidyl ether groups.

[0177] In particular, component b) contains, consists of, or essentially consists of at least one compound that conforms to the following formula (III): TIFF2026520472000028.tif34170[in the formula, n1 is 0, 1, 2, 3, or 4; n2 is 0, 1, 2, 3, or 4; The sum of n1 + n2 is equal to 1, 2, 3, or 4; Each Y is independently directly bonded, with #-O-CH2-, #-C(=O)-O-CH2-, and #-NR 6 -CH2-, or #-C(=O)-NR 7 -CH2-; Each Z is independently a direct bond, -CH2-OC(=O))-#, or -C(=O)-O-#; R 2 This is a direct link or linker; Each R 4 is independently H, optionally substituted alkyl, or optionally substituted alkenyl; Each R 6 and R 7 are independently H, alkyl, aryl, or a glycidyl group according to the following formula: TIFF2026520472000029.tif9170; The symbol # represents the bonding point to R 2 .

[0178] Regarding the photoinitiator of the present invention, the preferred embodiments of n1, n2, Y, Z, R 2 , and R 4 all apply equally to component b).

[0179] More specifically, component b) may contain, consist of, or consist essentially of at least one compound according to any one of the following formulas (III-a) to (III-n): TIFF2026520472000030.tif240170TIFF2026520472000031.tif151170[wherein, R 2 , R 4 , and R 5 are as defined herein; n'3, n'4, n'7, n' 14 , and n' 15 are independently 2, 3, or 4, preferably 2 or 3; n'5 and n'6 are 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 [These are independently 1, 2, or 3, preferably 1.]

[0180] Compounds of formulas (III-a), (III-b), (III-c), (III-e), (III-f), (III-g), and (III-h) are preferred. Compounds of formulas (III-a), (III-b), (III-c), and (III-e) are particularly preferred. More specifically, compound (III-a) is preferred.

[0181] More specifically, component b) is not limited to, but includes diglycidyl ether, 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, 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, 1,8-octanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, and 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, glycerol triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, di(trimethylolpropane)tetraglycidyl ether, pentaerythritol tetraglycidyl ether, diglycidylcyclohexane 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 triglycidyl ether, Hydrogenated bisphenol A diglycidyl ether, Hydrogenated bisphenol B diglycidyl ether, Hydrogenated bisphenol F diglycidyl ether, Hydrogenated bisphenol S diglycidyl ether, Bisphenol A diglycidyl ether, Bisphenol AP diglycidyl ether, Bisphenol AF diglycidyl ether, Bisphenol B diglycidyl ether, Bisphenol BP diglycidyl ether, Bisphenol C diglycidyl ether, Bisphenol C2 diglycidyl ether, Bisphenol F diglycidyl ether, Bisphenol G diglycidyl ether, Bisphenol M diglycidyl A Ter, bisphenol S diglycidyl ether, bisphenol P diglycidyl ether, bisphenol PH diglycidyl ether, bisphenol TMC diglycidyl ether, bisphenol Z diglycidyl ether, dinitrobisphenol A diglycidyl ether, tetrabromobisphenol A diglycidyl ether, diglycidyl phthalate, diglycidyl terephthalate, diglycidyl isophthalate, 4-(diglycidylamino)phenylglycidyl ether, 4,4'-methylenebis(N,N-diglycidylaniline), It comprises, consists of, or essentially consists of at least one compound selected from 4-[4-[bis(oxiran-2-ylmethyl)amino]phenoxy]-N,N-bis(oxiran-2-ylmethyl)aniline, 4-(2-(4-(bis(oxiran-2-ylmethyl)amino)phenoxy)ethoxy)-N,N-bis(oxiran-2-ylmethyl)benzeneamine, limonene dioxide (4-vinyl-1-cyclohexene dioxide), epoxidized vegetable oil, triglycidyl isocyanurate, or a combination thereof.

[0182] More specifically, component b) comprises, consists of, or essentially consists of at least one compound selected from 1,2,7,8-diepoxyoctane, trimethylolpropane triglycidyl ether, and 1,4-butanediol diglycidyl ether.

[0183] use The photoinitiator of the present invention can be used as a photoinitiation system in radiation-curable compositions, particularly UV-curable compositions or LED-curable compositions.

[0184] As used herein, "UV-curable composition" means a composition that is at least partially cured by exposure to UV light emitted from a mercury light source, particularly a mercury vapor lamp, and "LED-curable composition" means a composition that is at least partially cured by exposure to UV light emitted from an LED light source, particularly an LED light source having an emission band in the range of 365 to 420 nm.

[0185] Other curing methods, such as heating, may be combined with UV light.

[0186] The photoinitiators of the present invention can be used in photopolymerization reactions. Photopolymerization reactions can be used to photopolymerize (e.g., cure) one or more ethylenically unsaturated compounds. As used herein, the term “ethylenically unsaturated compound” means a compound containing a polymerizable carbon-carbon double bond. A polymerizable carbon-carbon double bond is a carbon-carbon double bond that can react with another carbon-carbon double bond in a polymerization reaction. Polymerizable carbon-carbon double bonds generally belong to a group selected from acrylates (including cyanoacrylates), methacrylates, acrylamides, methacrylamides, styrenes, maleates, fumarates, itaconates, allyls, propenyls, vinyls, and combinations thereof, preferably selected from acrylates, methacrylates, and vinyls, and more preferably selected from acrylates and methacrylates. A carbon-carbon double bond of a phenyl ring is not considered a polymerizable carbon-carbon double bond.

[0187] In one embodiment, the ethylenically unsaturated compound includes (meth)acrylate-functionalized compounds, particularly (meth)acrylate-functionalized compounds selected from (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, amine-modified acrylates, and mixtures thereof.

[0188] The photoinitiator of the present invention can be used to obtain a photoreactive oligomer. The photoreactive oligomer can be obtained by reacting the photoinitiator of the present invention with at least one compound having at least two hydroxyl-reactive groups (i.e., groups that can react with the hydroxyl groups of the photoinitiator). Examples of suitable hydroxyl-reactive groups include isocyanate groups, carboxylic acid groups, and their derivatives (i.e., esters and anhydrides). For example, the photoinitiator of the present invention can be used to obtain a photoreactive urethane oligomer, that is, the photoinitiator can be used as part or all of a polyol component that reacts with a polyisocyanate component to yield a urethane oligomer.

[0189] A urethane oligomer having a photoreactive portion in its skeleton can be called a photoreactive urethane oligomer. In particular, a photoreactive urethane oligomer can be a photoreactive urethane (meth)acrylate oligomer. A photoreactive urethane (meth)acrylate oligomer is, a) A polyol component comprising at least one photoinitiator of formula (I) according to the present invention and optionally one or more other polyols; b) Polyisocyanate components; and c) Hydroxyl-functionalized (meth)acrylate components It can be obtained by the reaction.

[0190] Photoreactive urethane oligomers can be used in combination with one or more ethylenically unsaturated compounds as defined above to obtain curable compositions. In particular, curable compositions may be coating compositions, ink compositions, varnish compositions, encapsulated or potting compositions, 3D printing compositions, molding compositions, sealant compositions, adhesive compositions, nail polish compositions, or dental compositions.

[0191] The curable composition comprising a photoreactive urethane oligomer based on the photoinitiator of the present invention may, advantageously, not require an additional photoinitiator. The cured product obtained by curing such a curable composition may exhibit a lower extractable amount compared to a conventional composition comprising a urethane oligomer and an additional photoinitiator.

[0192] The photoinitiator of the present invention can be used to obtain a photoreactive polyester oligomer; that is, the photoinitiator can be used as part or all of the polyol component that reacts with a polyacid component to yield a polyester oligomer.

[0193] The photoinitiator of the present invention can be used to obtain a polymerizable photoinitiator, that is, it can be used to obtain a polymerizable photoinitiator by converting at least a portion of the hydroxyl groups of the photoinitiator to (meth)acrylate groups through reaction with a (meth)acrylic agent such as (meth)acrylic acid, (meth)acrylic anhydride, or (meth)acrylic acid chloride.

[0194] The present invention will be described in more detail with reference to the following embodiments, but it should be understood that the present invention is not limited thereto. [Examples]

[0195] Example 1: The thioxanthone (TX)-based diol of formula (Io) was prepared according to the following scheme: TIFF2026520472000032.tif601702-(carboxymethoxy)thioxanthone (31.8 g, 0.1054 mol, Lambson); 1,4-butanediol diglycidyl ether (GE-21, CVC, 15 g, 0.1289 mol epoxide ring); benzyltriethylammonium chloride (BTEAC, 0.14 g, 0.3 wt%, Aldrich) as a catalyst; and 50 wt% cyclopentanone as a process solvent were placed in a three-necked flask equipped with a mechanical stirrer under nitrogen and heated to 125°C. The reaction was then continued at 125°C until the termination criteria of acid value (AV) < 2 mg KOH / gm and epoxy value (EV) < 2 mg KOH / gm were reached (approximately 3 hours). As the reaction progressed, AV or EV was adjusted as needed by adding CMTX or 1,4-butanediol diglycidyl ether. The final diol product (Io) was a dark brown liquid and had an acceptable FT-IR and 1 The 1H NMR spectral characteristics are shown.

[0196] Example 2: The thioxanthone (TX)-based triol of formula (Ip) was prepared according to the following scheme: TIFF2026520472000033.tif771702-(carboxymethoxy)thioxanthone (CMTX, 35.2 g, 0.1167 mol), trimethylolpropane triglycidyl ether (18.7 g, 0.136 mol epoxide ring, GE-30, CVC), benzyltriethylammonium chloride (BTEAC, 0.14 g, 0.26 wt%) as a catalyst, and cyclopentanone (54 g) as a process solvent were mixed and heated to 130°C. The reaction was then continued at 130°C until the termination criteria of acid value (AV) < 2 mg KOH / gm and epoxy value (EV) < 2 mg KOH / gm were reached (approximately 3 hours). Depending on the progress of the reaction, AV or EV was adjusted as needed by adding CMTX or trimethylolpropane triglycidyl ether. The final product (Ip) is a dark brown liquid, and the expected FT-IR and 1 The 1H NMR spectral characteristics are shown.

[0197] Example 3: The thioxanthone (TX)-based triol of formula (Iq) was prepared according to the following scheme: TIFF2026520472000034.tif771702-(carboxymethoxy)thioxanthone (CMTX, 31.8 g, 0.1054 mol); 1,2,7,8-diepoxyoctane (7.49 g, approximately 0.105 mol of epoxide rings); benzyltriethylammonium chloride (BTEAC, 0.14 g, 0.3 wt%) as a catalyst; and cyclopentanone (40 g, to produce approximately 50 wt% solution) as a process solvent were placed in a three-necked flask equipped with a mechanical stirrer under nitrogen and heated to 125°C. The reaction was continued at 125°C until the termination criteria of AV < 2 mg KOH / gm and EV < 2 mg KOH / gm were reached (approximately 3 hours). As the reaction progressed, AV or EV was adjusted as needed by adding CMTX or 1,2,7,8-diepoxyoctane. The final product (Iq) was the expected FT-IR and 1 The 1H NMR spectral characteristics are shown.

[0198] While embodiments are described herein in order to provide a clear and concise description, it will be understood that the embodiments can be combined or 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 aspects of the present invention described herein.

[0199] The above description of various forms of the present invention is presented for illustrative and explanatory purposes only. It is not intended to be exhaustive or to limit the invention to the exact forms disclosed. Many modifications or variations are possible in light of the above teachings. The forms discussed have been selected and described to best illustrate the principles of the present invention and their practical applications, thereby enabling those skilled in the art to utilize the invention in various forms and variations suited to specific intended uses. All such modifications and variations fall within the scope of the invention as determined by the appended claims, construed in accordance with fair, legal, and equitable terms.

Images