Polyhydroxylated Photoinitiators

Abstract

The present invention relates to novel photoinitiators having hydroxyl and / or (meth)acrylate groups. The present invention also relates to compositions comprising these photoinitiators and to their use for photopolymerizing ethylenically unsaturated compounds.

Description

[Technical field]

[0001] The present invention relates to novel photoinitiators having hydroxyl and / or (meth)acrylate groups. The present invention also relates to compositions comprising these photoinitiators and to their use for photopolymerizing ethylenically unsaturated compounds, in particular in aqueous curable compositions. [Background technology]

[0002] Radiation-curable compositions containing ethylenically unsaturated compounds can be polymerized by exposure to radiation, such as ultraviolet (UV) light. For rapid and effective curing, photoinitiators are often used. Photoinitiators form radical species upon irradiation with photons, initiating the free radical polymerization of unsaturated groups, resulting in hardening of the material.

[0003] Free radical photoinitiators can have two different mechanisms of action and are classified according to their mechanism as Norrish Type I and Norrish Type II photoinitiators. Norrish Type I photoinitiators cleave upon exposure to radiation to generate radical species that can initiate polymerization of unsaturated compounds. Norrish Type II photoinitiators are compounds that do not fragment upon exposure to radiation and therefore typically do not 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 photoinitiator and the co-initiator generates radical species that can initiate polymerization of UV-curable resins.

[0004] The most common Type II photoinitiators are diaryl ketones such as benzophenones (e.g., SpeedCure® BP available from Arkema) or thioxanthones such as 2-isopropylthioxanthone (SpeedCure® 2-ITX available from Arkema) or diethylthioxanthone (SpeedCure® DETX available from Arkema).

[0005] One well-recognized challenge when using UV-curing systems in coatings and adhesives applications is the fate of photo-by-products generated during the cure process. In the case of typical α-cleavage photoinitiators, the generation of benzaldehyde (and often related compounds) is often a significant concern, both in terms of toxicity and product odor. Such concerns become particularly important when the radiation-curable material is being considered for use in applications involving skin or food contact. A variety of effective approaches have been undertaken to reduce the odor and extractable by-product content of UV-curable materials. One approach has been to use copolymeric or polymeric photoinitiators that are chemically incorporated into the cured polymer matrix rather than remaining as small molecules in the irradiated material (see (a) Fouassier, JP: Rabek, JF eds. Radiation Curing in Science and Technology, 1993, Elsevier Appl. Sci., vol. 2, 283-321; (b) Fouassier, JP Photoinitiation, Photopolymerization and Photocuring, Fundamentals and Applications, 1995, Hanser Publishers, 71-73).

[0006] The use of polymerizable or polymeric H-abstraction photoinitiators offers the possibility of creating systems with, in principle, zero extractable components associated with the photoinitiating system. Various groups have presented systems based on poly(vinyl benzophenone) and its copolymers or polymers derived from acrylated benzophenone derivatives (see (a) David, C.; Demarteu, W.; Geuskens, G. Polymer, 1969, 10, 21-27; (b) Carlini, C.; Ciardelli, F.; Donati, D.; Gurzoni, F. Polymer, 1983, 24, 599-606). The direct use of acrylated benzophenones has also been disclosed (US Pat. No. 3,429,852). Unfortunately, these type II systems often suffer from challenges related to photoefficiency compared to similar small molecule photoinitiating systems. Therefore, it is often most desirable to use polymeric photoinitiators rather than polymeric photoinitiators.

[0007] The increasing demand for water-based polymerizable systems has prompted the development of water-soluble or water-dispersible photoinitiators. The market-leading product, SpeedCure 2959, has limited water solubility of 0.5% by weight, which is often below the required loading. Quaternary or tertiary salts of photoinitiators that show good water solubility have been tested, but the resulting coatings become more hydrophilic (hygroscopic) and cause swelling. The salts retard the radical polymerization, cause yellowing of the coating, and the high cost of these materials makes them unattractive to industry.

[0008] Thus, there continues to be a need in the art for improved H-abstraction photoinitiators useful in the manufacture of radiation curable adhesive and coating formulations that do not suffer from the above-identified shortcomings and still produce low odor products with little (or no) inherent extractable photochemical by-products. The present development satisfies this need.

[0009] The photoinitiators of the present invention have multiple hydroxyl groups which advantageously enhance their solubility in aqueous systems and polar solvents. The increased water solubility allows for higher photoinitiator concentrations, faster cure rates, and significantly improved ease of formulation. Furthermore, the hydroxyl groups provide suitable functionalization points since they can be easily (meth)acrylated by esterification with (meth)acrylic acid or transesterification with (C1-C6) alkyl (meth)acrylates, thus reducing the migration potential of the resulting polymerizable photoinitiators.

[0010] Curable compositions including the photoinitiators of the present invention may offer one or more of the following advantages: - Its low migration allows it to be used in sensitive applications (food and beverage packaging, food and beverage processing, pharmaceutical packaging, nail polish, dental products, textiles in contact with the human body, medical devices, water pipes), - Low viscosity, - Highly reactive to UV rays, - Less yellowing, - Low or no odor; - Good mechanical properties after curing (e.g. hardness, scratch resistance, solvent resistance). Summary of the Invention

[0011] The first aspect of the present invention is a compound represented by the following formula (I): The compound is according to TIFF2025504613000001.tif54170, where PI, L, M, X, Y, Z, m, n, p, and q are as defined herein.

[0012] Another aspect of the present invention is a method for the preparation of a compound of formula (I) according to the present invention, comprising the steps of: TIFF2025504613000002.tif110170, where PI, L, M, X, Y, Z, R", m, n, p and q are as described herein.

[0013] Another aspect of the present invention is a photoinitiator composition comprising a mixture of at least two different compounds of formula (I) according to the present invention.

[0014] Another aspect of the present invention is a photoinitiator composition comprising a compound of formula (I) according to the present invention and an amine synergist other than a compound of formula (I), preferably an amine synergist having a tertiary amine group.

[0015] The present invention also aims to provide a process for preparing a compound of formula (I) according to the present invention, in which at least a part of the M groups are (meth)acryloyl, which comprises reacting a compound of formula (I) in which all of the M groups are H with (meth)acrylic acid or a (C1-C6) alkyl (meth)acrylate in the presence of a catalyst.

[0016] The present invention also aims to provide a method for photopolymerizing one or more ethylenically unsaturated compounds, which comprises contacting the one or more ethylenically unsaturated compounds with a compound of formula (I) according to the present invention or with a photoinitiator composition according to the present invention and irradiating the mixture, in particular with visible, near UV and / or UV light.

[0017] Another aspect of the present invention is a method for producing a a) a compound of formula (I) according to the present invention or a photoinitiator composition according to the present invention; b) Ethylenically unsaturated compounds The curable composition comprises:

[0018] Another aspect of the present invention is a method for producing a a) a compound of formula (I) according to the present invention or a photoinitiator composition according to the present invention; c) Unsaturated polymer dispersions or emulsions The curable composition comprises:

[0019] Another aspect of the present invention is a method for preparing a cured product, which comprises curing the curable composition according to the present invention, in particular by exposing the curable composition to radiation, such as UV, near UV and / or visible light.

[0020] Another aspect of the invention is an inkjet printing method comprising jetting a curable composition according to the invention onto a substrate.

[0021] Another aspect of the invention is a substrate to which the curable composition according to the invention has been applied and cured, particularly substrates that are food and beverage packaging, pharmaceutical packaging, textiles, nails, teeth, medical devices, food and beverage processing equipment, water pipes.

[0022] Another aspect of the present invention is the use of a compound of formula (I) according to the present invention or a photoinitiator composition according to the present invention in a photopolymerization reaction.

[0023] Another aspect of the present invention is the use of a compound of formula (I) according to the present invention, or a photoinitiator composition according to the present invention, as a photoinitiator or photoinitiator system in a radiation curable composition, in particular as a photoinitiator or photoinitiator system in a UV or LED curable composition.

[0024] Another aspect of the present invention is the use of compounds of formula (I) according to the present invention, in which at least a portion of the M groups are (meth)acryloyl, for reducing the amount of extractables from a cured layer of a curable composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] [Definition] In this application, the term "including a / an" means "including one or more."

[0026] Unless otherwise stated, weight percentages in a compound or composition are expressed based on the weight of the compound or weight of the composition, respectively.

[0027] The term "(meth)acryloyloxy" means a radical of the formula -OC(=O)-CH(R)=CH2, where R is H or Me. The term "(meth)acryloyloxy" encompasses both an acryloyloxy radical, where R is H, and a methacryloyloxy radical, where R is Me.

[0028] The term "(meth)acryloyl" means a radical of formula -C(=O)-CH(R)=CH2, where R is H or Me. The term "(meth)acryloyl" encompasses both an acryloyl radical, where R is H, and a methacryloyl radical, where R is Me.

[0029] The term "photoreactive compound, group, or linker" refers to a compound, group, or linker that participates in and / or initiates a photochemical reaction upon exposure to electromagnetic radiation. Photoreactive compounds, groups, or linkers typically include a photoinitiator moiety and, optionally, one or more synergist moieties.

[0030] The term "photoinitiator moiety" means a moiety that contains a group capable of absorbing light and generating a reactive species useful for initiating a polymerization reaction.

[0031] The term "synergist moiety" means a moiety that contains a hydrogen donor group capable of reacting with an activated photoinitiator moiety by hydrogen abstraction to generate a free radical species.

[0032] The term "aryl" refers to an optionally substituted polyunsaturated aromatic group. An aryl may contain a single ring (i.e., phenyl) or more than one ring, in which at least one ring is aromatic. When an aryl contains more than one ring, the rings may be fused together via a covalent bond (e.g., biphenyl). The aromatic ring may optionally contain one to two additional fused rings (i.e., cycloalkyl, heterocycloalkyl, or heteroaryl). The term "aryl" also includes partially hydrogenated derivatives of the above carbocyclic systems. Examples include phenyl, naphthyl, biphenyl, phenanthrenyl, and naphthacenyl.

[0033] The term "alkyl" means a group of the formula -C n H 2n+1where n is 1 to 20. The alkyl group may be straight or branched. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, 2-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 2,2-dimethylbutyl, n-heptyl, 2-ethylhexyl, and the like.

[0034] The term "heteroatom-containing alkyl" means an alkyl interrupted by one or more heteroatoms independently selected from O, N or S.

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

[0036] The term "cycloalkyl" means a monovalent saturated alicyclic hydrocarbon group containing a ring. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl and isobornyl.

[0037] The term "heterocycloalkyl" means a cycloalkyl having at least one ring atom which is a heteroatom selected from O, N or S.

[0038] The term "alkoxy" means a radical of the formula -O-alkyl, wherein alkyl is as defined above.

[0039] The term "aryloxy" means a radical of the formula -O-aryl, where aryl is as defined above.

[0040] The term "thioalkyl" means a radical of the formula -S-alkyl, wherein alkyl is as defined above.

[0041] The term "thioaryl" means a radical of the formula -S-aryl, where aryl is as defined above.

[0042] The term "alkenyl" denotes a monovalent acyclic hydrocarbon radical containing at least one C=C double bond. Alkenyl may be linear or branched.

[0043] The term "alkynyl" denotes a monovalent acyclic hydrocarbon radical containing at least one C≡C triple bond. Alkynyl may be straight-chain or branched.

[0044] The term "aralkyl" means an aryl substituted with an alkyl group. An example of an aralkyl group is tolyl.

[0045] The term "alkaryl" means an alkyl substituted with an aryl group. An example of an alkaryl group is benzyl (-CH2-phenyl).

[0046] The term "aralkyloxy" means a radical of the formula -O-aralkyl, wherein aralkyl is as defined above.

[0047] The term "alkaryloxy" means a radical of the formula -O-alkaryloxy, where alkaryl is as defined above.

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

[0049] The term "alkylamino" means an alkyl substituted with at least one amino group.

[0050] The term "alkylthiol" means an alkyl substituted with at least one thiol group.

[0051] The term "hydroxyalkyl" means an alkyl substituted with at least one hydroxy group.

[0052] The term "haloalkyl" means an alkyl substituted with at least one halogen.

[0053] The term "alkylene" or "alkanediyl" means a group of the formula C m H 2m+2 By removing one hydrogen atom at each attachment point of the linker from an alkane of the formula: Alkylene may be divalent, trivalent, tetravalent, or have higher valence.

[0054] The term "alkoxylated" refers to a compound, group or linker that contains one or more oxyalkylene moieties, in particular one or more oxyethylenes selected from oxyethylene (-O-CH2-CH2-), oxypropylene (-O-CH2-CH(CH3)- or -O-CH(CH3)-CH2-), oxybutylene (-O-CH2-CH2-CH2-CH2-) and mixtures thereof. For example, an alkoxylated compound, group or linker may contain from 1 to 30 oxyalkylene moieties.

[0055] The term "linker" refers to a polyvalent group. A linker may link at least two parts of a compound together, in particular from 2 to 16 parts of a compound together. For example, a linker that links two parts of a compound together is called a bivalent linker, a linker that links three parts of a compound together is called a trivalent linker, etc.

[0056] The term "aliphatic compound, group or linker" refers to a non-aromatic acyclic compound, group or linker. It may be linear or branched, saturated or unsaturated. It may be substituted with one or more groups selected from, for example, alkyl, hydroxyl, halogen (Br, Cl, I), isocyanate, carbonyl, amine, carboxylic acid, -C(=O)-OR', -C(=O)-OC(=O)-R' (each R' is independently C1-C6 alkyl). It may contain one or more bonds selected from ether, ester, amide, urethane, urea, and mixtures thereof.

[0057] The term "acyclic compound, group or linker" means a compound, group or linker that does not contain any rings.

[0058] The term «alicyclic compound, group or linker» means a non-aromatic cyclic compound, group or linker. It may be substituted with one or more groups as defined for the term «aliphatic». It may contain one or more bonds as defined for the term «aliphatic».

[0059] The term "aromatic compound, group, or linker" means a compound, group, or linker that contains an aromatic ring, which is meant to comply with the Hückel aromaticity rule, in particular a compound that contains a phenyl group. It may be substituted with one or more groups as defined for the term "aliphatic". It may contain one or more bonds as defined for the term "aliphatic".

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

[0061] The term "unsaturated compound, group, or linker" means a compound, group, or linker that contains a double or triple carbon-carbon bond, in particular a double carbon-carbon bond.

[0062] The term "polyol" means a compound containing at least two hydroxyl groups.

[0063] The terms "polyether polyol" or "polyether linker" mean a polyol or linker, respectively, that contains at least two ether bonds.

[0064] The terms "polyester polyol" or "polyester linker" mean a polyol or linker, respectively, that contains at least two ester bonds.

[0065] The terms "polycarbonate polyol" or "polycarbonate linker" mean a polyol or linker, respectively, that contains at least two carbonate bonds.

[0066] The term "polyurethane linker" means a linker which comprises at least two urethane bonds.

[0067] The terms "polyorganosiloxane polyol" or "polyorganosiloxane linker" refer to a polyol or linker, respectively, that contains at least two organosiloxane bonds. The organosiloxanes can be, for example, dimethylsiloxane bonds.

[0068] The terms "polycaprolactone polyol" or "polycaprolactone linker" mean, respectively, a polyol or a linker comprising at least two units derived from the ring-opening polymerization of ε-caprolactone, in particular at least two -[(CH2)5-C(=O)O]- units.

[0069] The terms "polybutadiene polyol" or "polybutadiene linker" mean, respectively, a polyol or a linker comprising at least two units derived from the polymerization of butadiene, in particular at least two units selected from -CH-CH=CH-CH- and CH-CH(CH=CH)-.

[0070] The term "amino group" means R a1 and R b1 is independently H or optionally substituted alkyl, a1 R b1 The "primary amino group" refers to the R a1 and R b1 -NR a1 R b1 The secondary amino group is R a1 is H and R b1 is optionally substituted alkyl, -NR a1 R b1 means a group.

[0071] The term "carboxylic acid" means the group --COOH.

[0072] The term "isocyanate group" means the -N=C=O group.

[0073] The term "ester bond" means a -C(=O)-O- or -OC(=O)- bond.

[0074] The term "ether bond" means an --O-- bond.

[0075] The term "organosiloxane bond" means -Si(R c1 )2-O-bond (wherein, R c1 is an organic radical, in particular an organic radical selected from alkyl, alkoxy and aryl. The term "dimethylsiloxane bond" means the -Si(CH3)2-O- bond.

[0076] The term "carbonate bond" means an -OC(=O)-O- bond.

[0077] The term "urethane or carbamate bond" means a -NH-C(=O)-O- or -OC(=O)-NH- bond.

[0078] The term "polyisocyanate" means a compound containing at least two isocyanate groups.

[0079] The term "optionally substituted compound, group or linker" refers to a compound, group or linker optionally 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', -OC(=O)-R', -C(=O)-OR', -C(=O)-N(R'), -NR'-C(=O)-R', -C(=O)-OC(=O)-R' and -SO-N(R'), where each R' is independently H or an optionally substituted group selected from alkyl, aryl and alkylaryl.

[0080] [Compound of formula (I)] The compounds of the present invention have the following formula (I): TIFF2025504613000003.tif54170 (in the above formula, PI is the photoinitiator moiety; each L is independently selected from a direct bond or a linker containing 1 to 20 carbon atoms; each X is independently selected from a direct bond, a -P(=O)(R')- bond and a linker containing 1 to 6, particularly 1 to 4, more particularly 1 or 2 carbon atoms; R' is aryl, alkyl or alkoxy; Each Y is independently H, alkyl, or -Z'-(OM') m’ and; each Z and Z' is independently a linker containing 1 to 6, particularly 2 to 5, more particularly 2 to 4 carbon atoms; each M and M' is independently H or (meth)acryloyl; each m and m' is independently 1, 2 or 3, in particular 1; Each n is independently 0 or 1, particularly 1; Each p is independently 1, 2 or 3; in particular 1 or 2; q is 1, 2 or 3, in particular 1 or 2. Corresponds to.

[0081] -L-[C(=O)-X] n The - and -Z- moieties may be devoid of ester bonds, indeed the presence of ester bonds in said moieties is not compatible with transesterification reactions to functionalize compounds of formula (I) with (meth)acrylate groups.

[0082] The compound of formula (I) has a photoinitiator moiety PI. In one embodiment, the compound of formula (I) has a single photoinitiator moiety PI.

[0083] PI can be an optionally substituted aryl-containing photoinitiator moiety selected from benzophenone, thioxanthone, anthraquinone, xanthone, acridone, and phenyl.

[0084] It should be understood that an optionally substituted phenyl is different from an aryl containing a benzophenone, thioxanthone, anthraquinone, xanthone or acridone moiety. Thus, when the PI contains an optionally substituted phenyl, the phenyl and its optional substituents do not form or are not part of a benzophenone, thioxanthone, anthraquinone, xanthone or acridone moiety. When the PI contains an optionally substituted phenyl, at least one -C(=O)- group is directly bonded to the phenyl. The at least one -C(=O)- group may be present as a substituent on the phenyl group and / or may be present as a -L-[[C(=O)-X] carried by the phenyl group. n -NY-Z-(OM) m ] p It may be included in at least one of the arms (ie, L=direct bond and n=1 in at least one of the arms).

[0085] In particular, PI is represented by the following formulas (II) to (IX): TIFF2025504613000004.tif67170TIFF2025504613000005.tif69170(in the above formula E is S, O, C(=O) or NR1, especially S; R1 is H, optionally substituted alkyl, optionally substituted aryl; Each symbol represents a point of attachment to a linker, L; Each R a , R' a , R b , R' b , R c , R' c , R d , R' d , R e , R' e , R f , R' f , R g and R h are independently selected from H, F, Cl, Br, I, -OR2, -SR2, -N(R2), -NO2, -CN, -C(=O)R2, -OC(=O)R2, -C(=O)OR2, -C(=O)N(R2), -NR2-C(=O)-R2, -SO2-N(R2), -C(=O)-P(=O)R3R4, or an optionally substituted group selected from alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl, and heteroaryl; Two adjacent R a , R' a , R b , R' b , R c , R' c , R d , R' d , R e , R' e , R f , R' f , R g or R h The groups, together with the carbon atoms to which they are attached, may form a 5- to 8-membered ring; each R2 is independently H or an optionally substituted group selected from alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl, heteroaryl, and heteroatom-containing alkyl; R3 and R4 are independently an optionally substituted group selected from aryl, alkyl, alkoxy, or amino.

[0086] The PI may be a photoinitiator moiety that includes an optionally substituted benzophenone. In particular, the PI may be a benzophenone-containing moiety according to one of the formulae (II), (III) or (IV) described above. More particularly, the PI may be a benzophenone-containing moiety according to one of the formulae (II), (III) or (IV) described above, where R a , R' a , R b , R' b , R c and R' c are independently H, F, Cl, Br, I, -OR2, -SR2, -N(R2)2, -C(=O)R2, or an optionally substituted group selected from alkyl, heteroatom-containing alkyl, and aryl, and two adjacent R a , R' a , R b , R' b , R c , or R' c The groups, together with the carbon atoms to which they are attached, may form a 5- to 8-membered ring; in particular, R a , R' a , R b , R' b , R c and R' c are independently H or -C(=O)R2.

[0087] PI can be a photoinitiator moiety containing an optionally substituted thioxanthone. In particular, PI can be a thioxanthone-containing moiety according to one of the formulae (V), (VI) or (VII) described above, where X=S. More particularly, PI can be a thioxanthone-containing moiety according to one of the formulae (V), (VI) or (VII) described above, where X=S, where R d , R' d , R e , R' e , R f and R' f are independently H, F, Cl, Br, I, -OR2, -SR2, -N(R2)2, -C(=O)R2, or an optionally substituted group selected from alkyl, heteroatom-containing alkyl, and aryl, and two adjacent R d , R' d , R e , R' e , R f or R' f The groups, together with the carbon atoms to which they are attached, may form a 5- to 8-membered ring; in particular, R d , R' d , R e , R' e , R f and R' f are independently H or -C(=O)R2.

[0088] PI can be a photoinitiator moiety containing an optionally substituted anthraquinone. In particular, PI can be an anthraquinone-containing moiety according to one of the formulae (V), (VI) or (VII) described above, where X=-C(=O)-. More particularly, PI can be an anthraquinone-containing moiety according to one of the formulae (V), (VI) or (VII) described above, where X=-C(=O)-, where R d , R' d , R e , R' e , R f and R' fare independently H, F, Cl, Br, I, -OR2, -SR2, -N(R2)2, -C(=O)R2, or an optionally substituted group selected from alkyl, heteroatom-containing alkyl, and aryl, and two adjacent R d , R' d , R e , R' e , R f or R' f The groups, together with the carbon atoms to which they are attached, may form a 5- to 8-membered ring; in particular, R d , R' d , R e , R' e , R f and R' f are independently H or -C(=O)R2.

[0089] PI may be a photoinitiator moiety comprising an optionally substituted xanthone. In particular, PI may be a xanthone-containing moiety according to one of the formulae (V), (VI) or (VII) described above, where X=O. More particularly, PI may be a xanthone-containing moiety according to one of the formulae (V), (VI) or (VII) described above, where X=O, where R d , R' d , R e , R' e , R f and R' f are independently H, F, Cl, Br, I, -OR2, -SR2, -N(R2)2, -C(=O)R2, or an optionally substituted group selected from alkyl, heteroatom-containing alkyl, and aryl, and two adjacent R d , R' d , R e , R' e , R f or R' f The groups, together with the carbon atoms to which they are attached, may form a 5- to 8-membered ring; in particular, R d , R' d , R e , R' e , R f and R' f are independently H or -C(=O)R2.

[0090] PI can be a photoinitiator moiety containing an optionally substituted acridone. In particular, PI can be an acridone-containing moiety according to one of the formulae (V), (VI) or (VII) described above, where X=NR1. More particularly, PI can be an acridone-containing moiety according to one of the formulae (V), (VI) or (VII) described above, where X=NR1, where R d , R' d , R e , R' e , R f and R' f are independently H, F, Cl, Br, I, -OR2, -SR2, -N(R2)2, -C(=O)R2, or an optionally substituted group selected from alkyl, heteroatom-containing alkyl, and aryl, and two adjacent R d , R' d , R e , R' e , R f or R' f The groups, together with the carbon atoms to which they are attached, may form a 5- to 8-membered ring; in particular, R d , R' d , R e , R' e , R f and R' f are independently H or -C(=O)R2.

[0091] PI may be a photoinitiator moiety containing an optionally substituted phenyl. In particular, PI may be a phenyl-containing moiety according to one of the formulae (VIII) or (IX) described above. More particularly, PI may be a phenyl-containing moiety according to one of the formulae (VIII) or (IX) described above, where R g and R h are independently H, F, Cl, Br, I, -OR2, -SR2, -N(R2)2, -C(=O)R2, or an optionally substituted group selected from alkyl, heteroatom-containing alkyl, and aryl, and two adjacent R g or R h The groups, together with the carbon atoms to which they are attached, may form a 5- to 8-membered ring; in particular, Rg and R h are independently H, —C(═O)R2, or alkyl.

[0092] When PI corresponds to formula (VIII) or (IX), at least one -C(=O)- group is directly bonded to the phenyl group of formula (VIII) or (IX). Said -C(=O)- can be represented by the symbol · and / or the substituent R g or R h In other words, the phenyl moiety may be attached directly to the phenyl group of formula (VIII) or (IX). n -NY-Z-(OM) m ] p At least one of the arms has L=direct bond, n=1, and / or R g and R h At least one of is -C(=O)R2, where R2 is as defined above.

[0093] In particular, the PI may correspond to formula (VIII) or (IX) as described above. Such a compound may be an acetophenone-based photoinitiator or a phosphine oxide-based photoinitiator. More particularly, when the PI corresponds to formula (VIII) or (IX) as described above, the compound of formula (I) may have a compound of the following formula (X) or (XI) directly bonded to the phenyl group of the PI: TIFF2025504613000006.tif33170 (in the above formula R i and R' i is alkyl or R i and R' i may, together with the carbon atom to which they are attached, form a 5- to 8-membered ring. R j -OH or -NR l R' l and; R k and R' k is aryl, alkyl, alkoxy and -N(Y)-Z-(OM) m are independently selected from; R l and R' lis alkyl and -Z-(OM) m or R l and R' l may, together with the nitrogen atom to which they are attached, form a 5- to 8-membered ring; Each Y is independently H, alkyl, or -Z'-(OM') m' and; each Z and Z' is independently a linker containing 1 to 6, particularly 2 to 5, more particularly 2 to 4 carbon atoms; each M and M' is independently H or (meth)acryloyl; each m and m' is independently 1, 2 or 3, in particular 1; The symbol · represents the point of attachment to the phenyl group of PI. The compound may include a portion having the following structure:

[0094] The moieties of formula (X) or (XI) described above may be represented by the symbol · and / or the substituent R g or R h may be directly attached to the phenyl group of formula (VIII) or (IX).

[0095] When a moiety of formula (X) is directly attached to a phenyl group of formula (VIII) or (IX) by the symbol ·, R of said moiety of formula (X) j Ha-NR l R' l and R l and R' l At least one of them is -Z-(OM) m It is.

[0096] The portion of formula (X) is a substituent R g directly attached to the phenyl group of formula (VIII) or (IX), R j -OH or -NR l R' l and R l and R' l are independently selected from alkyl, or R l and R' l may be taken together with the nitrogen atom to which they are attached to form a 5- to 8-membered ring.

[0097] When the moiety of formula (XI) is directly attached to a phenyl group of formula (VIII) or (IX) by the symbol ·, said moiety of formula (XI) is an R group selected from aryl, alkyl, and alkoxy. k R' k HA-N(Y)-Z-(OM) m It is.

[0098] The moiety of formula (XI) is a substituent R h and is directly attached to the phenyl group of formula (VIII) or (IX), R k and R' k is independently selected from aryl, alkyl, and alkoxy.

[0099] When PI corresponds to formula (VIII) or (IX) described above, the phenyl moiety bears -L-[[C(=O)-X] n -NY-Z-(OM) m ] p At least one of the arms is a moiety of formula (X) [i.e., L=direct bond, n=1, and X=-CR i R' i -] or a moiety of formula (XI) [i.e., L=direct bond, n=1, X=-P(=O)(R k )-) and / or R g and R h At least one of is a moiety of formula (X) or (XI).

[0100] In a preferred embodiment, the compound of formula (I) according to the present invention is represented by formula (XII) to (XXV): TIFF2025504613000007.tif83170TIFF2025504613000008.tif79170TIFF2025504613000009.tif81170TIFF202550461300 0010.tif85170TIFF2025504613000011.tif87170TIFF2025504613000012.tif85170TIFF2025504613000013.tif99170 (in the above formula L, M, X, Y, Z, m and n are as described above for compounds of formula (I); R a , R' a , R b , R' b , R c , R' c , R d , R' d , R e , R' e , R f , R' f , R g and R h is as described above for the PI moieties of formulas (II) through (IX); R i and R' i is as described above for moieties of formula (X); R j -OH or -NR l R' l and; R k and R' k is independently selected from aryl, alkyl, and alkoxy; R l and R' l are independently selected from alkyl, or R l and R' l may form a 5- to 8-membered ring together with the nitrogen atom to which they are attached). This may be due to one of the following.

[0101] The compound of formula (I) may be a benzophenone-based photoinitiator, i.e. a compound containing an optionally substituted benzophenone moiety. In particular, the compound of formula (I) may be a benzophenone-based photoinitiator according to one of the formulae (XII), (XIII) or (XIV) described above.

[0102] The compound of formula (I) may be a thioxanthone-based photoinitiator, i.e. a compound comprising an optionally substituted thioxanthone moiety. In particular, the compound of formula (I) may be a thioxanthone-based photoinitiator according to one of the above-described formulae (XV), (XVI) or (XVII), in which E is S.

[0103] The compound of formula (I) may be an anthraquinone-based photoinitiator, i.e. a compound containing an anthraquinone moiety, which may be substituted. In particular, the compound of formula (I) may be an anthraquinone-based photoinitiator according to one of the above-described formulae (XV), (XVI) or (XVII), in which E is -C(=O)-.

[0104] The compound of formula (I) may be a xanthone-based photoinitiator, i.e. a compound comprising an optionally substituted xanthone moiety. In particular, the compound of formula (I) may be a xanthone-based photoinitiator according to one of the above-described formulae (XV), (XVI) or (XVII), in which E is O.

[0105] The compound of formula (I) may be an acridone-based photoinitiator, in other words, a compound containing an optionally substituted acridone moiety. In particular, the compound of formula (I) may be an acridone-based photoinitiator according to one of the above-described formulae (XV), (XVI) or (XVII), in which E is NR1.

[0106] The compounds of formula (I) are acetophenone-based photoinitiators, in other words, where Ph is an optionally substituted phenyl, and are represented by the symbol * represents the point of attachment to the carbon atom * In particular, the compound of formula (I) may be an acetophenone-based photoinitiator according to one of formulae (XVIII), (XIX) or (XX) described above.

[0107] The compound of formula (I) may be an acylphosphine oxide photoinitiator, i.e. a compound comprising the moiety -P(=O)-C(=O)-Ph, where Ph is an optionally substituted phenyl. In particular, the compound of formula (I) may be an acylphosphine oxide photoinitiator according to one of the formulae (XXI), (XXII), (XXIII) or (XXIV) described above.

[0108] In the compounds of formulae (I) and (XII) to (XXV), PI is linked to a linker L. Each L is independently selected from a direct bond or a linker comprising 1 to 20 carbon atoms. In particular, the linker comprising 1 to 20 carbon atoms may be a divalent or trivalent linker. In particular, the linker comprising 1 to 20 carbon atoms may further optionally comprise one or more heteroatoms, such as O or S. More particularly, the linker comprising 1 to 20 carbon atoms may be: - an acyclic linker, which may be saturated or unsaturated, in particular an acyclic linker having 1 to 6, 1 to 4 or 1 to 2 carbon atoms; or - cyclic linkers, which may be aromatic or non-aromatic, monocyclic or polycyclic, in particular cyclic linkers having from 6 to 20, from 7 to 15 or from 7 to 13 carbon atoms; It is possible.

[0109] In a preferred embodiment, each L is independently selected from a direct bond, 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 particularly, each L is a direct bond, an alkylene of formula (XXVI) or (XXVII), an oxyalkylene of formula (XXVIII), a thioalkylene of formula (XXIX), a ketoalkylene of formula (XXX), a ketoalkenylene of formula (XXXI), a ketoarylene of formula (XXXII), a ketocycloalkylene of formula (XXXIII), TIFF2025504613000014.tif107170 (in the above formula Each R m , R'm , R n , R' n , R" n , R o , R' o , R p , R' p , R q and R' q is independently H or alkyl, particularly H; Each R r and R' r are independently selected from H, F, Cl, Br, I, -OR2, -SR2, -N(R2), -NO2, -CN, -C(=O)R2, -OC(=O)R2, -C(=O)OR2, -C(=O)N(R2), -NR2-C(=O)-R2, -SO2-N(R2), -C(=O)-P(=O)R3R4, or an optionally substituted group selected from alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl, and heteroaryl; Two adjacent R r or R' r The groups, together with the carbon atoms to which they are attached, may form a 5- to 8-membered ring; each R2 is independently H or an optionally substituted group selected from alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl, heteroaryl, and heteroatom-containing alkyl; R3 and R4 are independently an optionally substituted group selected from aryl, alkyl, alkoxy, or amino; a is 1, 2, 3, 4, 5 or 6, in particular 1 or 2; b is 1, 2, 3, 4 or 5, in particular 1; c is 1, 2, 3, 4, 5 or 6, in particular 1 or 2; d is 1, 2, 3, 4, 5 or 6, in particular 1 or 2; e is 1, 2, 3, 4 or 5, in particular 1; f is 6 or 8; TIFF2025504613000015.tif12170The symbol · represents the point of attachment to the PI moiety; The symbol § stands for -C(=O)-XN(Y)-Z-(OM) m represents the point of attachment to the moiety) are independently selected from

[0110] More particularly, each L may be independently selected from a direct bond, an alkylene of formula (XXVI) or (XXVII), and an oxyalkylene of formula (XXVIII), as described above.

[0111] In one embodiment, q is 1, p is 2 and L is an alkylene of formula (XXVII), in particular R n , R' n and R" n is H; is an alkylene of formula (XXVII) in which a is 1;

[0112] In another embodiment, q is 2, p is 1 and each L is selected from the group consisting of a direct bond and an oxyalkylene of formula (XXVIII), in particular a direct bond and R o and R' o is H; and c is independently selected from oxyalkylene of formula (XXVIII):

[0113] When q is 2 and p is 1, at least one L can be an oxyalkylene of formula (XXVIII). For example, one L can be a direct bond and the other L can be an oxyalkylene of formula (XXVIII), or both L can be oxyalkylene of formula (XXVIII).

[0114] When L is a direct bond, it is directly attached to the -C(=O)-X- moiety (i.e., n is 1). When L is other than a direct bond, it is preferably directly attached to the -C(=O)-X- moiety (i.e., n is 1).

[0115] In the compounds of formulae (I) and (XII) to (XXV), when n is 1, each X is independently selected from a direct bond, a -P(=O)(R')- bond, and a linker containing 1 to 6, particularly 1 to 4, more particularly 1 to 3 carbon atoms. R' is aryl, alkyl or alkoxy. In particular, the linker containing 1 to 6 carbon atoms may be an acyclic linker, which may be saturated or unsaturated, preferably saturated.

[0116] In preferred embodiments, each X is independently selected from a direct bond, a C1-C6 alkylene, and -P(=O)(R')-, where R' is aryl, alkyl, or alkoxy; In particular, each X can be a direct bond, a group of the formula -(CR s R' s ) g -alkylene, and -P(=O)(R')-, where R' is phenyl; Here, each R s and R' s is independently H or alkyl, in particular alkyl; g is 1, 2, 3, 4, 5 or 6, in particular 1.

[0117] In particular, the formula -L-[C(=O)-X] n In the - moiety, when X is a -P(=O)(R')- bond, L is a direct bond.

[0118] In particular, the formula -L-[C(=O)-X] n In the - moiety, when X is a direct bond, then L is not a direct bond (in other words, n is 1).

[0119] When X is a -P(=O)(R')- bond, the compound of formula (I) has a single -N(Y)-Z-(OM) m moiety, where Y is other than H. When X is a -P(=O)(R')- bond, the compound of formula (I) may contain a single -N(Y)-Z-(OM) mWhen including a moiety (wherein Y is other than H), m may be 2 or 3, especially 3. Preferably, when X is a -P(=O)(R')- bond, the compound of formula (I) contains at least one -N(Y)-Z-(OM) m Part (where Y is -Z'-(OM') m' In such cases, m and m' are preferably 1 or 2, preferably 1. Alternatively, when X is a -P(=O)(R')- bond and the compound of formula (I) is a phosphine oxide photoinitiator, it may contain at least one -N(Y)-Z-(OM) m moiety, where Y is H. In such cases, m is preferably 3.

[0120] When X is other than a -P(=O)(R')- bond, the compound of formula (I) has at least two -N(Y)-Z-(OM) m The compound of formula (I) may contain at least two -N(Y)-Z-(OM) moieties (wherein Y is other than H), preferably at least two -N(Y)-Z-(OM) m Part (where Y is -Z'-(OM') m' X may be other than a -P(=O)(R')- bond and the compound of formula (I) may contain at least two -N(Y)-Z-(OM) m part (where Y is -Z'-(OM') m' When X is other than a -P(=O)(R')- bond, and the compound of formula (I) contains at least two -N(Y)-Z-(OM) m When including the moiety (where Y is alkyl), m can be 2 or 3, especially 3.

[0121] In the compounds of formulae (I) and (XII) through (XXV), each Y is independently H, alkyl or -Z'-(OM') m' Z' and M' are as described below.

[0122] In a preferred embodiment, each Y is independently alkyl or -Z'-(OM') m' , in particular methyl, ethyl or -Z'-(OM') m', more specifically -Z'-(OM') m' All of the Y groups are -Z'-(OM'). m' Alternatively, all of the Y groups may be alkyl. Alternatively, some of the Y groups may be -Z'-(OM') m' and some of the Y groups can be alkyl.

[0123] When Y is H, the following embodiments are preferred: - at least one of m, p or q is 2 or 3; or - L is a direct bond, n is 1 and X is a -P(=O)(R')- bond.

[0124] When Y is alkyl, at least one of m, p, or q is preferably 2 or 3, more preferably 3.

[0125] In the compounds of formulae (I) and (XII) to (XXV), each Z and Z' is independently a linker comprising from 1 to 6, particularly from 2 to 5, more particularly from 2 to 4 carbon atoms. In particular, the linker comprising from 1 to 6 carbon atoms may be an acyclic linker, which may be saturated or unsaturated, preferably saturated.

[0126] In a preferred embodiment, each Z and Z' is independently an alkylene; in particular, each Z and Z' is independently an alkylene of formula (XXXIV), (XXXV) or (XXXVI), and even more particularly an alkylene of formula (XXXIV). TIFF2025504613000016.tif71170 (in the above formula, each R t , R' t , R u , R' u , R v , R' v is independently H or alkyl, particularly H; R" u is H or alkyl, in particular alkyl; h is 1, 2, 3, 4, 5 or 6, in particular 2; each i is independently 1, 2 or 3, in particular 1; each j is independently 1, 2 or 3, in particular 1; The file is TIFF2025504613000017.tif13170.

[0127] The compounds of formulae (I) and (XII) to (XXV) may have a total number of -OM and -OM' groups of at least 2, particularly at least 3, more particularly at least 4. As used herein, the total number of OM and OM' groups in a compound corresponds to the sum of all OM and OM' groups in the compound. When a compound has a total number of OM and OM' groups less than 4, the compound preferably contains a -P(=O)(R')- bond. Thioxanthone-based photoinitiators, benzophenone-based photoinitiators, and acetophenone-based photoinitiators may have a total number of OM and OM' groups equal to 3 or 4. Phosphine oxide-based photoinitiators may have a total number of OM and OM' groups equal to 2, 3, or 4.

[0128] In one embodiment, all of the M and M' groups can be H. In another embodiment, all of the M and M' groups are (meth)acryloyl. In yet another embodiment, some of the M and M' groups are H and some of the M and M' groups are (meth)acryloyl.

[0129] In a preferred embodiment, the -L-[[C(=O)-X] carried by the photoinitiator moiety PI of the compound of formula (I) n -NY-Z-(OM) m ] p At least one of the arms comprises an amide bond, an amine bond, or an aminophosphine bond, preferably an amide bond or an aminophosphine bond. An amide bond may be formed when L is other than a direct bond, n is 1, and X is a bond. Preferably, the amide bond is a substituted amide bond, i.e., Y is not H. An amine bond may be formed when L is a bond, n is 1, and X is an alkylene. Preferably, the amine bond is a tertiary amine bond, i.e., Y is not H. An aminophosphine bond may be formed when L is a bond, n is 1, and X is -P(=O)(R')-.

[0130] In a preferred embodiment, the compounds of formulae (I) and (XII) to (XXV) contain at least one bond selected from an amide bond or an aminophosphine bond, preferably at least one amide bond. The at least one amide bond is preferably selected from the -L-[[C(=O)-X] bond of the compounds of formulae (I) and (XII) to (XXIV). n -NY-Z-(OM) m ] p At least one of the moieties is preferably a substituted amide bond, i.e. Y is not H.

[0131] In a preferred embodiment, the compound of formula (I) may be a benzophenone-based photoinitiator according to formula (XII), wherein: L is an alkylene of formula (XXVII); n is 1; X is a direct bond; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; Each R a and R' a are independently as described above for the PI moiety of formula (II), preferably R a and R' a are independently H or -C(=O)R2.

[0132] In a preferred embodiment, the compound of formula (I) may be a benzophenone-based photoinitiator according to formula (XIII) or (XIV), wherein: each L is independently a direct bond or an oxyalkylene of formula (XXVIII), preferably at least one of L is an oxyalkylene of formula (XXVIII) and the other L is a direct bond or an oxyalkylene of formula (XXVIII); n is 1; X is a direct bond; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; Each R b , R' b , R c and R' c are independently as described above for the PI moiety of formula (III) or (IV), preferably R b , R' b , R c and R' c are independently H or -C(=O)R2.

[0133] In a preferred embodiment, the compound of formula (I) may be a thioxanthone-based photoinitiator according to formula (XV), wherein E is S; L is an alkylene of formula (XXVII); n is 1; X is a direct bond; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; Each R d and R' d are independently as described above for the PI moiety of formula (V), preferably R d and R' d are independently H or -C(=O)R2.

[0134] In a preferred embodiment, the compound of formula (I) may be a thioxanthone-based photoinitiator according to formula (XVI) or (XVII), wherein: E is S; each L is independently a direct bond or an oxyalkylene of formula (XXVIII), preferably at least one of L is an oxyalkylene of formula (XXVIII) and the other L is a direct bond or an oxyalkylene of formula (XXVIII); n is 1; X is a direct bond; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; Each R e , R' e , R f and R' f are independently as described above for the PI moiety of formula (VI) or (VII), preferably R e , R' e , R f and R' f are independently H or -C(=O)R2.

[0135] In a preferred embodiment, the compound of formula (I) may be an anthraquinone-based photoinitiator according to formula (XV), wherein E is -C(=O)-; L is an alkylene of formula (XXVII); n is 1; X is a direct bond; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; Each R d and R' d are independently as described above for the PI moiety of formula (V), preferably R d and R' d are independently H or -C(=O)R2.

[0136] In a preferred embodiment, the compound of formula (I) may be an anthraquinone-based photoinitiator according to formula (XV) or (XVII), wherein: E is -C(=O)-; each L is independently a direct bond or an oxyalkylene of formula (XXVIII), preferably at least one of L is an oxyalkylene of formula (XXVIII) and the other L is a direct bond or an oxyalkylene of formula (XXVIII); n is 1; X is a direct bond; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; Each R e , R' e , R f and R' f are independently as described above for the PI moiety of formula (VI) or (VII), preferably R e , R' e , R f and R' f are independently H or -C(=O)R2.

[0137] In a preferred embodiment, the compound of formula (I) may be a xanthone-based photoinitiator according to formula (XV), wherein E is O; L is an alkylene of formula (XXVII); n is 1; X is a direct bond; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; Each R d and R' dare independently as described above for the PI moiety of formula (V), preferably R d and R' d are independently H or -C(=O)R2.

[0138] In a preferred embodiment, the compound of formula (I) may be a xanthone-based photoinitiator according to formula (XVI) or (XVII), wherein: E is O; each L is independently a direct bond or an oxyalkylene of formula (XXVIII), preferably at least one of L is an oxyalkylene of formula (XXVIII) and the other L is a direct bond or an oxyalkylene of formula (XXVIII); n is 1; X is a direct bond; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; Each R e , R' e , R f and R' f are independently as described above for the PI moiety of formula (VI) or (VII), preferably R e , R' e , R f and R' f are independently H or -C(=O)R2.

[0139] In a preferred embodiment, the compound of formula (I) may be an acridone-based photoinitiator according to formula (XV), wherein E is NR1; L is an alkylene of formula (XXVII); n is 1; X is a direct bond; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; Each R d and R' d are independently as described above for the PI moiety of formula (V), preferably R d and R' d are independently H or -C(=O)R2.

[0140] In a preferred embodiment, the compound of formula (I) may be an acridone-based photoinitiator according to formula (XVI) or (XVII), wherein E is NR1; each L is independently a direct bond or an oxyalkylene of formula (XXVIII), preferably at least one of L is an oxyalkylene of formula (XXVIII) and the other L is a direct bond or an oxyalkylene of formula (XXVIII); n is 1; X is a direct bond; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; Each R e , R' e , R f and R' f are independently as described above for the PI moiety of formula (VI) or (VII), preferably R e , R' e , R f and R' f are independently H or -C(=O)R2.

[0141] In a preferred embodiment, the compound of formula (I) may be an acetophenone-based photoinitiator according to formula (XVIII), wherein L is an alkylene of formula (XXVII); n is 1; X is a direct bond; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; R i and R' i are independently alkyl, or R i and R' i forms a ring; R j -OH or -NR l R' l and; R l and R' l are independently alkyl, or R l and R' l forms a ring; Each R g are independently as described above for the PI moiety of formula (VIII), and preferably each R g is H.

[0142] In a preferred embodiment, the compound of formula (I) may be an acetophenone-based photoinitiator according to formula (XIX), wherein each L is independently an alkylene of formula (XXVIII); n is 1; X is a direct bond; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; R i and R' i are independently alkyl, or R i and R' i forms a ring; R j -OH or -NR l R' l and; R l and R'l are independently alkyl, or R l and R' l forms a ring; Each R h are independently as described above for the PI moiety of formula (IX), and preferably each R h is H.

[0143] In a preferred embodiment, the compound of formula (I) may be an acetophenone-based photoinitiator according to formula (XX), wherein L is independently an alkylene of formula (XXVIII); n is 1; X is a direct bond; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; R i and R' i are independently alkyl; Each R h are independently as described above for the PI moiety of formula (IX), and preferably each R h is H.

[0144] In a preferred embodiment, the compound of formula (I) may be an acylphosphine oxide photoinitiator according to formula (XXI), wherein L is an alkylene of formula (XXVII); n is 1; X is a direct bond; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; R k and R' k is aryl, alkyl, alkoxy; R j -OH or -NR l R' l and; Each R g are independently as described above for the PI moiety of formula (VIII), and preferably each R g is independently H or alkyl.

[0145] In a preferred embodiment, the compound of formula (I) may be an acylphosphine oxide photoinitiator according to formula (XXII) or (XXIII), wherein L is a direct bond; n is 1; X is the formula -(CR s R' s ) g -alkylene; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; R k and R' k is aryl, alkyl, alkoxy; Each R g are independently as described above for the PI moiety of formula (VIII), and preferably each R g is independently H or alkyl; Each R h are independently as described above for the PI moiety of formula (IX), and preferably each R h is H or alkyl.

[0146] In a preferred embodiment, the compound of formula (I) may be an acylphosphine oxide photoinitiator according to formula (XXIV), wherein L is a direct bond; n is 1; X is the formula -(CR s R' s ) g -alkylene; Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; R k is aryl, alkyl, alkoxy; Each R h are independently as described above for the PI moiety of formula (IX), and preferably each R h is independently H or alkyl.

[0147] In a preferred embodiment, the compound of formula (I) may be an acylphosphine oxide photoinitiator according to formula (XXV), wherein Y is -Z'-(OM') m' and; Z and Z' are independently alkylene of formula (XXXIV); M and M' are independently H or (meth)acryloyl; m and m' are 1; R k is aryl, alkyl, alkoxy; Each R g are independently as described above for the PI moiety of formula (VIII), and preferably each R g is independently H or alkyl.

[0148] In a preferred embodiment, the compound of formula (I) may be an acylphosphine oxide photoinitiator according to formula (XXV), wherein Y is H; Z is an alkylene of formula (XXXIV); M is H or (meth)acryloyl; m is 3; R k is aryl, alkyl, alkoxy; Each R g are independently as described above for the PI moiety of formula (VIII), and preferably each R gis independently H or alkyl.

[0149] Particularly preferred examples of photoinitiators of formula (I) according to the present invention include, but are not limited to, the following compounds: TIFF2025504613000018.tif71170TIFF2025504613000019.tif96170TIFF202550461300002 0.tif84170TIFF2025504613000021.tif79170TIFF2025504613000022.tif54170TIFF20255 04613000023.tif67170TIFF2025504613000024.tif74170TIFF2025504613000025.tif75170TIFF2025504613000026.tif68170TIFF2025504613000027.tif74170Isomers thereof and combinations thereof.

[0150] The term "isomers thereof" refers to positional isomers, in other words compounds which differ from each other in the position of the substituents on the aryl moiety (ie, the benzophenone, thioxanthone, or phenyl moiety).

[0151] Methods for preparing compounds of formula (I) Compounds of formula (I) can be obtained using standard reactions.

[0152] At least one -C(=O)-N(Y)-Z-(OH) m Compounds of formula (I) having a moiety (i.e., a moiety containing an amide bond substituted with at least a hydroxylated group) can be prepared by reacting an amine having at least one hydroxylated group (i.e., HN(Y)-Z-(OH) m ) can be obtained by amidation of the corresponding ester or carboxylic acid.

[0153] The compound of formula (I) having at least one (meth)acryloyloxy group can be obtained by (meth)acrylation of the corresponding alcohol. Some or all of the hydroxyl groups of the compound of formula (I) can be converted to (meth)acryloyloxy groups by direct esterification with (meth)acrylic acid in the presence of an acid catalyst, or by transesterification with a (C1-C6) alkyl (meth)acrylate in the presence of a transesterification catalyst.

[0154] The present invention thus relates to a method for preparing a compound of formula (I) in which at least some of the M groups are (meth)acryloyl, comprising reacting a compound of formula (I) in which all of the M groups are H with (meth)acrylic acid or a (C1-C6) alkyl (meth)acrylate in the presence of a catalyst. As used herein, the term "(C1-C6) alkyl (meth)acrylate" refers to a compound of formula A'-OC(=O)-CHR=CH2, where A' is a C1-C6 alkyl and R is H or Me. When (meth)acrylic acid is used, the catalyst can be an acid catalyst. When (C1-C6) alkyl (meth)acrylate is used, the catalyst can be a transesterification catalyst, in particular a metal-based transesterification catalyst, more particularly a transesterification catalyst based on a metal selected from Zn, Zr, Ti or Sn, even more particularly Zn(acetylacetonate)2, Zr(acetylacetonate)4, Ti(isopropoxy)4 or nBuSnOOH.

[0155] Compounds of formula (XII) containing an amide bond (n is 1 and X is a direct bond) can be obtained by an acylation reaction followed by an amidation reaction with a hydroxylated amine. In particular, compounds of formula (XIIa) having a benzophenone moiety can be obtained by reacting an acyl halide (e.g., an acyl chloride) of formula (1) with a substituted phenyl of formula (2) in the presence of a Lewis acid (e.g., a metal halide, such as iron chloride or aluminum chloride) to form a diacid or diester of formula (3), which is then converted to an amide of formula (XIIa) by reaction with a hydroxylated amine of formula (4), according to the following scheme: TIFF2025504613000028.tif81170 (in the above formula, L, R a , R' a , Y, Z and m are as described herein; W is a halogen atom, in particular Cl; and R″ is H or alkyl, particularly methyl or ethyl).

[0156] Compounds of formula (XV) containing an amide bond (n is 1 and X is a direct bond) can be obtained by an acylation reaction followed by an amidation reaction with a hydroxylated amine. In particular, compounds of formula (XVa) having a thioxanthone (E is S) or anthraquinone (E is C(=O)) moiety can be obtained by reacting an acyl halide (e.g., acyl chloride) of formula (5) with a substituted phenyl of formula (6) in the presence of a Lewis acid (e.g., a metal halide, such as iron chloride or aluminum chloride) to form a diacid or diester of formula (7), which is then converted to an amide of formula (XVa) by reaction with a hydroxylated amine of formula (4), according to the following scheme: TIFF2025504613000029.tif81170 (in the above formula, E is S or C(=O); L, R d , R' d , Y, Z and m are as described herein; W is a halogen atom, in particular Cl; and R″ is H or alkyl, particularly methyl or ethyl).

[0157] Compounds of formula (XIIb) containing an amide bond (n is 1 and X is a direct bond) can also be synthesized by reacting a malonate ester of formula (9) with a haloalkyl or acyl halide substituted benzophenone of formula (8) where T is alkylene or C=O in the presence of a suitable base (e.g., sodium or potassium hydroxide, sodium or potassium carbonate, calcium oxide) according to the following scheme. Direct cross-coupling of a malonate ester of formula (9) with a halo-substituted benzophenone of formula (8) where T is a direct bond can also be possible with the aid of a transition metal catalyst (e.g., palladium catalyst). The resulting diester of formula (10) can then be converted to an amide of formula (XIIb) by reaction with a hydroxylated amine of formula (4). TIFF2025504613000030.tif76170 (in the above formula, R a , R' a , R" n , Y, Z and m are as described herein; T is a direct bond, alkylene or C=O; W is a halogen atom, in particular Cl; and R" is alkyl, particularly methyl or ethyl).

[0158] Compounds of formula (XVb) containing an amide bond (n is 1 and X is a direct bond) can also be synthesized by reacting malonate esters of formula (9) with haloalkyl or acyl halide substituted thioxanthones, anthraquinones, xanthones and acridones of formula (11) where T is alkylene or C=O in the presence of a suitable base (e.g., sodium or potassium hydroxide, sodium or potassium carbonate, calcium oxide) according to the following scheme. Direct cross-coupling of malonate esters of formula (9) with halo-substituted thioxanthones, anthraquinones, xanthones or acridones of formula (11) where T is a bond can also be possible with the aid of a transition metal catalyst (e.g., palladium catalyst). The resulting diesters of formula (12) can then be converted to amides of formula (XVb) by reaction with hydroxylated amines of formula (4). TIFF2025504613000031.tif77170 (in the above formula, E is S, O, C(=O) or NR1; R1, R d , R' d , R" n , Y, Z and m are as described herein; T is a direct bond, alkylene or C=O; W is a halogen atom, in particular Cl; and R" is alkyl, in particular methyl or ethyl).

[0159] Haloalkyl-substituted photoinitiators of formula (8) or (11) where T is alkylene can be prepared by halogenation of an alkyl-substituted photoinitiator, for example using free radical halogenation. For example, bromomethyl-substituted photoinitiators can be prepared by radical bromination of a methyl-substituted photoinitiator in the presence of a bromine source, such as N-bromosuccinimide, and a radical initiator, such as benzoyl peroxide.

[0160] Acyl halide substituted photoinitiators of formula (8) or (11) where T is C(=O) can be prepared by reaction of a carboxylic acid functionalized photoinitiator with a suitable halogenating agent, such as thionyl chloride.

[0161] Then, some or all of the OH groups in the compound of formula (XIIa), (XIIb), (XVa) or (XVb) can be converted to (meth)acryloyloxy groups by reaction with (meth)acrylic acid or a C1-C6 alkyl (meth)acrylate.

[0162] Compounds of formula (XIII), (XIV), (XVI) or (XVII) containing an amide bond (n is 1 and X is a direct bond) can be obtained by an acylation reaction followed by an amidation reaction with a hydroxylated amine. The benzophenone moiety (PI corresponds to formula (III) or (IV) described above), the thioxanthone moiety (PI corresponds to formula (VI) or (VII) described above and E is S), the anthraquinone moiety (PI corresponds to formula (VI) or (VII) described above and E is C(=O)), the xanthone moiety (PI corresponds to formula (VI) or (VII) described above and E is O), or the acridone moiety (PI corresponds to formula (VI) or (VII) described above and E is NR1). A hydroxylated photoinitiator of formula (13), having a substituent group of Q=alkylene, can be reacted with a halogenated ester of formula (14), where Q is alkylene, in the presence of a suitable base (e.g., sodium or potassium hydroxide, sodium or potassium carbonate, calcium oxide) according to the following scheme to form a diester of formula (15), which can then be converted to an amide of formula (XIIIa), (XIVa), (XVIa) or (XVIIa) by reaction with a hydroxylated amine of formula (4): TIFF2025504613000032.tif83170 (in the above formula, PI corresponds to formula (III), (IV), (VI) or (VII) as set forth above; Y, Z and m are as described herein; Q is alkylene; W is a halogen atom, in particular Cl; and R" is alkyl, in particular methyl or ethyl).

[0163] Some or all of the OH groups in the compounds of formula (XIIIa), (XIVa), (XVIa) or (XVIIa) can be converted to (meth)acryloyloxy groups by reaction with (meth)acrylic acid or a C1-C6 alkyl (meth)acrylate.

[0164] Compounds of formula (XVIII) containing an amide bond (n is 1 and X is a direct bond) can be obtained by an acylation reaction followed by a substitution reaction and an amidation reaction with a hydroxylated amine. In particular, compounds of formula (XVIIIa) can be prepared according to the following scheme by reaction of an aromatic malonate ester of formula (16) with an α-halo-substituted acyl halide of formula (17), such as α-bromoisobutyryl bromide, in the presence of a suitable Lewis acid catalyst, such as iron chloride or aluminum chloride. The intermediate α-haloketone (18) thus produced can be reacted with R j When R is -OH (e.g., sodium hydroxide), it is treated with an alkali metal hydroxide salt (19), or j Ga-NR l R' l (such as morpholine) can be reacted with an amine (20) to give a compound of formula (21), which can be further reacted with a hydroxylated amine of formula (4) to give a compound of formula (XVIIIa). TIFF2025504613000033.tif91170 (in the above formula, R g , R i , R' i , L, Y, Z and m are as described herein; R j -OH or -NR l R' l and; W is a halogen atom, in particular Br; M is a metal ion, in particular Na or K; R" is alkyl, particularly methyl or ethyl).

[0165] Compounds of formula (XX) containing an amide bond (n is 1 and X is a direct bond) can be prepared in a similar manner to compounds of formula (XVIII) without a substitution reaction. In particular, compounds of formula (XXa) can be prepared by the reaction of an aromatic ester of formula (16') with an α-halo-substituted acyl halide of formula (17), such as α-bromoisobutyryl bromide, in the presence of a suitable Lewis acid catalyst, such as iron chloride or aluminum chloride, according to the following scheme: The intermediate α-haloketone (18') can be directly reacted with a hydroxylated amine of formula (4) to give compounds of formula (XXa). TIFF2025504613000034.tif105170 (in the above formula, R h , R i , R' i , L, Y, Z and m are as defined herein; W is a halogen atom, in particular Br; R" is alkyl, in particular methyl or ethyl).

[0166] Compounds of formula (XIX) containing an amide bond (n is 1 and X is a direct bond) can be produced in a similar manner to compounds of formula (XVIII), i.e., by acylation followed by substitution and amidation with a hydroxylated amine. In particular, compounds of formula (XIXa) can be prepared according to the following scheme by reaction of an aromatic diester of formula (22) with an α-halo substituted acyl halide of formula (17), such as α-bromoisobutyryl bromide, in the presence of a suitable Lewis acid catalyst, such as iron chloride or aluminum chloride. The intermediate α-haloketone (23) can be reacted with R j When R is -OH, it is an alkali metal hydroxide (19) (e.g., sodium hydroxide) and j Ga-NR l R' l can be reacted with an amine (20) (such as morpholine) to give a compound of formula (24), which can be further reacted with a hydroxylated amine of formula (4) to give a compound of formula (XIXa). TIFF2025504613000035.tif95170 (in the above formula, R h , R i , R' i , L, Y, Z and m are as defined herein; R j -OH or -NR l R' l and; W is a halogen atom, in particular Br; M is a metal ion, in particular Na or K; R" is alkyl, particularly methyl or ethyl).

[0167] Some or all of the OH groups in the compound of formula (XVIIIa), (XIXa) or (XXa) can then be converted to (meth)acryloyloxy groups by reaction with (meth)acrylic acid or a C1-C6 alkyl (meth)acrylate.

[0168] Compounds of formula (XXI) containing an amide bond (n is 1 and X is a direct bond) can be produced by functionalization of a suitable aromatic acylphosphine oxide. In particular, compounds of formula (XXIa) where L is an alkylene of formula (XXVII) can be obtained by reaction of an aromatic acylphosphine oxide of formula (25) with an alkyl halide of formula (26) (e.g., bromomethyl methyl ether) in the presence of a suitable Lewis acid catalyst (e.g., zinc bromide) according to the following scheme to obtain an alkyl halide intermediate (27). Intermediate (27) can be further reacted with a metal salt of a malonate diester (28) to obtain a diester intermediate (29), which can then be reacted with a hydroxylated amine of formula (4) to obtain a compound of formula (XXIa). TIFF2025504613000036.tif85170 (in the above formula, R g , R k , R' k , Y, Z and m are as described herein; W is a halogen atom, particularly Br; M is a metal ion, in particular Na or K; R" is alkyl, particularly methyl or ethyl).

[0169] Compounds of formula (XXII) containing a tertiary amine linkage (L is a direct bond, n is 1, and X is alkylene) can be produced by functionalization of a suitable aromatic acylphosphine oxide. In particular, compounds of formula (XXIIa) can be obtained by reaction of an aromatic acylphosphine oxide of formula (25) with an α-halo-substituted acyl halide of formula (30) (e.g., chloroacetyl chloride) in the presence of a suitable Lewis acid catalyst according to the following scheme to give an alkyl halide intermediate of formula (31). Intermediate (31) can be further reacted with a hydroxylated amine of formula (4) to give compounds of formula (XXIIa). TIFF2025504613000037.tif70170 (in the above formula, R g , R k , R' k , Y, Z and m are as described herein; W is a halogen atom, particularly Cl).

[0170] Compounds of formula (XXIII) containing an amide bond (n is 1 and X is a direct bond) can be produced by functionalization of a suitable aromatic aldehyde followed by an amidation reaction with a hydroxylated amine. In particular, compounds of formula (XXIIIa) can be obtained by reaction of an aldehyde of formula (32) with a phosphine oxide of formula (33) according to the following scheme: The alcohol intermediate (34) thus obtained can be oxidized to an acylphosphine oxide using a suitable oxidation reagent (e.g. hydrogen peroxide in the presence of a catalyst such as vanadium(V) oxide). The diester intermediate (35) thus produced can be reacted with a hydroxylated amine of formula (4) to give compounds of formula (XXIIIa). TIFF2025504613000038.tif81170 (in the above formula, R h , R k , R'k , L, Y, Z and m are as described herein; R" is alkyl, particularly methyl or ethyl).

[0171] Compounds of formula (XXIV) containing a tertiary amine linkage (L is a direct bond, n is 1, and X is an alkylene) can be produced by functionalization of an appropriate aromatic acylphosphine oxide. In particular, compounds of formula (XXIVa) can be prepared by first converting a phosphinic acid of formula (36) to a phosphinic acid halide of formula (37) by reaction with a suitable halogenating reagent (such as thionyl chloride) according to the following scheme. The phosphinic acid halide (37) can be reacted with an α-halo-substituted acyl halide of formula (30) (such as chloroacetyl chloride) in the presence of a suitable Lewis acid catalyst to give an alkyl halide intermediate of formula (38). The intermediate (38) can be further reacted with a hydroxylated amine of formula (4) in the presence of a suitable base (e.g., an amine base such as triethylamine) to give a compound of formula (XXIVa). TIFF2025504613000039.tif81170 (in the above formula, R g , R k , Y, Z and m are as described herein; W and X are independently a halogen atom, in particular Cl.

[0172] Compounds of formula (XXV) can be produced by functionalization of suitable aromatic acylphosphine oxides. In particular, compounds of formula (XXVa) can be prepared according to the following scheme by first converting phosphinic acid of formula (36) to phosphinic acid halide of formula (37) by reaction with a suitable halogenating agent (such as thionyl chloride). The phosphinic acid halide is further reacted with hydroxylated amine of formula (4) in the presence of a suitable base (e.g., an amine base such as triethylamine) to obtain compounds of formula (XXVa). TIFF2025504613000040.tif38170 (in the above formula, R g , R k , Y, Z and m are as described herein; X is a halogen atom, in particular Cl).

[0173] Then, some or all of the OH groups in the compound of formula (XXIa), (XXIIa), (XXIIIa), (XXIVa) or (XXVa) can be converted to (meth)acryloyloxy groups by reaction with (meth)acrylic acid or a C1-C6 alkyl (meth)acrylate.

[0174] [Photoinitiator composition] The photoinitiator composition of the present invention comprises a mixture of at least two different photoinitiators, or a mixture of at least one photoinitiator and at least one amine synergist different from the photoinitiator.

[0175] In a first embodiment, the photoinitiator composition may comprise at least one compound of formula (I) described above and at least one compound according to one of the following formulae (XXXVII) or (XXXVIII): TIFF2025504613000041.tif110170, where PI, L, M, X, Y, Z, m, n, p and q are as described above; and R″ is H or alkyl.

[0176] The compound of formula (XXXVII) or (XXXVIII) may correspond to an intermediate or by-product obtained during the synthesis of the compound of formula (I). For example, when the compound of formula (I) is obtained in an amidation step of an ester or a carboxylic acid, as described above in the process for preparing the compound of formula (I), the compound of formula (XXXVII) or (XXXVIII) may correspond to the product that has partially reacted in the amidation reaction and contains an unreacted ester or acid group -COOR7.

[0177] In a second embodiment, the photoinitiator composition of the present invention may comprise a mixture of at least two, in particular at least three, different compounds of formula (I) as described above.

[0178] The different compounds of formula (I) may be selected from the following compounds: - All Y groups are -Z-(OM) m A compound, - compounds in which all of the Y groups are alkyl, and - Part of the Y group is -Z-(OM) m at least one compound in which some of the Y groups are alkyl; and combinations thereof.

[0179] In particular, the photoinitiator composition of the present invention comprises - All Y groups are -Z-(OM) m A compound of formula (I) - compounds of formula (I) in which all of the Y groups are alkyl, and - Part of the Y group is -Z-(OM) m at least one compound of formula (I) in which some of the Y groups are alkyl may include.

[0180] Said mixture can be obtained when the compound of formula (I) is prepared in the amidation step of the ester or carboxylic acid using a mixture of different amines as described above in the method for preparing the compound of formula (I). For example, the amidation reaction can be carried out using an amine having two -Z-OH groups (such as diethanolamine) and an amine having one -Z-OH group and one alkyl group (such as methylethanolamine). When all of the ester or carboxylic acid groups of the starting compound react with an amine having two -Z-OH groups, all of the Y groups of the resulting compound of formula (I) are -Z-OH. When all of the ester or carboxylic acid groups of the starting compound react with an amine having one -Z-OH group and one alkyl group, all of the Y groups of the resulting compound of formula (I) are alkyl. When some of the ester or carboxylic acid groups of the starting compound react with an amine having two -Z-OH groups and the other part of the ester or carboxylic acid groups of the starting compound react with an amine having one -Z-OH group and one alkyl group, some of the Y groups of the resulting compound of formula (I) are -Z-OH and the other part of the Y groups are alkyl.

[0181] In a third embodiment, the photoinitiator composition of the present invention can include a compound of formula (I) described above and a photoinitiator other than a compound of formula (I).

[0182] Photoinitiators other than compounds of formula (I) may be radical photoinitiators, in particular radical photoinitiators having Norrish Type I activity and / or Norrish Type II activity.

[0183] In one embodiment, the photoinitiator other than a compound of formula (I) can be a radical photoinitiator with Norrish Type I activity.

[0184] Non-limiting classes of radical photoinitiators suitable for use in the curable compositions of the present invention include, for example, benzoin, benzoin ethers, acetophenone, α-hydroxyacetophenone, benzil, benzil ketals, anthraquinones, phosphine oxides, acylphosphine oxides, α-hydroxyketones, phenylglyoxylates, α-aminoketones, benzophenones, thioxanthones, xanthones, acridine derivatives, phenazene derivatives, quinoxaline derivatives, triazine compounds, benzoyl formates, aromatic oximes, metallocenes, acylsilyl or acylgermanyl compounds, camphorquinone, polymeric derivatives thereof, and mixtures thereof.

[0185] Examples of suitable radical photoinitiators include, but are not limited to, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzylanthraquinone, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, benzil, benzoin, benzoin ether, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, Michler's ketone, 2,2-dialkoxybenzophenones, and 1-hydroxyphenyl ketones. Acetophenone, benzophenone, 4,4'-bis-(diethylamino)benzophenone, acetophenone, 2,2-diethyloxyacetophenone, diethyloxyacetophenone, 2-isopropylthioxanthone, thioxanthone, diethylthioxanthone, 1,5-acetonaphthylene, benzyl ketone, α-hydroxyketo, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzyl dimethyl ketal, 2,2-dimethoxy-1,2-diphenylethanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4 -(methylthio)phenyl]-2-morpholinopropanone-1,2-hydroxy-2-methyl-1-phenyl-propanone, oligomeric α-hydroxyketone, benzoylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, anisoin, anthraquinone, anthraquinone-2-sulfonic acid, sodium salt monohydrate, (benzene)tricarbonylchromium, benzyl, benzoin isobutyl ether, benzophenone / 1-hydroxycyclohexyl 4,4'-Dimethylaminobenzophenone, ...4'-Dimethylbenzyl, 2,5-Dimethylbenzophenone, 3,4-Dimethylbenzophenone, Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide / 2-Hydroxy-2-methylpropiophenone, 50 / 50 blend, 4'-Ethoxyacetophenone, 2,4,6-Trimethylbenzoyldiphenylphosphine oxide, Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, Ferrocene, 3'-Hydroxyacetophenone, 4'-Hydroxyacetophenone, 3-Hydroxybenzophenone, 4-Hydroxybenzophenone, 1 -hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-methylbenzophenone, 3-methylbenzophenone, methylbenzoyl formate, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, phenanthrenequinone, 4'-phenoxyacetophenone, (cumene)cyclopentadienyliron(II) hexafluorophosphate, 9,10-diethoxy and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthen-9-one and combinations thereof.

[0186] In particular, photoinitiators other than compounds of formula (I) are benzophenones such as SpeedCure® BP (benzophenone), SpeedCure® 7005 (polymeric benzophenone) or SpeedCure® 7006 (polymeric benzophenone); SpeedCure® 7010 (polymeric thioxanthone), SpeedCure® ITX (isopropylthioxanthone), or SpeedCure® CPTX (1-chloro-4- thioxanthones such as propoxythioxanthone; α-hydroxyacetophenones; acylphosphine oxides such as SpeedCure® BPO (phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide), SpeedCure® TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide), or SpeedCure® TPO-L (ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate). Preferably, the photoinitiator other than the compound of formula (I) is Speedcure® CPTX.

[0187] In one embodiment, the photoinitiator other than the compound of formula (I) can be a benzoyl formate, such as SpeedCure MBF (methylbenzoyl formate). In another embodiment, the photoinitiator other than the compound of formula (I) can be an acylphosphine oxide, such as SpeedCure® TPO-L (ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate). In a particularly preferred embodiment, the photoinitiator other than the compound of formula (I) can be an α-hydroxyacetophenone, such as SpeedCure 73 (2-hydroxy-2-methyl-1-phenylpropanone).

[0188] In another embodiment, the photoinitiator other than the compound of formula (I) may be a cationic photoinitiator, which is advantageously present when the composition comprises a cationically polymerizable compound as described below.

[0189] Suitable cationic photoinitiators include any type of photoinitiator that upon exposure to radiation, such as actinic radiation, forms a cation (e.g., a Bronsted acid or a Lewis acid) that initiates the reaction of the monomeric and (if present) oligomeric cationically polymerizable organic materials in the hardenable composition. For example, a cationic photoinitiator can be composed of a cationic portion and an anionic portion. The cationic portion of the photoinitiator molecule can be involved in the absorption of UV radiation, and the anionic portion of the molecule becomes a strong acid after UV absorption.

[0190] In particular, the photoinitiator other than a compound of formula (I) may be a cationic photoinitiator selected from onium salts having anions with weak nucleophilicity, such as halonium salts, iodonium salts (e.g., diaryliodonium salts such as bis(4-t-butylphenyl)iodonium perfluoro-1-butanesulfonate) or sulfonium salts (e.g., triarylsulfonium salts such as triarylsulfonium hexafluoroantimonate); sulfoxonium salts; diazonium salts; metallocene salts; and mixtures thereof.

[0191] The molar ratio between the compound of formula (I) and the photoinitiator other than the compound of formula (I) can be appropriately changed depending on the photoinitiator selected, the amount and type of polymerizable species intended to be photopolymerized, the radiation source and radiation conditions used, among other factors.However, typically, the molar ratio between the compound of formula (I) and the photoinitiator other than the compound of formula (I) can be 10 / 90 to 90 / 10, or 20 / 80 to 80 / 20, or 30 / 70 to 70 / 30, or 40 / 60 to 60 / 40, or 45 / 55 to 55 / 45.In a preferred embodiment, the molar ratio between the compound of formula (I) and the photoinitiator other than the compound of formula (I) can be 50 / 50 to 90 / 10, or 60 / 40 to 80 / 20, or 70 / 30 to 80 / 20, or about 75 / 25.

[0192] The weight ratio between the compound of formula (I) and the photoinitiator other than the compound of formula (I) may be from 10 / 90 to 90 / 10, or from 20 / 80 to 80 / 20, or from 30 / 70 to 70 / 30, or from 40 / 60 to 60 / 40, or from 45 / 55 to 55 / 45. In a preferred embodiment, the weight ratio between the compound of formula (I) and the photoinitiator other than the compound of formula (I) may be from 50 / 50 to 90 / 10, or from 60 / 40 to 80 / 20, or from 70 / 30 to 80 / 20, or about 75 / 25.

[0193] In a fourth embodiment, the photoinitiator composition may include a compound of formula (I) as described above and an amine synergist other than a compound of formula (I), preferably an amine synergist having a tertiary amine group.

[0194] Amine synergists may be introduced into the photoinitiator composition of the present invention to act synergistically with the Norrish type II photoinitiator and / or to reduce oxygen inhibition. The amine synergists are typically tertiary amines. When used in conjunction with the Norrish type II photoinitiator, the tertiary amines provide an active hydrogen donor site in the excited triplet state of the photoinitiator, thereby generating reactive alkylamino radicals, which can then initiate polymerization. The tertiary amines can also convert non-reactive peroxy species formed by the reaction of oxygen with free radicals into reactive alkylamino radicals, thereby reducing the effect of oxygen on cure.

[0195] Examples of suitable amine synergists include low molecular weight tertiary amines (i.e., molecular weights less than 200 g / mol), such as triethanolamine or N-methyldiethanolamine. Another type of amine synergist is the aminobenzoates. Examples of aminobenzoates include ethyl 4-(dimethylamino)benzoate (EDB), pentyl 4-(dimethylamino)benzoate, 2-ethylhexyl 4-(dimethylamino)benzoate, and 2-butoxyethyl 4-(dimethylamino)benzoate (BEDB).

[0196] The weight ratio between the compound of formula (I) and the amine synergist other than the compound of formula (I) may be from 10 / 90 to 90 / 10, or from 20 / 80 to 80 / 20, or from 30 / 70 to 70 / 30, or from 40 / 60 to 60 / 40, or from 45 / 55 to 55 / 45. In a preferred embodiment, the weight ratio between the compound of formula (I) and the amine synergist other than the compound of formula (I) may be from 10 / 90 to 60 / 40, or from 15 / 85 to 50 / 50, or from 20 / 80 to 40 / 60, or about 30 / 70.

[0197] [Photopolymerization method] The compounds of formula (I) described above or the photoinitiator compositions described above can be used in a photopolymerization process, i.e. a process for photopolymerizing (e.g. curing) one or more ethylenically unsaturated compounds.

[0198] A method for photopolymerizing one or more ethylenically unsaturated compounds includes contacting one or more ethylenically unsaturated compounds with a compound of formula (I) described above or a photoinitiator composition described above and irradiating the mixture, in particular with visible, near UV and / or UV light. When the compound of formula (I) contains a thioxanthone moiety, the mixture may be irradiated with an LED light source, in particular with an LED light source having an emission band in the range of 365-420 nm.

[0199] The ethylenically unsaturated compound can be as described below.

[0200] [Curable composition] [Composition A containing an ethylenically unsaturated compound] The present invention further relates to a curable composition comprising a compound of formula (I) as described above or a photoinitiator composition as described above, referred to as component a), and further comprising an ethylenically unsaturated compound, referred to as component b). This embodiment is referred to as composition A.

[0201] Composition A may comprise from 0.05 to 30%, from 0.1 to 20%, from 0.2 to 15%, from 0.5 to 10%, or from 1 to 5% by weight of a compound of formula (I), based on the total weight of the ethylenically unsaturated compounds.

[0202] Composition A may contain from 0.05 to 30%, 0.1 to 20%, 0.2 to 15%, 0.5 to 10%, or 1 to 5% by weight of a photoinitiator other than a compound of formula (I), based on the total weight of the ethylenically unsaturated compounds.

[0203] Composition A is - 0.05 to 30%, 0.1 to 20%, 0.2 to 15%, 0.5 to 10% or 1 to 5% of component a); - 70 to 99.95%, 80 to 99.9%, 85 to 99.8%, 90 to 99.5% or 95 to 99% of the composition b) where % is weight % based on the total weight of components a) and b).

[0204] Composition A comprises an ethylenically unsaturated compound. Composition A may comprise a mixture of ethylenically unsaturated compounds.

[0205] As used herein, the term "ethylenically unsaturated compound" refers to a compound that contains 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. The polymerizable carbon-carbon double bond is generally contained in a group selected from acrylate (including cyanoacrylate), methacrylate, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconate, allyl, propenyl, vinyl, and combinations thereof, preferably selected from acrylate, methacrylate, and vinyl, more preferably selected from acrylate and methacrylate. The carbon-carbon double bond of a phenyl ring is not considered to be a polymerizable carbon-carbon double bond.

[0206] In one embodiment, the ethylenically unsaturated compound comprises a (meth)acrylate-functionalized compound, in particular a (meth)acrylate-functionalized compound selected from (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, amine-modified acrylates, and mixtures thereof.

[0207] The total amount of ethylenically unsaturated compounds (including (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, and amine-modified acrylates) in composition A may be from 40 to 99.5 wt%, particularly from 50 to 95 wt%, and more particularly from 60% to 90 wt%, based on the weight of the composition. In particular, composition A may contain from 40 to 80 wt%, or from 40 to 75 wt%, or from 40 to 70 wt%, or from 40 to 65 wt%, or from 40 to 60 wt%, based on the weight of the composition. Alternatively, composition A may contain from 60 to 99.5 wt%, or from 65 to 99.5 wt%, or from 70 to 99.5 wt%, or from 75 to 99.5 wt%, or from 80 to 99.5 wt%, based on the weight of the composition.

[0208] As used herein, the term "(meth)acrylate-functionalized compound" refers to a compound containing a (meth)acrylate group, particularly an acrylate group. The term "(meth)acrylate-functionalized monomer" refers to a monomer containing a (meth)acrylate group, particularly an acrylate group. The term "(meth)acrylate-functionalized oligomer" refers to an oligomer containing a (meth)acrylate group, particularly an acrylate group. The term "(meth)acrylate group" includes acrylate groups (-O-CO-CH=CH2) and methacrylate groups (-O-CO-C(CH3)=CH2).

[0209] In one embodiment, the ethylenically unsaturated compound comprises a (meth)acrylate functionalized monomer.The ethylenically unsaturated compound may comprise a mixture of (meth)acrylate functionalized monomers.

[0210] The (meth)acrylate functionalized monomer may have a molecular weight of less than 600 g / mol, particularly from 100 to 550 g / mol, and more particularly from 200 to 500 g / mol.

[0211] The (meth)acrylate functionalized monomer may have 1 to 6 (meth)acrylate groups, especially 1 to 3 (meth)acrylate groups.

[0212] The (meth)acrylate-functionalized monomers may include a mixture of (meth)acrylate-functionalized monomers having different functionalities. For example, the (meth)acrylate-functionalized monomers may include 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.

[0213] In one embodiment, the (meth)acrylate functionalized monomer comprises a mono(meth)acrylate functionalized monomer, which can advantageously function as a reactive diluent to reduce the viscosity of the composition.

[0214] Examples of suitable mono(meth)acrylate functionalized monomers include, but are not limited to, mono-(meth)acrylate esters of aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched, or alicyclic and may be a mono-, di-, or polyalcohol, provided that only one hydroxyl group is esterified with (meth)acrylic acid); mono-(meth)acrylate esters of aromatic alcohols (such as phenol, including alkylated phenols); mono-(meth)acrylate esters of alkylaryl alcohols (such as benzyl alcohol); oligomers and polymers of diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol, and the like. mono-(meth)acrylate esters of glycols; mono-(meth)acrylate esters of monoalkyl ethers of glycols and oligoglycols; mono-(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) fatty alcohols, where the fatty alcohol may be linear, branched or alicyclic and may be a mono-alcohol, dialcohol or polyalcohol, provided that only one hydroxyl group of the alkoxylated fatty 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)acrylates, and the like.

[0215] The following compounds are specific examples of mono(meth)acrylate functionalized monomers suitable for use in Composition A: methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; n-dodecyl (meth)acrylate; tridecyl (meth)acrylate. TETRADECYL(METH)ACRYLATE;HEXADECYL(METH)ACRYLATE;2-HYDROXYETHYL(METH)ACRYLATE;2-AND 3-HYDROXYPROPYL(METH)ACRYLATE;2-METHOXYETHYL(METH)ACRYLATE;2-ETHOXYETHYL(METH)ACRYLATE;2-AND 3-ETHOXYPROPYL(METH)ACRYLATE;TETRAHYDROFURFURYL(METH)ACRYLATE;ALKOXYLATED TETRAHYDROFURFURYL(METH)ACRYLATE;2-(2-ETHOXYETHOXY)ETHYL(METH)ACRYLATE;CYCLOHEXYL(METH)ACRYLATE 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;methoxypolyethylene glycol (meth)acrylate;hydroxyethyl-butyl urethane (meth)acrylate;3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate;and combinations thereof.

[0216] In one embodiment, the (meth)acrylate functionalized monomer may include a (meth)acrylate functionalized monomer containing two or more (meth)acrylate groups per molecule.

[0217] Examples of suitable (meth)acrylate functionalized monomers containing two or more (meth)acrylate groups per molecule include acrylate and methacrylate esters of polyhydric alcohols (organic compounds containing two or more, e.g., 2 to 6, hydroxyl groups per molecule). Specific examples of suitable polyhydric alcohols include C 2-20 Alkylene glycol (carbon chain may be branched C 2-10Glycols having alkylene groups may be preferred; for example, ethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, tetramethylene glycol (1,4-butanediol), 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol, cyclohexane-1,4-dimethanol, bisphenols, and hydrogenated bisphenols, as well as their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives, diethylene glycol, glycerin, alkoxylated glycerin, triethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, alkoxylated trimethylolpropane, ditrimethylolpropane, alkoxylated glycerin, dipropylene glycol, tripropylene glycol, trimethylolpropane, alkoxylated trimethylolpropane, ditrimethylolpropane, alkoxylated glycerin, dipropylene glycol, tripropylene glycol, trimethylolpropane, alkoxylated glycerin, dipropylene glycol, tripropylene glycol, trimethylolpropane, alkoxylated glycerin, dipropylene glycol, tripropylene glycol, trimethylolpropane, alkoxylated glycerin, dipropylene glycol, tripropylene glycol, trimethylolpropane, alkoxylated glycerin, dipropylene glycol, tripropylene glycol, trimethylolpropane, alkoxylated glycerin, dipropylene glycol, tripropylene glycol, alkoxylated glycerin, di ... alkoxylated ditrimethylolpropane, pentaerythritol, alkoxylated pentaerythritol, dipentaerythritol, alkoxylated dipentaerythritol, cyclohexanediol, alkoxylated cyclohexanediol, cyclohexanedimethanol, alkoxylated cyclohexanedimethanol, norbornene dimethanol, alkoxylated norbornene dimethanol, norbornane dimethanol, alkoxylated norbornane dimethanol, aromatic ring-containing polyols, cyclohexane-1,4-dimethanol ethylene oxide adducts, bisphenol ethylene oxide adducts, hydrogenated bisphenol ethylene oxide adducts, bisphenol propylene oxide adducts, hydrogenated bisphenol propylene oxide adducts, cyclohexane-1,4-dimethanol propylene oxide adducts, sugar alcohols and alkoxylated sugar alcohols. Such polyhydric alcohols may be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.) so long as they contain at least two (meth)acrylate functional groups per molecule.

[0218] Exemplary (meth)acrylate functionalized monomers containing two or more (meth)acryloyloxy groups per molecule 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. Acrylates;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;Tricyclodecane dimethanol di(meth)acrylate;Metal di(meth)acrylates;Modified metal di(meth)acrylates Acrylates;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;Can 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 alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and combinations thereof;

[0219] Composition A may comprise 0 to 99.5 wt%, in particular 5 to 90 wt%, more particularly 10 to 80 wt%, even more particularly 15 to 75 wt%, and even more particularly 20 to 70 wt% of (meth)acrylate-functionalized monomer based on the total weight of the composition. In particular, composition A may comprise 5 to 50 wt%, or 10 to 50 wt%, or 15 to 50 wt%, or 20 to 50 wt%, or 25 to 50 wt%, or 30 to 50 wt% of (meth)acrylate-functionalized monomer based on the total weight of the composition. Alternatively, composition A may comprise 50 to 99.5 wt%, or 55 to 99.5 wt%, or 60 to 99.5 wt%, or 65 to 99.5 wt%, or 70 to 99.5 wt% of (meth)acrylate-functionalized monomer based on the total weight of the composition.

[0220] In one embodiment, the ethylenically unsaturated compound comprises a (meth)acrylate-functionalized oligomer.The ethylenically unsaturated compound may comprise a mixture of (meth)acrylate-functionalized oligomers.

[0221] The (meth)acrylate functionalized oligomer may be selected to enhance, among other properties, the flexibility, strength and / or modulus of a cured polymer prepared using Composition A.

[0222] The (meth)acrylate functionalized oligomer may have 1 to 18 (meth)acrylate groups, particularly 2 to 6 (meth)acrylate groups, and more particularly 2 to 6 acrylate groups.

[0223] The (meth)acrylate functionalized oligomers may have a number average molecular weight of 600 g / mol or more, in particular from 800 to 15000 g / mol, and more particularly from 1000 to 5000 g / mol.

[0224] In particular, the (meth)acrylate-functionalized oligomer may be selected from the group consisting of (meth)acrylate-functionalized urethane oligomers (often also referred to as "urethane (meth)acrylate oligomers", "polyurethane (meth)acrylate oligomers" or "carbamate (meth)acrylate oligomers"), (meth)acrylate-functionalized epoxy oligomers (often also referred to as "epoxy (meth)acrylate oligomers"), (meth)acrylate-functionalized polyether oligomers (often also referred to as "polyether (meth)acrylate oligomers"), (meth)acrylate-functionalized polydiene oligomers (often also referred to as "polydiene (meth)acrylate oligomers"), (meth)acrylate-functionalized polycarbonate oligomers (often also referred to as "polycarbonate (meth)acrylate oligomers"), and (meth)acrylate-functionalized polyester oligomers (often also referred to as "polyester (meth)acrylate oligomers") and mixtures thereof.

[0225] Preferably, the (meth)acrylate-functionalized oligomer comprises a (meth)acrylate-functionalized urethane oligomer, more preferably an acrylate-functionalized urethane oligomer.

[0226] Advantageously, the (meth)acrylate-functionalized oligomer comprises a (meth)acrylate-functionalized urethane oligomer having two (meth)acrylate groups, more preferably an acrylate-functionalized urethane oligomer having two acrylate groups.

[0227] Exemplary polyester (meth)acrylate oligomers include the reaction products of acrylic acid or methacrylic acid or mixtures or synthetic equivalents thereof with hydroxyl-terminated polyester polyols. The reaction process can be carried out such that all or essentially all of the hydroxyl groups of the polyester polyol are (meth)acrylated, especially when the polyester polyol is difunctional. The polyester polyols can be produced by polycondensation reactions of polyhydroxyl-functional components (especially diols) with polycarboxylic acid-functional compounds (especially dicarboxylic acids and anhydrides). The polyhydroxyl-functional components and polycarboxylic acid-functional components can each have a linear, branched, alicyclic or aromatic structure and can be used individually or in mixtures.

[0228] Examples of suitable epoxy (meth)acrylates include the reaction products of acrylic or methacrylic acid, or mixtures thereof, with epoxy resins (polyglycidyl ethers or esters).The epoxy resins are in particular 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 resins, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecaprylamide ...hexylmethyl-3',4'-epoxycyclohexylmethyl-3',4'-epoxycyclohexylmethyl-3',4' Carboxylates, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxy di(3,4-epoxycyclohexylmethyl)ether of ethylene glycol, ethylene bis(3,4-epoxycyclohexanecarboxylate), 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycidyl ethers of polyether polyols obtained by addition of one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerol, diglycidyl esters of aliphatic long-chain dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of phenol, cresol, butylphenol, or polyether alcohols obtained by addition of alkylene oxides to these compounds, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy butyl stearic acid, epoxy octyl stearic acid, epoxidized linseed oil, epoxidized polybutadiene, and the like.

[0229] Suitable polyether (meth)acrylate oligomers include, but are not limited to, the condensation reaction products of acrylic or methacrylic acid or their synthetic equivalents or mixtures with polyetherols, which are polyether polyols (such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol). Suitable polyetherols can be linear or branched materials containing ether linkages and terminal hydroxyl groups. Polyetherols can be prepared by ring-opening polymerization of cyclic ethers, such as tetrahydrofuran or alkylene oxides (e.g., ethylene oxide and / or propylene oxide), with starter molecules. Suitable starter molecules include water, polyhydroxyl-functional materials, polyester polyols, and amines.

[0230] Suitable polyurethane (meth)acrylate oligomers (also referred to as "urethane (meth)acrylate oligomers") for use in Composition A include urethanes based on aliphatic, cycloaliphatic and / or aromatic polyester polyols and polyether polyols and aliphatic, cycloaliphatic and / or aromatic polyester diisocyanates and polyether diisocyanates capped with (meth)acrylate end groups. Suitable polyurethane (meth)acrylate oligomers include, for example, aliphatic polyester-based urethane di- and tetra-acrylate oligomers, aliphatic polyether-based urethane di- and tetra-acrylate oligomers, and aliphatic polyester / polyether-based urethane di- and tetra-acrylate oligomers.

[0231] Polyurethane (meth)acrylate oligomers can be prepared by reacting an aliphatic, cycloaliphatic and / or aromatic polyisocyanate (e.g., diisocyanate, triisocyanate) with an OH-terminated polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polyorganosiloxane polyol (e.g., polydimethylsiloxane polyol), or polydiene polyol (e.g., polybutadiene polyol), or a combination thereof, to form an isocyanate-functionalized oligomer, which is then reacted with a hydroxyl-functionalized (meth)acrylate, such as hydroxyethyl acrylate or hydroxyethyl methacrylate, to provide terminal (meth)acrylate groups. For example, polyurethane (meth)acrylate oligomers can contain 2, 3, 4 or more (meth)acrylate functional groups per molecule. As known in the art, other addition sequences can also be performed to prepare polyurethane (meth)acrylates. For example, a hydroxyl-functionalized (meth)acrylate can be first reacted with a polyisocyanate to obtain an isocyanate-functionalized (meth)acrylate, which can then be reacted with an OH-terminated polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polydimethylsiloxane polyol, polybutadiene polyol, or a combination thereof. In yet another embodiment, a polyisocyanate can be first reacted with a polyol, including any of the aforementioned types of polyols, to obtain an isocyanate-functionalized polyol, which can then be reacted with a hydroxyl-functionalized (meth)acrylate to obtain a polyurethane (meth)acrylate. Alternatively, all components can be combined and reacted simultaneously.

[0232] Suitable acrylic (meth)acrylate oligomers (sometimes referred to in the art as "acrylic oligomers") include oligomers that may be described as materials having an oligomeric acrylic backbone that is functionalized with one or more (meth)acrylate groups (which may be at the terminus of the oligomer or pendant to the acrylic backbone). The acrylic backbone may be a homopolymer, random copolymer, or block copolymer of repeating units of acrylic monomers. The acrylic monomers may be any monomeric (meth)acrylate, such as C1-C6 alkyl (meth)acrylates, as well as functionalized (meth)acrylates, such as (meth)acrylates with hydroxyl, carboxylic acid, and / or epoxy groups. Acrylic (meth)acrylate oligomers may be prepared using any procedure known in the art, such as by oligomerizing monomers, at least a portion of which are functionalized with hydroxyl, carboxylic acid, and / or epoxy groups (e.g., hydroxyalkyl (meth)acrylates, (meth)acrylic acid, glycidyl (meth)acrylate), to obtain a functionalized oligomeric intermediate, which is then reacted with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functional groups.

[0233] Composition A may comprise 0 to 99.5 wt%, in particular 5 to 90 wt%, more particularly 10 to 80 wt%, even more particularly 15 to 75 wt%, even more particularly 20 to 70 wt% of the (meth)acrylate-functionalized oligomer based on the total weight of the composition. In particular, composition A may comprise 5 to 50 wt%, or 10 to 50 wt%, or 15 to 50 wt%, or 20 to 50 wt%, or 25 to 50 wt%, or 30 to 50 wt% of the (meth)acrylate-functionalized oligomer based on the total weight of the composition. Alternatively, composition A may comprise 50 to 99.5 wt%, or 55 to 99.5 wt%, or 60 to 99.5 wt%, or 65 to 99.5 wt%, or 70 to 99.5 wt% of the (meth)acrylate-functionalized oligomer based on the total weight of the composition.

[0234] In one embodiment, the ethylenically unsaturated compound comprises an amine-modified acrylate.The ethylenically unsaturated compound may comprise a mixture of amine-modified acrylates.

[0235] Amine-modified acrylates are obtained by reacting an acrylate-functionalized compound with an amine-containing compound (aza-Michael addition). The amine-modified acrylates contain at least one remaining acrylate group (i.e., an acrylate group that did not react with the amine-containing compound during the aza-Michael addition) and / or at least one (meth)acrylate group (which may not be reactive towards primary or secondary amines).

[0236] The acrylate-functionalized compounds can be the acrylate-functionalized monomers and / or acrylate-functionalized oligomers described above.

[0237] The amine-containing compound contains a primary or secondary amino group, and optionally a tertiary amino group. The amine-containing compound may contain more than one primary and / or secondary amino group. The amine-containing compound may be selected from monoethanolamine (2-aminoethanol), 2-ethylhexylamine, octylamine, cyclohexylamine, sec-butylamine, isopropylamine, diethylamine, diethanolamine, dipropylamine, dibutylamine, 2-(methylamino)ethano-1,2-methoxyethylamine, bis(2-hydroxypropyl)amine, diisopropylamine, dipentylamine, dihexylamine, bis(2-ethylhexyl)amine, 1,2,3,4-tetrahydroisoquinoline, N-benzylmethylamine, morpholine, piperidine, dioctylamine, and di-cocoamine, dimethylaminopropylamine, dimethylaminopropylaminopropylamine, 1,4-bis(3-aminopropyl)piperazine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(3-aminopropyl)piperazine, aniline, and optionally substituted benzocaine (ethyl-4-aminobenzoate).

[0238] Examples of commercially available amine modified acrylates include CN3705, CN3715, CN3755, CN381 and CN386, all available from Arkema. Polymeric or multi-amino types are also suitable.

[0239] Composition A may comprise from 0 to 25% by weight, particularly from 2.5 to 20% by weight, more particularly from 5 to 15% by weight of the amine-modified acrylate, based on the total weight of the composition.

[0240] In a first embodiment, the ethylenically unsaturated compound b) consists essentially of one or more (meth)acrylate-functionalized monomers as described above and, optionally, one or more (meth)acrylate-functionalized oligomers as described above.

[0241] In a second embodiment, the ethylenically unsaturated compound b) consists essentially of one or more (meth)acrylate-functionalized monomers as described above and, optionally, one or more amine-modified acrylates as described above.

[0242] In a third embodiment, the ethylenically unsaturated compound b) consists essentially of a mixture of one or more (meth)acrylate-functionalized monomers as described above and one or more (meth)acrylate-functionalized oligomers as described above.

[0243] In a fourth embodiment, the ethylenically unsaturated compound b) consists essentially of one or more (meth)acrylate-functionalized oligomers as described above and, optionally, one or more (meth)acrylate-functionalized monomers as described above.

[0244] In a fifth embodiment, the ethylenically unsaturated compound b) consists essentially of one or more (meth)acrylate-functionalized oligomers as described above and, optionally, one or more amine-modified acrylates as described above.

[0245] In a sixth embodiment, the ethylenically unsaturated compound b) consists essentially of a mixture of one or more (meth)acrylate-functionalized monomers as described above, one or more (meth)acrylate-functionalized oligomers as described above, and one or more amine-modified acrylates as described above.

[0246] [Composition B containing unsaturated polymer dispersion or emulsion] The present invention further relates to a curable composition comprising a compound of formula (I) as described above or a photoinitiator composition as described above, referred to as component a), and further comprising an unsaturated polymer dispersion or emulsion, referred to as component c). This embodiment is referred to as composition B.

[0247] Composition B may comprise from 0.05% to 30%, from 0.1% to 20%, from 0.2 to 15%, from 0.5 to 10%, or from 1 to 5% by weight of a compound of formula (I), based on the total weight of the composition.

[0248] Composition B may comprise from 0.05 to 30%, from 0.1 to 20%, from 0.2 to 15%, from 0.5 to 10%, or from 1 to 5% by weight of a photoinitiator other than a compound of formula (I), based on the total weight of the ethylenically unsaturated polymer.

[0249] Composition B is - 0.05 to 30%, 0.1 to 20%, 0.2 to 15%, 0.5 to 10% or 1 to 5% of component a); - 70 to 99.95%, 80 to 99.9%, 85 to 99.8%, 90 to 99.5% or 95 to 99% of the composition c) where % is by weight based on the total weight of components a) and c).

[0250] As used herein, the term "unsaturated polymer dispersion or emulsion" means a dispersion or emulsion that includes an ethylenically unsaturated polymer.

[0251] The unsaturated polymer dispersion or emulsion can be an aqueous polymer dispersion or emulsion. In one embodiment, the unsaturated polymer dispersion is a polyurethane dispersion (PUD), an acrylic dispersion, and mixtures thereof, especially PUD. In one embodiment, the unsaturated polymer emulsion is an unsaturated polyester emulsion. In one embodiment, the unsaturated polymer emulsion is an emulsion of (meth)acrylate-functionalized oligomers as described above, especially an emulsion of (meth)acrylate-functionalized oligomers selected from (meth)acrylate-functionalized urethane oligomers, (meth)acrylate-functionalized epoxy oligomers, (meth)acrylate-functionalized polyether oligomers, (meth)acrylate-functionalized polydiene oligomers, (meth)acrylate-functionalized polycarbonate oligomers, (meth)acrylate-functionalized polyester oligomers, and mixtures thereof.

[0252] As used herein, the term "polyurethane dispersion" means a dispersion that includes a polyurethane polymer or a polyurethane copolymer, such as a polyurethane-acrylate copolymer.

[0253] Polyurethane dispersions are typically made by first forming a polyurethane prepolymer that contains end groups, such as isocyanate (NCO) groups, and that can undergo a subsequent chain extension reaction. The polyurethane prepolymer can be diluted with an organic solvent or a reactive diluent. Dilution advantageously reduces the viscosity of the prepolymer, facilitating its subsequent dispersion in water. The prepolymer can undergo a chain extension reaction before or after dispersion in water to increase the length of the polymer chains and / or add additional functionality to the polyurethane.

[0254] In one embodiment, the polyurethane dispersion comprises a polyurethane polymer and optionally a reactive diluent. The polyurethane polymer may have ethylenically unsaturated groups. The polyurethane polymer may be formed by chain extending at least one isocyanate-terminated ethylenically unsaturated polyurethane prepolymer (P) with a chain extender (E) having at least two isocyanate-reactive groups.

[0255] The prepolymer (P) is (i) one or more isocyanate-reactive components containing at least one ethylenic unsaturation, preferably selected from active hydrogen-containing (meth)acrylates; (ii) one or more polyisocyanates, preferably diisocyanates; (iii) one or more isocyanate-reactive components containing ionic, potentially ionic or hydrophilic ether groups, preferably ionic groups derived from acidic groups, in particular said component (iii) having two isocyanate-reactive groups, more particularly two OH groups; and (iv) optionally, one or more isocyanate-reactive components other than component (i) or component (iii), preferably having two isocyanate-reactive groups, in particular OH groups, such that the molar ratio of components (i), (ii), (iii) and (iv) results in a polyurethane prepolymer containing terminal isocyanate groups. can be formed by reacting

[0256] Component (i) may be a polyol component comprising a monoalcohol (i-1) having at least 1, preferably 1 to 5 (meth)acrylate groups, and optionally a diol (i-2) having at least 1, preferably 1 to 4 (meth)acrylate groups. Component (i) containing ethylenic unsaturation may be selected from polyester (meth)acrylates, epoxy (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, hydroxy-containing (meth)acrylates (e.g., partial (meth)acrylic acid esters of alkylene polyols, which may be alkoxylated, or partial (meth)acrylic acid esters of polyols obtained from dipolyol ethers of said alkylene polyols), and combinations thereof.

[0257] Component (iii) may be a diol having an acidic group or a salt thereof. The acidic group may be a carboxylic acid (-COOH) group, a carboxylate (-COO - ) group, a phosphonic acid (-P(=O)(OH)2) group, a phosphonate (-P(=O)(OR)2) group, a sulfonic acid (-S(=O)2OH) group, a sulfonate (-S(=O)2OR) group, a phosphate (-OP(=O)(OR)2) group, where each R is independently a counter ion, a hydrogen atom, or an optionally substituted hydrocarbyl.

[0258] Component (iv) can be a monomeric or oligomeric monoalcohol or polyol, preferably a diol. More particularly, component (iv) is an oligomer, such as a polyether or polyester diol.

[0259] The chain extender (E) may be selected from polyols and / or polyamines, more preferably from diols and / or diamines, even more preferably from diamines.

[0260] The reactive diluent (D) may be a compound having one or more ethylenically unsaturated groups that may be used in the preparation of the polyurethane prepolymer as a diluent for diluting the polyurethane prepolymer during the formation of the polyurethane dispersion. The reactive diluent may react with the acrylate group on the dispersed polyurethane during the actinic radiation curing step by free radical reaction. When added to the polyurethane prepolymer, the reactive diluent may be used to control the viscosity of the polyurethane prepolymer. In particular, the reactive diluent (D) may be a mono(meth)acrylate functionalized monomer as described above for composition A. The reactive diluent (D) may comprise about 10% to about 90% by weight, preferably 10 to 50% by weight, based on the solid content of the dispersion.

[0261] In another embodiment, the polyurethane dispersion may be a dispersion comprising a polyurethane-acrylate copolymer (also called a PUA dispersion), which can be obtained by reacting the above-described isocyanate-terminated ethylenically unsaturated polyurethane prepolymer (P) with a (meth)acrylate monomer, for example an ester of (meth)acrylic acid and a monoalcohol having from 1 to 20, preferably from 4 to 12, carbon atoms.

[0262] As used herein, the term "acrylic dispersion" refers to a dispersion that includes an acrylic polymer or acrylic copolymer that contains residual ethylenic unsaturation.

[0263] As used herein, the term "unsaturated polyester emulsion" means an emulsion that includes an unsaturated polyester.

[0264] As used herein, the term "emulsion of a (meth)acrylate-functionalized oligomer" means an emulsion that includes a (meth)acrylate-functionalized oligomer.

[0265] Emulsions of (meth)acrylate-functionalized oligomers can be obtained by emulsifying one or more (meth)acrylate-functionalized oligomers in water containing a surfactant, in particular a polymeric amphiphilic surfactant (protective colloid).

[0266] [Common features of Composition A and Composition B] The above-described Composition A and Composition B are - Amine synergists; - cationically polymerizable compounds; - additives; - Solvent The composition may further comprise one or more compounds selected from:

[0267] [Amine synergists] The polymerizable composition of the present invention may include an amine synergist. The polymerizable composition may include a mixture of amine synergists.

[0268] The amine synergist can be as described above for the photoinitiator composition.

[0269] [Cationic polymerizable compounds] The composition of the present invention may further comprise a cationically polymerizable compound. The composition of the present invention may comprise a mixture of cationically polymerizable compounds.

[0270] When the composition includes a cationically polymerizable compound, the composition may be a hybrid free radical / cationic composition, ie, a composition that cures by both free radical and cationic polymerization.

[0271] The term "cationically polymerizable compound" refers to a compound that contains a polymerizable functional group, such as a carbon-carbon double bond substituted with a heterocyclic group or an electron donating group, that polymerizes via a cationic mechanism in which a cationic initiator transfers charge to a cationically polymerizable compound, which then becomes reactive and initiates chain propagation by reaction with another cationically polymerizable compound.

[0272] The cationically polymerizable compound may be selected from epoxy-functionalized compounds, oxetanes, oxolanes, cyclic acetals, cyclic lactones, thiiranes, thietanes, spiroorthoesters, ethylenically unsaturated compounds other than (meth)acrylates, derivatives thereof, and mixtures thereof.

[0273] In a preferred embodiment, the cationically polymerizable compound may be selected from epoxy-functionalized compounds, oxetanes and mixtures thereof, in particular aromatic epoxy-functionalized compounds, cycloaliphatic epoxy-functionalized compounds, oxetanes and mixtures thereof.

[0274] Suitable epoxy-functionalized compounds capable of cationically polymerizing are glycidyl ethers, particularly mono-, di-, tri- and polyglycidyl ether compounds, and alicyclic ether compounds, including those containing residues of carboxylic acids, such as alkyl carboxylic acid residues, alkylcycloalkyl carboxylic acid residues and dialkyldicarboxylic acid residues. For example, epoxy-functionalized compounds include 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 resins, 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( ... epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl)ether of ethylene glycol, ethylenebis(3,4-epoxycyclohexanecarboxylate), epoxyhexahydrodioctylphthalate, epoxyhexahydro-di-2-ethylhexylphthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerol, diglycidyl esters of aliphatic long-chain dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of phenol, cresol, butylphenol, or polyether alcohols obtained by adding alkylene oxides to these compounds, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy butyl stearic acid, epoxy octyl stearic acid, epoxidized linseed oil, and epoxidized polybutadiene.

[0275] Suitable oxetanes capable of cationically polymerizing include trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-ethyl-3-phenoxymethyloxetane, and bis(3-ethyl-3-methyloxy)butane, 3-ethyl-3-oxetanemethanol.

[0276] Suitable cationically polymerizable oxolanes include tetrahydrofuran and 2,3-dimethyltetrahydrofuran.

[0277] Suitable cationically polymerizable cyclic acetals include trioxane, 1,3-dioxolane, and 1,3,6-trioxanecyclooctane.

[0278] Suitable cationically polymerizable cyclic lactones include β-propiolactone and ε-caprolactone.

[0279] Suitable cationically polymerizable thiiranes include ethylene sulfide, 1,2-propylene sulfide, and thioepichlorohydrin.

[0280] Suitable cationically polymerizable thietanes include 3,3-dimethylthietane.

[0281] Suitable cationically polymerizable spiroorthoesters are compounds obtainable by reaction of an epoxy compound with a lactone.

[0282] Suitable ethylenically unsaturated compounds other than cationically polymerizable (meth)acrylates include vinyl ethers such as ethylene glycol divinyl ether, triethylene glycol divinyl ether, and trimethylolpropane trivinyl ether; aliphatic vinyl monomers such as vinylcyclohexane; olefins such as isobutylene; dienes such as butadiene; vinyl alkyl ethers; vinyl aromatic monomers such as styrene and alkylstyrenes; unsaturated polymers such as polybutadiene; derivatives of the above organic materials; and the like, at least some of which may also be polymerizable by free radical mechanisms.

[0283] The composition of the present invention, when it comprises a cationically polymerizable compound, may further comprise a polyol. Suitable polyols are as described above.

[0284] The curable composition of the present invention may comprise from 0 to 50% by weight, particularly from 5 to 40% by weight, more particularly from 10 to 30% by weight of a cationically polymerizable compound, based on the total weight of the curable composition.

[0285] [Additives] The curable composition of the present invention may include additives. The curable composition may include a mixture of additives.

[0286] In particular, the additives may be selected from sensitizers, stabilizers (antioxidants, light blockers / absorbers, polymerization inhibitors), antifoaming agents, flow or leveling agents, colorants, pigments, dispersants (wetting agents, surfactants), slip additives, fillers, chain transfer agents, thixotropic agents, matting agents, impact modifiers, waxes, mixtures thereof, and any other additives conventionally used in coating, sealant, adhesive, molding, 3D printing or ink technology.

[0287] The curable composition may include a sensitizer.

[0288] To extend the sensitivity of the photoinitiator to longer wavelengths, a sensitizer can be introduced into the curable composition of the present invention, for example, a sensitizer can absorb light at a longer or shorter wavelength than the photoinitiator and transfer the energy to the photoinitiator, returning it to its ground state.

[0289] Examples of suitable sensitizers include anthracene and carbazole.

[0290] The concentration of the sensitizer in the curable composition will vary depending on the photoinitiator used, but typically the curable composition is formulated to contain from 0 to 5 wt %, particularly from 0.1 to 3 wt %, and more particularly from 0.5 to 2 wt %, of the sensitizer, based on the total weight of the curable composition.

[0291] The curable composition may include a stabilizer.

[0292] Stabilizers may be incorporated into the curable compositions of the present invention to provide suitable storage stability, processing stability, and shelf life. Advantageously, one or more such stabilizers are present at each stage of the method used to prepare the curable compositions to protect against undesired reactions during processing of the ethylenically unsaturated components of the curable compositions. As used herein, the term "stabilizer" refers to a compound or substance that retards or prevents reaction or curing of actinic radiation-curable functional groups present in the composition in the absence of actinic radiation. However, it is advantageous to select the amount and type of stabilizer such that the composition remains curable when exposed to actinic radiation (i.e., the stabilizer does not interfere with radiation curing of the composition). Typically, stabilizers effective for the purposes of the present invention would be classified as free radical stabilizers (i.e., stabilizers that function by inhibiting free radical reactions).

[0293] Any stabilizer known in the art related to (meth)acrylate functionalized compounds can be utilized in the present invention. Quinones represent a particularly preferred class of stabilizers that can be used in the context of the present invention. As used herein, the term "quinone" includes both quinones and hydroquinones, as well as their ethers, such as monoalkyl, monoaryl, monoaralkyl, and bis(hydroxyalkyl) ethers of hydroquinone. Hydroquinone monomethyl ether is one example of a suitable stabilizer that can be utilized. Other stabilizers known in the art, such as hydroquinone (HQ), 4-tert-butylcatechol (TBC), 3,5-di-tert-butyl-4-hydroxytoluene (BHT), phenothiazine (PTZ), pyrogallol, phosphite compounds, triphenylantimony, and tin (II) salts, can also be used.

[0294] The concentration of stabilizer in the curable composition will vary depending on the particular stabilizer or combination of stabilizers selected for use, as well as the degree of stabilization desired and the susceptibility of the components in the curable composition to degradation in the absence of the stabilizer. Typically, however, the curable composition is formulated to contain 5 to 5000 ppm of stabilizer. According to certain embodiments of the present invention, the reaction mixture during each stage of the process used to prepare the curable composition contains at least some stabilizer, for example at least 10 ppm of stabilizer.

[0295] The polymerizable composition may include a colorant. The colorant may be a dye, a pigment, and a mixture thereof. The term "dye" as used herein means a colorant having a solubility of 10 mg / L or more in the medium in which it is introduced at 25°C. The term "pigment" is defined in DIN 55943 as a colorant that is substantially insoluble in the application medium under relevant ambient conditions and thus has a solubility therein of less than 10 mg / L at 25°C. The term "CI" is used as an abbreviation for Color Index.

[0296] The colorant may be a pigment. Organic and / or inorganic pigments may be used. If the colorant is not a self-dispersed pigment, the inkjet ink preferably also comprises a dispersant, more preferably a polymeric dispersant. The pigment may be black, cyan, magenta, yellow, red, orange, violet, blue, green, brown, and mixtures thereof. The pigment may be selected from those disclosed by HERBST, Willy et al. Industrial Organic Pigments, Production, Properties, Applications. 3rd Edition. Wiley-VCH, 2004. ISBN 3527305769.

[0297] The polymerizable composition of the present invention may include a dispersant. Dispersants may be used to disperse insoluble materials, such as pigments or fillers, in the polymerizable composition.

[0298] The dispersant may be a polymeric dispersant, a surfactant, and mixtures thereof.

[0299] Typical polymeric dispersants are copolymers of two, three, four, five or more monomers. The properties of the polymeric dispersant depend on both the nature of the monomers and their distribution within the polymer. Copolymeric dispersants preferably have the following polymer composition: - random copolymers (e.g. ABBAABAB); - alternating copolymers (e.g., ABABABAB); - gradient copolymers (e.g., AAABAABBABBB); - Block copolymers (e.g., AAAAAABBBBBB); - graft copolymers (polymer backbone and polymer side chains attached to the backbone); and mixed forms of these copolymers.

[0300] The polymeric dispersant may have a number average molecular weight Mn between 500 and 30,000, more preferably between 1,500 and 10,000.

[0301] Commercially available examples of polymeric dispersants include: - DISPERBYK® Dispersants available from BYK CHEMIE GMBH; - SOLSPERSE® dispersants available from LUBRIZOL; - TEGO® DISPERSE dispersants from EVONIK; - DISPEX®, EFKA®, and JONCRYL® dispersants from BASF; - DISPONER® dispersants from ELEMENTIS.

[0302] [solvent] The curable compositions of the present invention may be solvent-based or water-based. As used herein, the term "solvent" refers to a non-reactive organic solvent, i.e., a solvent containing carbon and hydrogen atoms that does not react when exposed to actinic radiation used to cure the curable compositions described herein.

[0303] Advantageously, the curable compositions of the present invention may be formulated to be solvent-free, i.e., free of any non-reactive volatile materials (materials having a boiling point of 150° C. or less at atmospheric pressure). For example, the curable compositions of the present invention may contain little or no non-reactive solvent, e.g., less than 10 wt. %, or less than 5 wt. %, or less than 1 wt. %, or even 0 wt. % non-reactive solvent, based on the total weight of the curable composition. As used herein, the term non-reactive solvent refers to a solvent that does not react when exposed to actinic radiation used to cure the curable compositions described herein.

[0304] In one embodiment, the curable composition of the present invention can be water-based. In particular, the curable composition of the present invention can be a water-based polyurethane.

[0305] [Composition] The curable compositions of the present invention may be formulated as a one-component or one-part system, i.e., the curable composition may be cured directly, i.e., not combined with another component or second part before being cured.

[0306] In a first embodiment, the curable composition of the present invention comprises: a) a compound of formula (I) or a photoinitiator composition described above; b) ethylenically unsaturated compounds or unsaturated polymer dispersions or emulsions; c) optionally an amine synergist; d) optionally a cationically polymerizable compound; e) optional additives; f) Optionally, a solvent may include.

[0307] Preferably, the composition of the first embodiment does not contain any components other than components a) to f).

[0308] In preferred embodiments of the invention, the curable compositions are liquid at 25° C. In various embodiments of the 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 500 mPa.s, or less than 250 mPa.s, or less than 100 mPa.s, measured at 25° C. using a Brookfield Viscometer Model DV-II with a 27 spindle (spindle speed typically varies between 20 rpm and 200 rpm depending on viscosity). In advantageous embodiments of the invention, the viscosity of the curable composition is from 10 to 10,000 mPa.s, or from 10 to 5,000 mPa.s, or from 10 to 1,000 mPa.s, or from 10 to 500 mPa.s, or from 10 to 250 mPa.s, or from 10 to 100 mPa.s, at 25° C.

[0309] The curable compositions described herein may be compositions that undergo curing by free radical polymerization. In certain embodiments, the curable compositions may be photocured (i.e., cured by exposure to actinic radiation, such as light, particularly visible or UV light). When the compound of formula (I) is a thioxanthone, the composition may be cured by an LED light source.

[0310] The curable composition of the present invention can be an ink composition, an overprint varnish composition, a coating composition, an adhesive composition, a sealant composition, a molding composition, a dental composition, a cosmetic composition or a 3D printing composition, in particular an ink composition.

[0311] 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, composites, antistatic layers, electronic applications, recyclable materials, smart materials that can detect and respond to stimuli, packaging materials, personal care products, cosmetics, articles used in agriculture, water or food processing, or animal husbandry, and biomedical materials. Thus, the curable compositions of the present invention find utility in the manufacture of biocompatible articles. Such articles may, for example, exhibit high biocompatibility, low cytotoxicity, and / or low extractables.

[0312] The compositions according to the invention can in particular be used to obtain cured products and 3D printed articles according to the following methods.

[0313] [Method of preparing the cured product and 3D printed article] The method of preparing a cured product according to the present invention comprises curing the composition according to the present invention. In particular, the composition may be cured by exposing the composition to radiation. More particularly, the composition may be cured by exposing the composition to UV, near UV, and / or visible radiation. When the compound of formula (I) is a thioxanthone, the composition may be cured by exposing the composition to an LED light source, in particular an LED light source having an emission band in the range of 365-420 nm.

[0314] Curing can be accelerated or promoted by providing energy to the curable composition, such as by heating the curable composition. Thus, 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 actinic radiation, and further curing is achieved by heating the partially cured article. For example, a product (e.g., a 3D printed article) 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.

[0315] Prior to curing, the curable composition may be applied to a substrate surface by any known common method, such as spraying, jetting, knife coating, roller coating, casting, drum coating, dipping, and combinations thereof. Indirect application using transfer techniques may also be used.

[0316] The substrate to which the curable composition is applied and cured can be any type of substrate. Suitable substrates are described in more detail below. When used as an adhesive, the curable composition can be placed between two substrates and cured, whereby the cured composition bonds the substrates together to provide an adhesive article. The curable composition of the present invention can also be formed or cured in bulk form (e.g., the curable composition can be poured into a suitable mold and then cured).

[0317] The cured product obtained by the method of the present invention can be an ink, an overprint varnish, a coating, an adhesive, a sealant, a molding, a dental material, a cosmetic, or a 3D printed article.

[0318] The 3D printed article can in particular be obtained by means of a method for preparing a 3D printed article, which comprises printing the 3D article with the composition of the invention. In particular, the method can comprise printing the 3D article layer by layer or continuously.

[0319] Multiple layers of the curable composition according to the present invention can be applied to a substrate surface; the multiple layers can be cured simultaneously (e.g., by exposure to a single dose of radiation) or each layer can be cured sequentially prior to application of an additional layer of the curable composition.

[0320] The curable compositions described herein can be used as resins in three-dimensional printing applications. Three-dimensional (3D) printing, also known as additive manufacturing, is a method in which 3D digital models are produced by the addition of component materials. 3D printed objects are produced by utilizing computer-aided design (CAD) data of the object to sequentially build up two-dimensional (2D) layers or slices that correspond to cross sections of the 3D object. Stereolithography (SL) is a type of additive manufacturing in which liquid resin is selectively exposed to radiation to harden it and form each 2D layer. The radiation can be in the form of electromagnetic waves or electron beams. The most commonly applied energy sources are ultraviolet, visible light, or infrared.

[0321] In stereolithography and other photocurable 3D printing processes, a low intensity light source is typically applied to irradiate each layer of photocurable resin to form the desired article. As a result, the polymerization rate of the photocurable resin and the green strength of the printed article are important criteria for whether a particular photocurable resin will sufficiently polymerize (cure) upon irradiation and have sufficient green strength to maintain its integrity throughout the 3D printing process and post-processing.

[0322] The curable compositions of the present invention are particularly useful as 3D printing resin formulations, i.e. compositions intended for use in producing three-dimensional articles using 3D printing techniques. Such three-dimensional articles may be free-standing / self-supporting and may consist essentially or consist of the cured compositions of the present invention. The three-dimensional articles may also be composites comprising at least one component consisting essentially or consist of the cured compositions described above and at least one additional component consisting of one or more materials other than such cured compositions (e.g., a metal component or a thermoplastic component or an inorganic filler or fiber reinforcement). The curable compositions of the present invention are particularly useful in digital light printing (DLP), although other types of three-dimensional (3D) printing methods (e.g., SLA, inkjet, multi-jet printing, piezoelectric printing, actinic radiation curing extrusion, gel lamination printing) can also be performed using the curable compositions of the present invention. The curable compositions of the present invention can be used in three-dimensional printing operations together with another material that serves as a scaffold or support for the article formed from the curable compositions of the present invention.

[0323] The curable compositions of the present invention are therefore useful for implementing various types of three-dimensional fabrication or printing techniques, including methods in which the construction of a three-dimensional article is carried out 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, UV or other actinic radiation. For example, a new layer can be formed on the top surface of a growing object or on the bottom surface of a growing object. The curable compositions of the present invention can also be advantageously used for the production of three-dimensional objects by additive manufacturing carried out in succession. For example, objects can be produced from liquid interfaces. Suitable methods of this type are sometimes referred to in the art as "continuous liquid interface (or interphase) production (or printing)" ("CLIP") methods. Such methods are described, for example, in WO 2014 / 126830; WO 2014 / 126834; WO 2014 / 126837; and Tumbleston et al., “Continuous Liquid Interface Production of 3D Objects,” Science Vol. 347, Issue 6228, pp. 1349-1352 (March 20, 2015), the entire disclosures of which are incorporated herein by reference in their entirety for all purposes.

[0324] The curable composition may be delivered by ejection from a print head rather than delivered from a tank. This type of method is commonly referred to as inkjet or multi-jet 3D printing. One or more UV curing sources mounted directly behind the inkjet print head cure the curable composition immediately after it is applied to the build surface substrate or to a previously applied layer. This method allows the use of two or more print heads that can apply different compositions to different areas of each layer. For example, compositions of different colors or different physical properties can be applied simultaneously to create 3D printed parts of various compositions. In a typical usage, a support material (which is later removed during post-processing) is deposited simultaneously with the composition used to create the desired 3D printed part. The print head can operate at temperatures from about 25°C to about 100°C. The viscosity of the curable composition is less than 30 mPa·s at the operating temperature of the print head.

[0325] The method for preparing a 3D printed article comprises: a) providing (e.g., coating) a first layer of a curable composition according to the present invention onto a surface; b) at least partially curing the first layer to provide a cured first layer; c) providing (e.g., coating) a second layer of a curable composition over the cured first layer; d) at least partially curing the second layer to provide a cured second layer adhered to the cured first layer; and e) repeating steps c) and d) as many times as desired to build a three-dimensional article. may include.

[0326] After the 3D article has been printed, it may be subjected to one or more post-treatment steps, which may be selected from one or more of the following steps, either simultaneously or sequentially: removal of any printed support structures, removal of residual resin by washing with water and / or organic solvents, post-curing using heat treatment and / or actinic radiation. Post-treatment steps can be used to convert the freshly printed article into a finished functional article ready for use in its intended application.

[0327] [Inkjet printing method] The ink jet printing method according to the present invention comprises jetting the polymerizable composition of the present invention onto a substrate.

[0328] The substrate onto which the polymerizable composition is jetted can be any type of substrate described above.

[0329] The polymerizable composition can be jetted by one or more printheads, which eject small droplets in a controlled manner through a nozzle onto a substrate moving relative to the printhead.

[0330] The printhead may be a piezoelectric head or a continuous printhead.

[0331] Inkjet printing can be performed in a single pass or multi-pass print mode.

[0332] The inkjet printing process may further include a UV curing step. In inkjet printing, a UV curing device may be placed in combination with the printhead of the inkjet printer and move therewith such that the liquid UV curable inkjet ink is exposed to curing radiation immediately after jetting.

[0333] In a particularly preferred embodiment, the UV curing step is carried out using a UV LED light source.

[0334] To facilitate curing, the inkjet printer may include one or more oxygen scavenging units that provide a blanket of nitrogen or other relatively inert gas (e.g., CO2) at adjustable position and with adjustable inert gas concentration to reduce the oxygen concentration in the curing environment.

[0335] [Base material] The substrate to which the binder or polymerizable composition of the present invention is applied can be any type of substrate.

[0336] The substrate may be a ceramic, metallic, mineral, cellulosic, animal-based or polymeric substrate. The substrate may also be a part of the human body, such as a tooth or a nail.

[0337] The substrate can be porous or substantially non-porous. The substrate can be transparent, translucent or opaque.

[0338] Examples of ceramic substrates include alumina-based ceramics and zirconia-based ceramics.

[0339] Examples of metallic substrates include titanium, gold, silver, copper, brass, steel and bronze.

[0340] Examples of mineral substrates include glass, asbestos and basalt.

[0341] Examples of cellulosic substrates include plain paper or resin-coated paper (e.g., polyethylene or polypropylene coated paper). There is no practical limit to the type of paper, and it includes newsprint, magazine paper, office paper, wallpaper, as well as higher basis weight papers, usually referred to as paperboard, such as white chipboard, corrugated cardboard, and packaging board. Further examples of cellulosic substrates include bamboo, cotton, flax, hemp, jute, lyocell, modal, rayon, raffia, ramie, and sisal.

[0342] Examples of cellulosic substrates include wool, fur, silk and leather.

[0343] Examples of polymer substrates include polyethylene, polypropylene, polycarbonate, polyvinyl chloride, polyethylene terephthalate, polyethylene naphthalate, polylactide, polyamide, polyimide, polyacrylonitrile, polyurethane, acrylonitrile butadiene styrene.

[0344] There is no limit to the shape of the substrate: it can be a sheet, a film, a nonwoven or woven mat, or a three-dimensional article.

[0345] In particular, the substrate may be selected from food and beverage packaging, pharmaceutical packaging, textiles, nails, teeth, medical devices, food and beverage processing equipment, water pipes.

[0346] [use] The compounds of formula (I) as described above or the photoinitiator compositions as described above may be used as photoinitiating systems in radiation curable compositions, in particular UV or LED curable compositions.

[0347] As used herein, a "UV curable composition" means a composition that is at least partially cured by exposure to UV light emitted by a mercury light source, particularly a mercury lamp, and an "LED curable composition" means a composition that is at least partially cured by exposure to UV light emitted by an LED light source, particularly an LED light source having an emission band in the range of 365-420 nm.

[0348] Other curing methods such as heat may be combined with UV light.

[0349] The compound of formula (I) described above or the photoinitiator composition described above can be used in a photopolymerization reaction, which can be used to photopolymerize (e.g., cure) one or more of the ethylenically unsaturated compounds described above.

[0350] The compound of formula (I) described above or the photoinitiator composition described above can be used in the curable composition described above.In particular, the curable composition can be an ink composition, an overprint varnish composition, a coating composition, an adhesive composition, a sealant composition, a molding composition, a dental composition, a cosmetic composition or a 3D printing composition.

[0351] The inventive curable compositions can be used to obtain a cured product. In particular, the cured product can be an ink, an overprint varnish, a coating, an adhesive, a sealant, a molding, a cosmetic product, or a 3D printed article.

[0352] When a curable composition comprises a compound of formula (I) in which at least a portion of the M groups are (meth)acryloyl, the cured product obtained therefrom may exhibit reduced amounts of extractables because at least a portion of the compound of formula (I) is chemically bonded to the cured polymer matrix.

[0353] The present invention therefore also relates to the use of compounds of formula (I) in which at least a portion of the M groups are (meth)acryloyl to obtain cured products having reduced amounts of extractables, which can be assessed in comparison to cured products obtained with conventional photoinitiators (i.e. non-polymerizable or polymeric photoinitiators).

[0354] Extractables can be any component that migrates from the cured product. In particular, extractables can be photoinitiators or residues thereof.

[0355] Ink migration can occur in a variety of ways: Penetrating migration - through the substrate to the back of the print; Set-off migration - from the printed side of the substrate to the backside of the substrate while it is stacked or stored in a roll; Gas phase transition - volatile compounds evaporate when heated; Concentration Extraction - Important compounds are concentrated during cooking or sterilization.

[0356] The amount of extractables can be quantitatively measured using a suitable analytical method, such as liquid chromatography-mass spectrometry (LC-MS). For example, the curable composition can be applied in a 12 μm thick film onto a glass substrate and crosslinked using a UV Hg lamp. The resulting cured film is removed from the glass plate, weighed, and immersed in a solvent such as acetonitrile or dichloromethane. Finally, the liquid fraction is evaporated and the residue corresponding to the extractables portion is weighed to determine the amount of uncured product (not trapped within the photocurable network).

[0357] Analytical methods such as Nuclear Magnetic Resonance (NMR), Liquid Chromatography Mass Spectrometry (LC-MS) or Gas Chromatography Mass Spectrometry (GC-MS) can then be used to identify the nature of the extractables and to elaborate their corresponding contents.

[0358] In particular, the cured product may have less than 5%, less than 2%, less than 1%, less than 0.5%, less than 0.25%, or less than 0.1% extractables based on the weight of the cured product.

[0359] Although embodiments are described herein in a manner that allows a clear and concise specification to be written, it is intended and will be understood that the embodiments can be variously combined or separated without departing from the invention, For example, it will be understood that all preferred features described herein are applicable to all aspects of the invention described herein.

[0360] In some embodiments, the invention described herein may be construed as excluding any element or process step that does not materially affect the basic and novel characteristics of the invention. In addition, in some embodiments, the invention may be construed as excluding any element or process step not specified herein.

[0361] Although the invention has been illustrated and described herein with reference to specific embodiments, it is not intended that the invention be limited to the details shown. Rather, various modifications can be made in the details, within the scope of the claims and equivalents, without departing from the invention. EXAMPLES

[0362] [material] All materials used in the examples are readily available from standard commercial sources such as Sigma-Aldrich and Tokyo Chemical Industry Co., Ltd. unless otherwise specified. 2-(Chlorothio)benzoyl chloride was prepared according to the procedure described in U.S. Pat. No. 4,101,558 (The Sherwin-Williams Company). Ucecoat 2805 is a UV-curable polyurethane dispersion available from Allnex. SpeedCure 2959 is a hydroxyacetophenone photoinitiator available from Arkema.

[0363] [Synthesis of Intermediate 1a: Diethyl 2,2'-[(4-benzoyl-1,3-phenylene)bis(oxy)]diacetate] TIFF2025504613000042.tif32170To a stirred solution of 2,4-dihydroxybenzophenone (85.0 g, 0.397 mol) in 2-butanone (500 mL) was added potassium iodide (6.6 g, 0.0397 mol), potassium carbonate (345.5 g, 2.5 mol) and ethyl chloroacetate (102 g, 0.833 mol). The reaction mixture was heated to reflux for 5 h, then cooled to room temperature and poured into water. The organic phase was separated and washed with an equal volume of water to give a clear, colorless aqueous phase. The organic phase was separated, dried (MgSO4) and concentrated under reduced pressure to give intermediate 1a as a pale yellow oil that solidified over time. (145 g, 95%). 1 H NMR (400MHz, CDCl3);7.83(dd,J=8.5 and 1.5Hz,2H),7.53(m,1H),7.43(m,3H),6.55(dd,J=8.5 and 2.0Hz,1H),6.48(d,J=2.0H) z,1H),4.66(s,2H),4.40(s,2H),4.30(q,J=7.0Hz,2H),4.17(q,J=7.0Hz,2H),1.32(t,J=7.0Hz,3H),1.23(t,J=7.0Hz,3H). ν max / cm -1 2984, 2938, 1746, 1651, 1607, 1581.

[0364] [Synthesis of benzophenone polyol 1 according to the present invention] TIFF2025504613000043.tif39170 A mixture of intermediate 1a (467 g, 1.21 mol) and diethanolamine (256 g, 2.44 mol) was heated to 100-105 °C with stirring. Ethanol was removed by distillation at atmospheric pressure. The mixture was heated for 15 h and then cooled to approximately 80 °C. The product was concentrated under reduced pressure to remove residual ethanol. The product was cooled to room temperature. The desired polyol 1 was obtained as a pale yellow solid (610 g, 100%). 1 H NMR(400MHz,D2O);7.42(d,J=8.5Hz,2H),7.36(t,J=7.5Hz,1H),7.20(t,J=7.5Hz,2H),7.08(d,J=8.5Hz,1H),6.40(m 2H),4.78(s,2H),4.59(s,2H),3.67-3.55(m,4H),3.50(t,J=5.5Hz,2H),3.45(t ,J=6.0Hz,2H),3.39-3.33(m,4H),3.26(t,J=6.0Hz,2H),3.20(t,J=5.5Hz,2H). ν max / cm -1 3352(br),2935,1640,1601,1578.

[0365] [Synthesis of Intermediate 2a: [(9-oxo-9H-thioxanthenyl)methyl]propanedioate diethyl ester (mixture of isomers)] TIFF2025504613000044.tif27170A solution of diethyl benzylmalonate (220 g, 880 mmol) and 2-(chlorothio)benzoyl chloride (200 g, 966 mol) in dichloromethane (1 L) was added over 3 h to a stirred ice-cold suspension of anhydrous iron(III) chloride (428 g, 2.64 mol) in dichloromethane (1.5 L), and the resulting deep red solution was allowed to warm to room temperature and stirred for an additional 16 h. The mixture was poured into ice water (ca. 2 L) and the biphasic mixture was stirred vigorously for 0.5 h. The mixture was filtered and the layers separated. The organic layer was collected and concentrated under reduced pressure (30-35 °C). Toluene was added to the crude residue (1.5 h) and the resulting solution was washed with 5% hydrochloric acid (2×500 mL), water (500 mL), saturated sodium bicarbonate solution (2×500 mL) and brine (300 mL). The organic phase was dried (MgSO4) and concentrated under reduced pressure to give the desired thioxanthone intermediate 2a as a yellow / orange liquid (305 g, 90%, isomeric mixture; 2-isomer was the major isomer). 1 H NMR (400MHz, CDCl3); 8.63-8.45(m,2H),7.65-7.40(m,5H),4.24-4.12(m,4H),3.75(t,J=8.0Hz,1H),3.36-3.33(m,2H),1.27-1.18(m,6H). ν max / cm -1 2981,1727,1636,1591.

[0366] [Synthesis of thioxanthone polyol 2 according to the present invention] TIFF2025504613000045.tif41170A mixture of intermediate 2a (50.0 g, 130 mmol) and diethanolamine (26.0 g, 247 mmol) was heated at 110-115 °C for 5 h, and the ethanol was removed by distillation. The resulting mixture was thoroughly dried under reduced pressure to give the crude product (59.0 g). 7 g of this crude material was purified by column chromatography (eluted with 5:1 dichloromethane-methanol) to give pure polyol 2 as a pale yellow solid (2.7 g, 39%, isomeric mixture; 2-isomer was the major isomer). 1H NMR(400MHz,d6-DMSO);8.49(dd,J=1.0 and 8.0Hz,1H),8.39(s,1H),7.85-7.60(m,5H),4 .92(t,J=5.0Hz,2H),4.68(t,J=5.0Hz,2H),4.47(t,J=6.5Hz,1H),3.35-3.41(m,18H). ν max / cm -1 3365(br),2937,1618,1588.

[0367] [Synthesis of thioxanthone polyol 3 according to the present invention] TIFF2025504613000046.tif34170 Intermediate 1a (109 g; 282 mmol), 2-(methylamino)ethanol (127 g; 1.69 mol), and absolute ethanol (150 mL) were mixed in a 500 mL flask and the resulting mixture was stirred at room temperature for 1 h. A yellow, clear solution was obtained. The mixture was heated to 75-80 °C for 18 h and then cooled to room temperature. Ethanol was evaporated from the reaction mixture under vacuum at 60 °C, then the reaction mixture was heated to 83 °C and most of the unreacted 2-(methylamino)ethanol was evaporated at 30-50 mbar. The viscous residue was dissolved in water (150 mL) at 60 °C and the aqueous solution was then evaporated at 50-75 °C (50 mbar). The viscous product was further dried at 80° C. (50 mbar) for 2.5 h to give the desired polyol 3 as a highly viscous yellow liquid (116 g; 92%). 1 H-NMR(400MHz,DMSO-d6):7.79-7.76(m,2H),7.59(t,J=7.3Hz,1H),7.48-7.45(m,2H),7.30-7.25(m,1H),6.62-6.57(m,1H),6.54-6.52(m ,1H),4.97-4.72(m,4H),3.60-3.57(m,2H),3.52-3.49(m,2H),3.47- 3.35(m,4H),3.30-3.27(m,1H),3.25-3.22(m,1H),3.04-2.79(m,6H).

[0368] [Synthesis of thioxanthone polyol 4 according to the present invention] TIFF2025504613000047.tif37170 A mixture of intermediate 2a (118 g, 0.307 mol) and 2-(methylamino)ethanol (138 g, 1.84 mol) was heated at 105-110 °C for 8 h. The mixture was cooled to approximately 80 °C and poured into water (1 L). The resulting homogeneous solution was stirred and cooled to room temperature over 2 h. The desired product precipitated immediately. The solid product was collected by filtration and washed on the filter with water (3 × 150 mL). The solid was dried to constant weight in a vacuum oven at 55 °C and approximately 50 mbar to give the desired polyol 4 as a pale yellow powder (87 g, 64%). 1 H NMR(400MHz,d6-DMSO);8.48(d,J=8.0Hz,1H),8.34(s,1H),7.84-7.60(m,5H),4.95-4.89(m,1H),4.65(br s, 1H), 4.95-4.27 (m, 1H), 3.51-3.18 (m, 10H), 2.93-2.54 (m, 6H). ν max / cm -1 3382(br),2929,1622,1584. m / z(ESI)443.0[MH + ].

[0369] [UV curing experiment] A formulation containing 2g of water-based resin Ucecoat 2805 (Allnex), 0.04g of photoinitiator (2 phr = 2 parts by weight per 100 parts by weight of resin), and 0.10g of triethanolamine (5 phr as amine synergist) was prepared by mixing the materials together and stirring at room temperature for approximately 30 minutes. The PI and amine co-initiator were completely dissolved in the resin within this time. The formulation was then cured under a Hg lamp (30% intensity) to a 24 μm film using a belt speed of 20 m / min. The number of passes under the Hg lamp required to achieve full cure (as determined by the thumb twist test, where pressure is applied while twisting the thumb until no marks are left on the cured film surface) is given below: TIFF2025504613000048.tif43170

[0370] The cure speed of the two polyols of the present invention in a waterborne resin system is comparable to the state-of-the-art SpeedCure 2959; the cure speed is significantly improved compared to the formulation in which no photoinitiator is present.

Claims

1. The following formula (I): (In the above formula PI is the photoinitiator moiety; each L is independently selected from a direct bond or a linker containing 1 to 20 carbon atoms; each X is independently selected from a direct bond, a -P(=O)(R')- bond, and a linker containing 1 to 6, particularly 1 to 4, and more particularly 1 to 3 carbon atoms; R' is aryl, alkyl or alkoxy; Each Y is independently H, alkyl, or -Z'-(OM'). ｍ' and each Z and Z' is independently a linker containing 1 to 6, particularly 2 to 5, and more particularly 2 to 4 carbon atoms; each M and M' is independently H or (meth)acryloyl; each m and m' is independently 1, 2 or 3, especially 1; Each n is independently 0 or 1, particularly 1; Each p is independently 1, 2 or 3; in particular 1 or 2; q is 1, 2 or 3, in particular 1 or 2; Provided that the following conditions are met: The compound of formula (I) has a -P(=O)(R')- bond or at least two -N(Y)-Z-(OM) ｍ a moiety, wherein Y is other than H; When L is a direct bond, it is attached directly to the -C(=O)-X- moiety; ・-L-[C(=O)-X] ｎ There is no ester bond in the - and -Z- moieties. Compound by.

2. PI is an optionally substituted aryl-containing photoinitiator moiety selected from benzophenone, thioxanthone, anthraquinone, xanthone, acridone, and phenyl; With the proviso that when PI is an optionally substituted phenyl, at least one -C(=O)- group is directly bonded to said phenyl; In particular, PI is represented by the following formula (II) to (IX): (In the above formula E is S, O, C(=O) or NR １ , in particular S; R １ is H, optionally substituted alkyl, optionally substituted aryl; Each symbol represents a point of attachment to a linker, L; Each R ａ , R' ａ , R ｂ , R' ｂ , R ｃ , R' ｃ , R ｄ , R' ｄ , R ｅ , R' ｅ , R ｆ , R' ｆ , R ｇ and R ｈ is H, F, Cl, Br, I, -OR ２ , -SR ２ , -N(R ２ ) ２ , -NO ２ , -CN, -C(=O)R ２ , -O-C(=O)R ２ , -C(=O)OR ２ , -C(=O)N(R ２ ) ２ , -NR ２ -C(=O)-R ２ , -SO ２ -N(R ２ ) ２ , -C(=O)-P(=O)R ３ R ４ or an optionally substituted group selected from alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl, and heteroaryl; Two adjacent R ａ , R' ａ , R ｂ , R' ｂ , R ｃ , R' ｃ , R ｄ , R' ｄ , R ｅ , R' ｅ , R ｆ , R' ｆ , R ｇ Or R ｈ The groups, together with the carbon atoms to which they are attached, may form a 5- to 8-membered ring; Each R ２ is independently H or an optionally substituted group selected from alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl, heteroaryl, and heteroatom-containing alkyl; R ３ and R ４ is independently an optionally substituted group selected from aryl, alkyl, alkoxy, or amino; With the proviso that when PI corresponds to formula (VIII) or (IX), at least one -C(=O)- group is represented by the symbol · and / or the substituent R ｇ Or R ｈ directly attached to the phenyl moiety of formula (VIII) or (IX) The compound according to claim 1, which corresponds to one of the following:

3. PI corresponds to formula (VIII) or (IX) and is directly bonded to the phenyl group of PI, the following formula (X) or (XI): (In the above formula R ｉ and R' ｉ is alkyl or R ｉ and R' ｉ may, together with the carbon atom to which they are attached, form a 5- to 8-membered ring. R ｊ is -OH or -NR ｌ R' ｌ and R ｋ and R' ｋ is aryl, alkyl, alkoxy and -N(Y)-Z-(OM) ｍ are independently selected from; R ｌ and R' ｌ is alkyl and -Z-(OM) ｍ or R ｌ and R' ｌ may, together with the nitrogen atom to which they are attached, form a 5- to 8-membered ring; The symbol " represents the point of attachment to the PI moiety. The compound of claim 2 comprising a moiety having the formula:

4. Formulae (XII) to (XXV) (In the above formula L, M, X, Y, Z, m and n are as defined in claim 1; R ａ , R' ａ , R ｂ , R' ｂ , R ｃ , R' ｃ , R ｄ , R' ｄ , R ｅ , R' ｅ , R ｆ , R' ｆ , R ｇ and R ｈ is as claimed in claim 2; R ｉ and R' ｉ is as claimed in claim 3; R ｊ is -OH or -NR ｌ R' ｌ and R ｋ and R' ｋ is independently selected from aryl, alkyl, and alkoxy; R ｌ and R' ｌ are independently selected from alkyl, or R ｌ and R' ｌ may form a 5- to 8-membered ring together with the nitrogen atom to which they are attached.

4. The compound according to claim 1 , wherein

5. each L is independently selected from a direct bond, C1-C6 alkylene, C1-C6 oxyalkylene, C1-C6 alkenylene, C1-C6 thioalkylene, C1-C6 ketoalkylene, C1-C6 ketoalkenylene, C7-C13 ketoarylene, C6-C13 ketocycloalkylene; More particularly, each L is a direct bond, an alkylene of formula (XXVI) or (XXVII), an oxyalkylene of formula (XXVIII), a thioalkylene of formula (XXIX), a ketoalkylene of formula (XXX), a ketoalkenylene of formula (XXXI), a ketoarylene of formula (XXXII), a ketocycloalkylene of formula (XXXIII). (In the above formula Each R ｍ , R' ｍ , R ｎ , R' ｎ , R" ｎ , R ｏ , R' ｏ , R ｐ , R' ｐ , R ｑ and R' ｑ is independently H or alkyl, in particular H; Each R ｒ and R' ｒ are independently H, halogen, alkyl, cycloalkyl, heterocycloalkyl, alkoxy, aryloxy, thioalkyl, thioaryl, arsenyl, arsinyl, aryl, aralkyl, alkaryl, heteroaryl, -C(=O)R ２ , -NR ３ R ４ , alkylamino, alkylthiol, hydroxyalkyl, haloalkyl, -NO ２ , -CN, -C(=O)OR ３ , -C(=O)NR ３ R ４ , —OH and —SH; Two adjacent R ｒ A group or two adjacent R' ｒ The groups may, together with the carbon atoms to which they are attached, form a 5- to 8-membered ring; a is 1, 2, 3, 4, 5 or 6, in particular 1 or 2; b is 1, 2, 3, 4 or 5, in particular 1; c is 1, 2, 3, 4, 5 or 6, in particular 1 or 2; d is 1, 2, 3, 4, 5 or 6, in particular 1 or 2; e is 1, 2, 3, 4 or 5, in particular 1; f is 6 or 8; The symbol · represents the point of attachment to the PI moiety; The symbol § represents -C(=O)-X-N(Y)-Z-(OM). ｍ represents the point of attachment to the moiety) 5. The compound according to claim 1 , wherein the compound is independently selected from

6. each X is independently selected from a direct bond, alkylene, and -P(=O)(R')-; In particular, each X is a direct bond, a group of the formula -(CR ｓ R' ｓ )g- alkylene and -P(=O)(R')-, where R' is phenyl; Here, each R ｓ and R' ｓ is independently H or alkyl, in particular alkyl; 6. A compound according to claim 1, wherein g is 1, 2, 3, 4, 5 or 6, in particular 1.

7. Each Y is independently alkyl or -Z'-(OM') ｍ' , in particular methyl, ethyl or -Z'-(OM') ｍ' and more particularly -Z'-(OM') ｍ' 7. The compound according to claim 1 , wherein

8. All of the Y groups are -Z'-(OM') ｍ' 8. The compound according to claim 1 , wherein

9. 8. The compound of claim 1, wherein all of the Y groups are alkyl.

10. A portion of the Y group is -Z'-(OM') ｍ' and some of the Y groups are alkyl.

11. Each Z and Z' is independently an alkylene; in particular each Z and Z' is independently an alkylene of formula (XXXIV), (XXXV) or (XXXVI), even more particularly an alkylene of formula (XXXIV). (In the above formula, each R ｔ , R' ｔ , R ｕ , R' ｕ , R ｖ , R' ｖ is independently H or alkyl, in particular H; R" ｕ is H or alkyl, in particular alkyl; h is 1, 2, 3, 4, 5 or 6, in particular 2; Each i is independently 1, 2 or 3, in particular 1; each j is independently 1, 2 or 3, in particular 1; 11. The compound according to any one of claims 1 to 10,

12. A compound according to any one of claims 1 to 11 having a total of at least 2, particularly at least 3, more particularly at least 4 -OM and -OM' groups.

13. 13. The compound of claim 1, wherein all of the M and M' groups are H.

14. 13. The compound of any one of claims 1 to 12, wherein all of the M and M' groups are (meth)acryloyl.

15. 13. A compound according to any one of claims 1 to 12, wherein some of the M and M' groups are H and some of the M and M' groups are (meth)acryloyl.

16. 13. A compound according to any one of claims 1 to 12, comprising at least one bond selected from an amide bond or an aminophosphine bond, preferably at least one amide bond.

17. 17. A method for the preparation of a compound of formula (I) according to claim 1, comprising the steps of: wherein PI, L, M, X, Y, Z, m, n, p and q are as defined in claims 1 to 16; R" is H or alkyl. A photoinitiator composition comprising at least one compound according to one of the preceding claims.

18. 17. A photoinitiator composition comprising a mixture of at least two, in particular at least three, different compounds of formula (I) according to any one of claims 1 to 16.

19. In the different compounds, all of the Y groups are -Z-(OM). ｍ a compound in which all of the Y groups are alkyl; and a compound in which some of the Y groups are -Z-(OM). ｍ and a portion of the Y groups are alkyl; and combinations thereof; in particular mixtures are those in which all of the Y groups are -Z-(OM) ｍ a compound in which all of the Y groups are alkyl; and a compound in which some of the Y groups are -Z-(OM). ｍ 20. The photoinitiator composition of claim 18, comprising a compound wherein some of the Y groups are alkyl.

20. 17. A photoinitiator composition comprising a compound of formula (I) according to any one of claims 1 to 16 and an amine synergist other than a compound of formula (I), preferably an amine synergist having a tertiary amine group.

21. A process for preparing a compound of formula (I) according to any one of claims 1 to 16, in which at least a part of the M groups are (meth)acryloyl, comprising reacting a compound of formula (I) in which all of the M groups are H with (meth)acrylic acid or a (C1-C6) alkyl (meth)acrylate in the presence of a catalyst.

22. 22. The method of claim 21, wherein a (C1-C6) alkyl (meth)acrylate is used and the catalyst is a transesterification catalyst.

23. A method for photopolymerizing one or more ethylenically unsaturated compounds, comprising contacting one or more ethylenically unsaturated compounds with a compound of formula (I) according to any one of claims 1 to 16 or with a photoinitiator composition according to any one of claims 17 to 20 and irradiating the mixture, in particular with visible, near UV and / or UV light.

24. a) a compound of formula (I) according to any one of claims 1 to 16 or a photoinitiator composition according to any one of claims 17 to 20; b) Ethylenically unsaturated compounds 1. A curable composition comprising:

25. a) a compound of formula (I) according to any one of claims 1 to 16 or a photoinitiator composition according to any one of claims 17 to 20; c) Unsaturated polymer dispersions or emulsions 1. A curable composition comprising:

26. 26. The curable composition of claim 25, wherein the unsaturated polymer dispersion or emulsion is a polyurethane dispersion, an acrylic dispersion, an unsaturated polyester emulsion, or an emulsion of a (meth)acrylate functionalized oligomer, and mixtures thereof, in particular, the unsaturated polymer dispersion or emulsion is a polyurethane dispersion.

27. 27. The curable composition of any one of claims 24 to 26, which is water-based.

28. 28. The curable composition of any one of claims 24 to 27, which is an ink composition, an overprint varnish composition, a coating composition, an adhesive composition, a sealant composition, a molding composition, a dental composition, a cosmetic composition, or a 3D printing composition.

29. 29. A method for preparing a cured product, comprising curing the curable composition according to any one of claims 24 to 28, in particular by exposing the curable composition to radiation, such as UV, near UV and / or visible light.

30. 29. A method of inkjet printing comprising jetting the curable composition of any one of claims 24 to 28 onto a substrate.

31. 29. Substrates to which the curable composition according to any one of claims 24 to 28 has been applied and cured, in particular food and beverage packaging, pharmaceutical packaging, textiles, nails, teeth, medical devices, food and beverage processing equipment, water pipes.

32. 27. Use of a compound of formula (I) as defined in any one of claims 1 to 16 or a photoinitiator composition as defined in any one of claims 17 to 20 in a photopolymerization reaction.

33. 21. Use of a compound of formula (I) as defined in any one of claims 1 to 16, or a photoinitiator composition as defined in any one of claims 17 to 20, as a photoinitiator or photoinitiating system in a radiation curable composition, in particular a UV or LED curable composition.

34. 17. Use of a compound of formula (I) according to any one of claims 1 to 16, wherein at least a portion of the M groups are (meth)acryloyl, for reducing the amount of extractables from a cured layer of a curable composition.

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