Phosphine oxide-based photoinitiators

Abstract

The present invention relates to phosphine oxide-based photoinitiators, to a method for producing said photoinitiators and to precursors which can be used for producing said photoinitiators. The invention also relates to a photoinitiator composition, a curable composition, a method of preparing a cured product, an inkjet printing method, a 3D printing method and a method of coating nails. The invention also relates to a photoinitiator composition or a precursor of a photoinitiator. The invention also relates to the use of a photoinitiator or a photoinitiator composition.

Description

Technical Field

[0001] The present invention relates to phosphine oxide-based photoinitiators, methods for preparing the photoinitiators, and precursors that can be used to prepare the photoinitiators. The present invention also relates to photoinitiator compositions, curable compositions, methods for preparing cured products, inkjet printing methods, 3D printing methods, and methods for coating nails. The present invention also relates to photoinitiator compositions or photoinitiator precursors. The present invention also relates to uses of the photoinitiators or photoinitiator compositions. Background Art

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

[0003] Free radical photoinitiators can adopt two different modes of action and are categorized by their mode of action as Norrish Type I and Norrish Type II photoinitiators. Norrish Type I photoinitiators cleave upon exposure to radiation, generating free radical species capable of initiating polymerization of unsaturated compounds. Norrish Type II photoinitiators are compounds that do not fragment upon exposure to radiation and therefore typically do not initiate free radical chain polymerization unless a co-initiator is present. Upon exposure to radiation, the interaction between the Type II photoinitiator and the co-initiator results in the generation of free radical species that can initiate polymerization of UV-curable resins.

[0004] In the field of photocurable 3D printing, printing equipment that uses longer wavelength (above 385nm) light sources to achieve the curing of photoactive resins is becoming increasingly dominant. In formulations designed for these printers, phosphine oxide derivatives such as acylphosphine oxides are the preferred class of photoinitiators due to their strong absorption in the wavelength range of interest. Acylphosphine oxides are classified as Norrish Type I initiators and include the following compounds:

[0005] (a) Laromer 819 (also known as Irgacure, 819, Speedcure BPO or BAPO, bis-(2,4,6-trimethylbenzoyl)phenylphosphine oxide), which has the following structure:

[0006]

[0007] (b) Speedcure TPO (also known as 2,4,6-trimethylbenzoyldiphenylphosphine oxide), which has the following structure:

[0008]

[0009] (c) Speedcure TPO-L (also known as ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate), which has the following structure:

[0010]

[0011] However, based on new toxicological tests, TPO was recently classified as a Category 1B reproductive toxin. This limits its use in many applications. Similar reclassification of TPO-L and BAPO is expected.

[0012] Furthermore, mesitylene glycol (2,4,6-trimethylbenzaldehyde), a compound typically released from TPO under UV light, can migrate from the cured product and contaminate any adjacent materials. In the case of food, migration of small molecule fragments can lead to off-flavor and odor issues. Furthermore, mesitylene glycol is classified as a skin irritant, so migration from the cured article could pose a health hazard. Low molecular weight photoinitiators such as TPO, TPO-L, and BPO may also migrate from the cured product and may also pose a health hazard.

[0013] The consumption of biocompatible 3D printing materials is increasing due to reduced production time and the formulation of specially designed products. These materials are particularly sought in new medical applications such as implants, prostheses, surgical guides, tissue engineering products, hearing aids, dental products, and wearable devices (shoes, jewelry, earplugs and glasses). The development of FDA-approved 3D printing biomaterials and the creation of low-cost 3D printing materials are two major challenges facing this field. Given that UV-curable 3D printing materials will come into contact with the human body, biocompatible resins must undergo biological evaluation and testing for cytotoxicity, genotoxicity or delayed hypersensitivity reactions. Attention is mainly focused on developing UV-curable resins to make 3D parts free of residual monomers or low molecular weight additives in order to meet health and safety standards and produce durable and high-performance biomedical devices without concerns about toxicity or side effects.

[0014] 3D printers equipped with longer wavelength irradiation (such as LED lamps) are experiencing a surge in popularity due to the high penetration depth of UV-A LED light, lower biohazards, and cost-effectiveness. Acylphosphine oxides have a red-shifted absorption band between 350 and 420 nm and are therefore effective photoinitiators for many LED light emission ranges. Unfortunately, low molecular weight acylphosphine oxides can result in undesirable residues and photoproducts (e.g., mesitylene aldehyde) and will readily migrate to the surface of the cured 3D part. Therefore, high molecular weight polymeric photoinitiators appear more advantageous because they do not produce small molecule photoproducts and therefore pose fewer toxicological concerns.

[0015] Document EP 3378875 relates to a photopolymerization initiator, which is a compound having a structure in which one or more carbonyl groups attached to a carbon atom are further directly bonded to the aromatic ring of an aromatic acyl group bonded to a phosphorus atom in an acylphosphine oxide structure.

[0016] Document US10590264 discloses a photopolymerization initiator which is an acylphosphine oxide.

[0017] EP 3149013 discloses polyfunctional monoacylphosphine oxides and bisacylphosphine oxides useful as photoinitiators, and photocurable compositions.

[0018] Therefore, there is a need for cost-effective and efficient photoinitiators for making radiation-curable adhesive and coating formulations that exhibit high curing activity, low toxicity, and reduced migration from the coated article.

[0019] The present invention satisfies the above needs. In particular, the present invention provides cost-effective and efficient photoinitiators for making curable compositions that exhibit high curing activity, low toxicity, and reduced migration from coated articles.

[0020] This is achieved by the (phosphine oxide-based) photoinitiators according to the invention.

[0021] The photoinitiators according to the present invention may advantageously have a high molecular weight (i.e. a molecular weight greater than 500 Daltons) and therefore exhibit a lower tendency to migrate and a lower bioaccessibility (reduced tendency to be absorbed through the skin or via the gastrointestinal tract) compared to smaller molecules such as TPO, TPO-L and BPO.

[0022] Such photoinitiators can therefore mimic the good curing properties of classic TPO / BPO initiators with reduced toxicity issues.

[0023] Finally, the photoinitiators according to the invention can be prepared from cheap and readily available materials, which makes such initiators available in a cost-effective manner. Summary of the Invention

[0024] A first object of the present invention is to provide a photoinitiator according to formula (1) or (2):

[0025]

[0026] wherein Ar, R1, R'1, R2, R'2, R3, Q1, Q2, Q3, and Q4 are as defined herein.

[0027] The present invention further relates to a process for preparing a photoinitiator of formula (1) or (2) according to the present invention, wherein the process comprises reacting at least one precursor of formula (30) or (31) with at least one product of formula (32):

[0028]

[0029] R'1-R'2 (32)

[0030] wherein Ar, R1, R2, R3, R'1, R'2, Q1, Q2 and Q3 are as defined herein.

[0031] The present invention also relates to precursors of formula (30) or (31):

[0032]

[0033] wherein Ar, R1, R2, R3, Q1, Q2 and Q3 are as defined herein.

[0034] The present invention further relates to a process for preparing a precursor of formula (30) or (31) according to the present invention, wherein the process comprises reacting at least one precursor of formula (33) or (34) with a compound of at least one of formulae (35) to (42):

[0035]

[0036] Among them, Ar, R1, R2, R3, Q1, Y1, Y2, G, R 14 、R 15 、R 16 、R 17 , Z 1a , Z 1b , Z 2 , Z 3 and Z 4 As defined herein.

[0037] The present invention also relates to a precursor of formula (33) or (34)

[0038]

[0039] wherein Ar, R1, R2, R3, Q1 and G are as defined herein.

[0040] The present invention also relates to a process for preparing a precursor of formula (33) or (34) according to the present invention, wherein the process comprises reacting at least one phosphine oxide of formula (48) or (49) with at least one cyclic anhydride of formula (50) to provide a precursor according to formula (33) or (34), wherein G is OH:

[0041]

[0042] wherein Ar, R1, R2, R3, and Q1 are as defined herein;

[0043] The method optionally comprises the following additional steps:

[0044] - reacting a precursor according to formula (33) or (34) wherein G is OH with an acyl halide of formula (51) to provide a precursor according to formula (33) or (34) wherein G is -OC(=O)-J

[0045] Hal-C(=O)-J (51)

[0046] wherein Hal and J are as defined herein; or

[0047] - reacting a precursor according to formula (33) or (34) wherein G is OH with a halogenating agent, in particular thionyl chloride, to provide a precursor according to formula (33) or (34) wherein G is a halogen atom.

[0048] The present invention further relates to a process for preparing a photoinitiator of formula (1) or (2) according to the present invention, wherein the process comprises reacting at least one precursor of formula (52) or (53) with a compound of at least one of formulae (35) to (42):

[0049]

[0050] Among them, Ar, R1, R2, R3, R'1, R'2, Q1, Y1, Y2, G, R 14 、R 15 、R 16 、R 17 , Z 1a , Z 1b , Z 2 , Z 3 and Z 4 As defined herein.

[0051] The present invention also relates to precursors of formula (52) or (53):

[0052]

[0053]

[0054] wherein Ar, R1, R2, R3, R'1, R'2, Q1 and G are as defined herein.

[0055] The present invention also relates to a process for preparing a precursor of formula (52) or (53) according to the present invention, wherein the process comprises reacting at least one precursor of formula (33) or (34) with at least one product of formula (32) to provide a precursor of formula (52) or (53), wherein G is OH:

[0056]

[0057] R'1-R'2 (32)

[0058] wherein Ar, R1, R2, R3, R'1, R'2 and Q1 are as defined herein;

[0059] The method optionally comprises the following additional steps:

[0060] - reacting a precursor according to formula (52) or (53) wherein G is OH with an acyl halide of formula (51) to provide a precursor according to formula (52) or (53) wherein G is -OC(=O)-J

[0061] Hal-C(=O)-J (51)

[0062] wherein Hal is a halogen atom and J is an alkyl or aryl group, in particular a tert-butyl group; or

[0063] - reacting a precursor according to formula (52) or (53) wherein G is OH with a halogenating agent, in particular thionyl chloride, to provide a precursor according to formula (52) or (53) wherein G is a halogen atom.

[0064] The present invention further relates to a process for preparing a photoinitiator of formula (5) or (6) according to the present invention, wherein the process comprises reacting at least one precursor of formula (33) or (34) with at least one product of formula (54):

[0065]

[0066] HX-L4-X'H (54)

[0067] wherein Ar, R1, R2, R3, Q1, G, X, X' and L4 are as defined herein.

[0068] The present invention also relates to a photoinitiator composition comprising:

[0069] - a mixture of at least two photoinitiators of formula (1) according to the invention;

[0070] - a mixture of at least two photoinitiators of formula (2) according to the invention;

[0071] - at least one photoinitiator of formula (1) according to the invention and at least one photoinitiator of formula (2) according to the invention

[0072] a mixture of precursors of (30); or

[0073] - at least one photoinitiator of formula (2) according to the invention and at least one photoinitiator of formula (2) according to the invention

[0074] (31) a mixture of precursors.

[0075] The present invention further relates to a photoinitiator composition comprising a photoinitiator of formula (1) or (2) according to the present invention and a photoinitiator different from the photoinitiator of formula (1) or (2), in particular selected from MBF (methyl benzoylformate), 73 (2-hydroxy-2-methyl-1-phenylpropanone), 7005 (polymerized benzophenone) photoinitiator.

[0076] The present invention also relates to a process for the photopolymerization of one or more ethylenically unsaturated compounds, comprising contacting one or more ethylenically unsaturated compounds with a photoinitiator of formula (1) or (2) according to the invention or a photoinitiator composition according to the invention and irradiating the mixture, in particular with UV, near-UV, visible, infrared and / or near-infrared radiation.

[0077] The present invention further relates to a curable composition comprising:

[0078] a) a photoinitiator of formula (1) or (2) according to the invention or a photoinitiator composition according to the invention; and

[0079] b) Ethylenically unsaturated compounds.

[0080] The present invention further relates to a method for preparing a cured product, which comprises curing the curable composition according to the present invention, preferably by exposing the curable composition to radiation, such as UV, near UV, visible, infrared and / or near infrared radiation.

[0081] The present invention further relates to a 3D printing method comprising printing a 3D article with the composition according to the invention, in particular printing layer by layer or continuously.

[0082] The present invention further relates to an inkjet printing method comprising jetting the curable composition according to the present invention onto a substrate.

[0083] The present invention also relates to a method for coating nails, wherein the method comprises applying a composition according to the invention to the nails and curing the composition on the nails.

[0084] The present invention also relates to the use of a photoinitiator of formula (1) or (2) according to the invention or a photoinitiator composition according to the invention as a photoinitiator or photoinitiating system in a radiation-curable composition, preferably a UV- or LED-curable composition.

[0085] The present invention also relates to the use of a photoinitiator of formula (1) or (2) according to the invention or a photoinitiator composition according to the invention for curing one or more ethylenically unsaturated compounds.

[0086] The present invention also relates to the use of a photoinitiator of formula (1) or (2) according to the invention or a photoinitiator composition according to the invention for obtaining cured products having a reduced amount of extractables. DETAILED DESCRIPTION

[0087] The invention will now be described in more detail without limitation in the following description.

[0088] definition

[0089] The term "alkyl" refers to a group of the formula -C n H 2n+1 wherein n is 1 to 20. The alkyl group may be linear or branched. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, 2-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 2,2-dimethylbutyl, n-heptyl, 2-ethylhexyl, and the like.

[0090] The term "aryl" means an optionally substituted polyunsaturated aromatic group. The aryl group may contain a single ring (i.e., phenyl) or more than one ring, wherein at least one ring is aromatic. When the aryl group comprises more than one ring, the rings may be fused, connected via covalent bonds (e.g., biphenyl). The aromatic ring may optionally comprise one to two additional fused rings (i.e., cycloalkyl, heterocycloalkyl, or heteroaryl). The term "aryl" also encompasses partially hydrogenated derivatives of the above-mentioned carbocyclic ring systems. Examples include phenyl, naphthyl, biphenyl, phenanthrenyl, and tetraphenylene.

[0091] The term "arylene" means a substituent that is derived from an aromatic hydrocarbon (arene) and is divalent.

[0092] The term "halogen" denotes an atom selected from Cl, Br, F and I.

[0093] The term "cycloalkyl" means a monovalent saturated alicyclic hydrocarbon group comprising a ring. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and isobornyl.

[0094] The term "heterocycloalkyl" refers to a cycloalkyl group having at least one ring atom which is a heteroatom selected from O, N or S.

[0095] The term "alkoxy" means a group of the formula -O-alkyl, wherein alkyl is as defined above.

[0096] The term "aryloxy" means a group of the formula -O-aryl, wherein aryl is as defined above.

[0097] The term "thioalkyl" means a group of the formula -S-alkyl, wherein alkyl is as defined above.

[0098] The term "thioaryl" means a group of the formula -S-aryl, wherein aryl is as defined above.

[0099] The term "linking moiety" means a multivalent group. A linking moiety can link at least two parts of a compound together, and in particular, can link two to 16 parts of a compound together. For example, a linking moiety that links two parts of a compound together is called a divalent linking moiety, a linking moiety that links three parts of a compound together is called a trivalent linking moiety, and so on.

[0100] The term "hydrocarbon linking moiety" means a linking moiety having a carbon backbone that may be optionally interrupted by one or more heteroatoms selected from N, O, S, Si, and mixtures thereof. The hydrocarbon linking moiety may be aliphatic, alicyclic, or aromatic. The hydrocarbon linking moiety may be saturated or unsaturated. The hydrocarbon linking moiety may be optionally substituted.

[0101] The term "aliphatic" refers to a non-aromatic, acyclic compound. It may be linear or branched, saturated or unsaturated. It may be substituted with one or more groups, for example, selected from alkyl, hydroxy, halogen (Br, Cl, I, F), isocyanate, carbonyl, amine, carboxylic acid, -C(=O)-OR', -C(=O)-OC(=O)-R', each R' independently being a C1-C6 alkyl. It may contain one or more bonds selected from ether, ester, amide, carbamate, urea, and mixtures thereof.

[0102] The term "acyclic" refers to a compound that does not contain any rings.

[0103] The term "alicyclic" refers to a non-aromatic cyclic compound. It may be substituted with one or more groups as defined by the term "aliphatic". It may contain one or more bonds as defined by the term "aliphatic".

[0104] The term "aromatic" refers to compounds containing aromatic rings, which means that they obey Huckel's rules for aromaticity, particularly compounds containing a phenyl group. It may be substituted with one or more groups as defined by the term "aliphatic". It may contain one or more bonds as defined by the term "aliphatic".

[0105] The term "saturated" refers to a compound that does not contain any carbon-carbon double bonds or carbon-carbon triple bonds.

[0106] The term "unsaturated" refers to compounds containing carbon-carbon double bonds or carbon-carbon triple bonds, particularly carbon-carbon double bonds.

[0107] The term "polyether polyol" or "polyether linking moiety" means a polyol comprising at least two ether bonds (in other words, a compound comprising at least two hydroxyl groups) or a linking moiety, respectively.

[0108] The term "polyester polyol" or "polyester linking moiety" means a polyol or linking moiety, respectively, comprising at least two ester bonds.

[0109] The term "polycarbonate polyol" or "polycarbonate linking moiety" means a polyol or linking moiety, respectively, comprising at least two carbonate linkages.

[0110] The term "polyurethane linking moiety" means a linking moiety comprising at least two urethane bonds.

[0111] The term "polyorganosiloxane polyol" or "polyorganosiloxane linking moiety" means a polyol or linking moiety comprising at least two organosiloxane bonds, respectively. The organosiloxane may be, for example, a dimethylsiloxane bond.

[0112] The term "polycaprolactone polyol" or "polycaprolactone linking moiety" means a polyol or linking moiety 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.

[0113] The term "polybutadiene polyol" or "polybutadiene linking moiety" means a polyol or linking moiety comprising at least two units derived from the polymerization of butadiene, in particular at least two units selected from -CH2-CH=CH-CH2- and CH2-CH(CH=CH2)-.

[0114] The term "isocyanate group" means a -N=C=O group.

[0115] The term "isocyanurate linking moiety" means a linking moiety comprising an isocyanurate moiety, particularly a moiety of the formula:

[0116]

[0117] Photoinitiator of formula (1) or (2)

[0118] The present invention relates to a photoinitiator. The photoinitiator is according to the following formula (1) or (2):

[0119]

[0120] wherein Ar, R1, R'1, R2, R'2, R3, Q1, Q2, Q3, and Q4 are as defined herein.

[0121] In formulas (1) and (2), each Ar is independently an optionally substituted arylene. In particular, each Ar can independently be an optionally substituted phenylene. Phenylene can be o-phenylene, m-phenylene or p-phenylene (substituted or unsubstituted). Ortho, meta and para refer to the positions of the free radicals of the divalent phenylene. Preferably, each Ar can independently be m-phenylene substituted by one or more optionally substituted groups selected from alkyl, aryl, alkoxy, aryloxy, thioalkyl and thioaryl. More preferably, each Ar is a group of formula (4):

[0122]

[0123] In formulas (1) and (2), R1 and R2 are independently H or an optionally substituted group selected from alkyl and aryl groups; or R1 and R2 together with the carbon atoms to which they are attached form a ring. Such a ring may be selected from a 5-8 membered ring, for example a 5-membered ring, a 6-membered ring, a 7-membered ring or an 8-membered ring, and may preferably be a 6-membered ring. Such a ring (preferably a 6-membered ring) is preferably an alicyclic ring. In particular, R1 and R2 may both be H, or R1 and R2 together with the carbon atoms to which they are attached may form a 6-membered ring, preferably a 6-membered alicyclic ring. Preferably, R1 and R2 are both H.

[0124] In formulae (1) and (2), one of R'1 and R'2 is H and the other of R'1 and R'2 is selected from -OR 4 、-SR 5 、-NR 6 R 7 、-C(R 8 )(CO-W 1 -R 9 )(CO-W 2 -R 10 )、-C(R 11 )(CO-W 3 -R 12 )(CN) and -C(R 13 )(CN)2; or R'2 is H and R'1 and Q2 together with the atoms to which they are attached form a 5-7 membered ring; or R'2 is H and R'1 and Q3 together with the atoms to which they are attached form a 5-8 membered ring;

[0125] in:

[0126] -R 4 、R 5 、R 6 and R 7is independently H or an optionally substituted group selected from alkyl, polyoxyalkylene, cycloalkyl, heterocycloalkyl, aryl and heteroaryl; or R 6 and R 7 Together with the nitrogen atom to which they are attached, they form a 5-7 membered ring;

[0127] -R 8 、R 11 and R 13 are independently H or optionally substituted alkyl, preferably H;

[0128] -R 9 、R 10 and R 12 is independently an optionally substituted group selected from alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl, or R 9 and R 10 Together with the atoms to which they are attached, they form a 5-7 membered ring,

[0129] -W 1 、W 2 and W 3 are independently selected from a bond or an oxygen atom.

[0130] In one embodiment, one of R'1 and R'2 is H and the other of R'1 and R'2 is -OR 4 In this case, R 4 Preferred is an optionally substituted alkyl group.

[0131] In another embodiment, one of R'1 and R'2 is H and the other of R'1 and R'2 is -SR 5 In this case, R 5 Preferred is an optionally substituted alkyl group.

[0132] In another embodiment, one of R'1 and R'2 is H and the other of R'1 and R'2 is -NR 6 R 7 In this case, R 6 and R 7 Together with the nitrogen atom to which they are attached, they preferably form a 5- to 7-membered ring; more preferably an optionally substituted ring selected from morpholine, piperidine, pyrrolidine, oxazolidine, piperazine, thiazolidine, thiomorpholine and azepane.

[0133] In another embodiment, one of R'1 and R'2 is H and the other of R'1 and R'2 is -C(R 8 )(CO-W 1 -R 9 )(CO-W 2 -R 10 ). In this case, R8 、R 9 、R 10 、W 1 and W 2 Preferably defined as follows:

[0134] -R 8 It is H;

[0135] -W 1 and W 2 is independently a bond or an oxygen atom; and

[0136] -R 9 and R 10 is independently optionally substituted alkyl.

[0137] In another embodiment, R'2 is H and R'1 forms a 5-8 membered ring with Q2 or Q3. In such a case, the photoinitiator is preferably according to formula (5) or (6)

[0138]

[0139] in:

[0140] -X and X' are independently selected from O, S and NR 19 ;

[0141] -R 19 is H or optionally substituted alkyl;

[0142] -L0 is an optionally substituted C1-C4 alkylene group.

[0143] In formula (1) and (2), each R3 is independently an optionally substituted group selected from alkyl, aryl and alkoxy. In particular, each R3 can be independently an optionally substituted phenyl, methoxy or ethoxy. Preferably, each R3 is independently phenyl or ethoxy.

[0144] In formulae (1) and (2), Q1 is an optionally substituted aryl group or a group of formula (3):

[0145]

[0146] in:

[0147] -Each R a are independently optionally substituted groups selected from alkyl, aryl, alkoxy, aryloxy, thioalkyl, and thioaryl; and

[0148] -y is a number selected from 0 to 5.

[0149] In one embodiment, Q1 can be an unsubstituted aryl group, such as phenyl.

[0150] In another embodiment, Q1 may be a substituted group with 1 to 5, preferably 2 to 4, substituents R as described in detail above. a Preferably, such a substituent is a methyl group.

[0151] According to a preferred embodiment, Q1 can be a phenyl group or a group of formula (3a):

[0152]

[0153] In formulas (1) and (2), Q2 and Q3 are independently -OR 14 、-SR 15 、-NR 16 R 17 、-O-[CH2-CH(OH)-Y1] a -Z 1 、-SZ 2 、-N(R 18 )-Z 3 or -O-Cyhex-Y2-Z 4 ; or Q2 and R'1 together with the atoms to which they are attached form a 5-7 membered ring; or Q3 and R'1 together with the atoms to which they are attached form a 5-7 membered ring;

[0154] in:

[0155] -R 14 and R 15 are independently H or an optionally substituted group selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl;

[0156] -R 16 、R 17 and R 18 is independently H or an optionally substituted group selected from alkyl and aryl; or R 16 and R 17 Together with the nitrogen atom to which they are attached, they form a 5-7 membered ring;

[0157] -Cyhex is a cyclohexylene group substituted by a hydroxyl group, preferably represented by the following formula:

[0158]

[0159] -Y1 is a bond, -CH2-O-* or -CH2-C(=O)-O-*;

[0160] -Y2 is a bond, -CH2-OC(=O))-# or -C(=O)-O-#;

[0161] -a is 0 or 1;

[0162] -Z 1 , Z2 , Z 3 and Z 4 are independently phosphine oxide-containing moieties;

[0163] - The symbol * represents the part Z 1 connection points;

[0164] - The symbol # represents the part Z 4 connection point.

[0165] In one embodiment, Q2 and Q3 are independently -OR 14 In this case, R 14 It is preferably an optionally substituted alkyl group, more preferably a methyl group or an ethyl group.

[0166] In another embodiment, Q2 and Q3 are independently -O-[CH2-CH(OH)-Y1] a -Z 1 In this case, Z 1 Preferably, it is a group of formula (7);

[0167]

[0168] in:

[0169] -Ar, Y1, R1, R2, R'1, R'2, R3, Q1 and a are as defined above;

[0170] - L1 is the connecting part; and

[0171] -b is a number selected from 1 to 15, particularly 1 to 5, more particularly 1 to 3.

[0172] In formula (7), a may be equal to 0. Alternatively, in formula (7), a may be equal to 1 and Y1 is preferably a bond or -CH2-O-*, more preferably -CH2-O-*.

[0173] In another embodiment, Q2 and Q3 are independently -SR 15 In this case, R 15 Preferred is an optionally substituted alkyl group.

[0174] In another embodiment, Q2 and Q3 are independently -SZ 2 In this case, Z 2 Preferred are groups of formula (8):

[0175]

[0176] in:

[0177] -Ar, R1, R2, R'1, R'2, R3 and Q1 are as defined above;

[0178] - L2 is the connecting part; and

[0179] -b' is a number selected from 1 to 15, particularly 1 to 5, more particularly 1 to 3.

[0180] In another embodiment, Q2 and Q3 are independently -NR 16 R 17 In this case, R 16 and R 17 Preferably, R is independently selected from H or an optionally substituted group selected from alkyl and aryl. 16 and R 17 Together with the nitrogen atom to which they are attached, they can form a 5-7 membered ring.

[0181] In another embodiment, Q2 and Q3 are independently -N(R 18 )-Z. In this case, R 18 is preferably H or an optionally substituted group selected from alkyl and aryl; and Z 3 Preferred are groups of formula (9):

[0182]

[0183] in:

[0184] -Ar, R1, R2, R'1, R'2, R3, R 18 and Q1 is as defined above;

[0185] - L3 is the connecting part; and

[0186] -b" is a number selected from 1 to 15, particularly 1 to 5, more particularly 1 to 3.

[0187] In another embodiment, Q2 and Q3 are independently -O-Cyhex-Y2-Z 4 In this case, Z 4 Preferably, it is a group of formula (7) or a group of formula (10) as defined above;

[0188]

[0189] in:

[0190] -Ar, Y2, R1, R2, R'1, R'2, R3, Q1 are as defined above;

[0191] - L4 is the connecting part; and

[0192] -b'' is a number selected from 1 to 15, in particular 1 to 5, more particularly 1 to 3.

[0193] In formulas (7), (8), (9) and (10), each linking moiety L1, L2, L3 and L4 can independently be a divalent, trivalent, tetravalent, pentavalent, hexavalent, heptavalent, octavalent, nonavalent, decavalent, elevenvalent, dodecavalent, thirteenvalent, fourteenvalent, pentavalent or hexavalent linking moiety. More particularly, each linking moiety L1, L2, L3 and L4 can independently be a divalent, trivalent, tetravalent, pentavalent or hexavalent linking moiety. Even more particularly, each linking moiety L1, L2, L3 and L4 can independently be a divalent, trivalent or tetravalent linking moiety.

[0194] Each linking portion L1, L2, L3 and L4 can be independently selected from an aromatic linking portion, an aliphatic linking portion, an alicyclic linking portion, a polyether linking portion, a polythioether linking portion, a polyalkyleneimine linking portion, a polyester linking portion, a polycarbonate linking portion, a polycaprolactone linking portion, a polyurethane linking portion, a polyorganosiloxane linking portion, a polybutadiene linking portion and a combination thereof. Preferably, each linking portion L1, L2, L3 and L4 is independently selected from an aromatic linking portion, an aliphatic linking portion, an alicyclic linking portion, a polyether linking portion, a polythioether linking portion, a polyalkyleneimine linking portion, a polyester linking portion, a polyorganosiloxane linking portion and a combination thereof.

[0195] Each linking moiety L1, L2, L3 and L4 may be independently selected from:

[0196] - a trivalent moiety corresponding to formula (11):

[0197]

[0198] in:

[0199] -R 20 and R 21 are independently straight or branched chain alkylene groups;

[0200] -a' is an integer equal to 0 or 1;

[0201] - a trivalent moiety corresponding to formula (12):

[0202]

[0203] in:

[0204] - R4 and R'4 are independently H or methyl;

[0205] - R5 is H, alkyl or alkoxy, preferably R5 is alkyl;

[0206] - each c is independently an integer from 0 to 2, provided that no more than one c is equal to 0, preferably each c is equal to 1 or one c is equal to 0 and the other two c are equal to 1;

[0207] - each d is independently an integer from 2 to 4, in particular 2;

[0208] - each e is independently an integer from 0 to 10, in particular from 1 to 6;

[0209] - a trivalent moiety according to formula (13):

[0210]

[0211] in:

[0212] -R'5 is H, alkyl or alkoxy, preferably R'5 is alkyl;

[0213] - Each R6 is independently a linear or branched alkylene group;

[0214] - each c' is independently an integer from 0 to 2, provided that no more than one c' is equal to 0, preferably each c' is equal to 1 or one c' is equal to 0 and the other two c' are equal to 1;

[0215] - a trivalent moiety according to formula (14a), (14b) or (14c):

[0216]

[0217]

[0218] where R f is H or methyl;

[0219] - a tetravalent moiety according to formula (15a) or (15b):

[0220]

[0221] in:

[0222] - Each R7 is independently a linear or branched alkylene group;

[0223] - R8 and R'8 are independently H or methyl;

[0224] - each f is independently an integer from 0 to 2, provided that no more than one f is equal to 0, preferably each f is equal to 1;

[0225] - each g is independently an integer from 2 to 4, in particular 2;

[0226] - each h is independently an integer from 0 to 10, in particular from 1 to 6;

[0227] - a tetravalent moiety according to formula (16):

[0228]

[0229] in

[0230] - R9 and R'9 are independently H or methyl;

[0231] -Each R 10 are independently H, alkyl or alkoxy, preferably R 10 is an alkyl group;

[0232] - each i is independently an integer from 2 to 4, in particular 2;

[0233] - each j is independently an integer from 0 to 10, in particular from 1 to 6;

[0234] - a tetravalent, pentavalent or hexavalent moiety according to formula (17):

[0235]

[0236] in:

[0237] -R 24 and R' 24 are independently H or methyl;

[0238] - each i* is independently an integer from 2 to 4, in particular 2;

[0239] - each j* is independently an integer from 0 to 10, in particular from 1 to 6;

[0240] -k' is an integer from 1 to 3;

[0241] - a hexavalent moiety according to formula (18):

[0242]

[0243] in

[0244] -R 11 and R' 11 are independently H or methyl;

[0245] - each k is independently an integer from 2 to 4, in particular 2;

[0246] - each l is independently an integer from 0 to 10, in particular from 1 to 6;

[0247] - a hexavalent moiety according to formula (19):

[0248]

[0249] in:

[0250] -R 25 and R' 25 are independently H or methyl;

[0251] - each l* is independently an integer from 2 to 4, in particular 2;

[0252] - each m* is independently an integer from 0 to 10, in particular from 1 to 6;

[0253] - a divalent moiety according to one of the formulae (20) to (28):

[0254] -(CR 12 R' 12 ) m -(20)

[0255] -[(CR 13 R' 13 ) n -O] o -(CR 13 R' 13 ) n -(twenty one)

[0256] -[(CR 14 R' 14 ) p -O] q -(CR 15 R' 15 ) r -[O-(CR 14 R' 14 ) p ] q -(twenty two)

[0257] -[(CR 16 R' 16 ) s -C(=O)O] t -(CR 17 R' 17 ) u -(23a)

[0258] -(CR 17 R' 17 ) u -[(CR 16 R' 16 ) s -C(=O)O] t -(23b)

[0259] -[(CR 18 R' 18 ) v -OC(=O)-(CR19 R' 19 ) w -C(=O)-O] x -(CR 18 R' 18 ) v -(twenty four)

[0260] -[(CR 20 R' 20 ) y -S] z -(CR 20 R' 20 ) y -(25)

[0261] -(CR 21 R' 21 ) m' -C(=O)-O-(CR 22 R' 22 ) n' -OC(=O)-(CR 21 R' 21 ) m' -(26)

[0262] -(CR 23 R' 23 ) m” -Cy-[L-Cy] n” -(CR 23 R' 23 ) m” -(27)

[0263]

[0264] in:

[0265] -R 12 , R' 12 、R 15 , R' 15 、R 17 , R' 17 、R 18 , R' 18 、R 19 , R' 19 、R 21 、

[0266] R' 21 、R 22 , R' 22 、R 23 and R' 23 are independently H or alkyl;

[0267] -R 13, R' 13 、R 14 , R' 14 、R 16 , R' 16 、R 20 , R' 20 、R 26 and R' 26 are independently H or methyl;

[0268] -Cy is an optionally substituted ring, in particular an optionally substituted cyclohexylene or phenylene;

[0269] -L is a bond or linking moiety, such as Alk, -C(=O)-, -C(=O)-O-Alk-O-

[0270] C(=O)-, -SO-, -SO2-, -C(=CCl2)- and -Alk-Ph-Alk-;

[0271] -Alk is an optionally substituted alkylene group;

[0272] -Ph is optionally substituted phenylene;

[0273] - m, n', r, v, u and w are independently integers from 2 to 20;

[0274] - each m" is independently an integer from 0 to 20;

[0275] - n, n*, p and y are independently integers from 2 to 4;

[0276] -n" is an integer equal to 0 or 1;

[0277] - m', o, t, x and z are independently an integer from 1 to 20;

[0278] - Each o* is independently an integer from 0 to 10, in particular from 1 to 6.

[0279] - each q is independently an integer from 0 to 20, provided that at least one q is not 0;

[0280] -s is an integer from 3 to 12;

[0281] Preferably, L1, L2 and L3 are independently a divalent linking moiety selected from the group consisting of an alkylene group such as 1,3-propanediyl, 1,3- or 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,8-octanediyl, 1,9-nonanediyl, 1,10-decanediyl, 1,12-decanediyl, 2-methyl-1,3-propanediyl, 2,2-diethyl-1,3-propanediyl, 3-methyl-1,5-pentanediyl, 3,3-dimethyl-1,5-pentanediyl, 2,2-dimethyl-1,3-propanediyl, 2,2-diethyl-1,3-propanediyl, 3,3-dimethyl-1,5-pentanediyl, 2,2-dimethyl-1,3-prop ... alkyl-1,3-propanediyl, 2,4-diethyl-1,5-pentanediyl; alkoxylated derivatives of the aforementioned alkylene groups, preferably ethoxylated and / or propoxylated derivatives of the aforementioned alkylene groups; derivatives of the aforementioned alkylene groups, preferably esterified by ring-opening polymerization of lactones such as ε-caprolactone; residues of di-, tri-, tetra- or polyoxyalkylene groups containing no hydroxyl groups, for example di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol, di-, tri- or tetrabutylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, poly(ethylene glycol-co-propylene glycol);

[0282] - a divalent moiety according to formula (S1):

[0283]

[0284] in:

[0285] -Each R 27 are independently alkyl, haloalkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkaryl, alkoxy, or aryloxy;

[0286] - each L5 is independently a bond or a hydrocarbon linker, which is optionally interrupted by one or more functional groups selected from ethers and esters;

[0287] -p * is 0 to 100;

[0288] - a tetravalent moiety according to formula (S2):

[0289]

[0290] in:

[0291] -Each R 28 are independently alkyl, haloalkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkaryl, alkoxy, or aryloxy;

[0292] - each L6 is independently a hydrocarbon linking moiety, which is optionally interrupted by one or more functional groups selected from ether, ester and amino groups;

[0293] -q* is 0 to 100;

[0294] - a polyvalent moiety according to formula (S3) or (S4):

[0295]

[0296] in:

[0297] -Each R 29 and R 30 are independently alkyl, haloalkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkaryl, alkoxy, or aryloxy;

[0298] - each L7 and L8 is independently a hydrocarbon linking moiety, which is optionally interrupted by one or more functional groups selected from ether, ester and amino groups;

[0299] - r* and t* are independently 0 to 100;

[0300] -s* is 2 to 18;

[0301] -u* is 1 to 9.

[0302] According to some embodiments, L1 and L4 may independently be the residue of a polyol (ie, the residue obtained by removing the OH group of a polyol). Suitable polyols (referred to herein as P OHExamples of the alkylene glycol include ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 1,3- or 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5- Pentylene glycol, neopentyl glycol, 2,4-diethyl-1,5-pentanediol, 3,3-butylethyl-1,5-pentanediol, cyclohexanediol, cyclohexane-1,4-dimethanol, norbornene dimethanol, norbornane dimethanol, tricyclodecanediol, tricyclodecane dimethanol, dicyclopentadiene glycol, hydroquinone bis(2-hydroxyethyl) ether, catechol, resorcinol, cashew diol, phloroglucinol, pyrogallol, tris(hydroxyphenyl)methane, tris(hydroxyphenyl)ethyl Alkane, bisphenol A, B, F or S, hydrogenated bisphenol A, B, F or S, trimethylolmethane, trimethylolethane, trimethylolpropane, di(trimethylolpropane), triethylolpropane, pentaerythritol, di(pentaerythritol), tri(pentaerythritol), glycerol, di-, tri- or tetraglycerol, polyglycerol, di-, tri- or tetra(ethylene glycol), di-, tri- or tetra(1,2-propylene glycol), di-, tri- or tetra(1,3-propylene glycol), di-, tri- or tetra( 1,4-Butanediol), poly(ethylene glycol), poly(propylene glycol), poly(trimethylene glycol), poly(tetramethylene glycol), poly(ethylene glycol-co-propylene glycol), sugar alcohols, i.e., erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, or iditol), dianhydrohexanols (i.e., isosorbide, isomannite, isoiditol), tris(2-hydroxyethyl)isocyanurate, hydroxylated vegetable oils, C 36 - dimer diols, polybutadiene polyols, polyester polyols, polyether polyols, polyorganosiloxane polyols (e.g. Silmer OH A0-UP, Silmer OH C50, Silmer OH J10, Silmer OH Di-10, Silmer OH Di-50, Silmer OHT A0, Silmer OHT Di-10, Silmer OHT Di-50, Silmer OHT Di-100, Silmer OHT Di-400, Silmer OHT E13 available from Siltech or Silmer OHT Di-10, Silmer OHT Di-50, Silmer OHT Di-100, Silmer OHT Di-400, Silmer OHT E13 available from Sinosil OF0035, OF0042, OF0156A, OF0156B, OF1300-M1100, OF1300-M2000, OF1300-M4000, OF6053, OF6055, OF9020), polycarbonate polyols, and alkoxylated (eg ethoxylated and / or propoxylated) derivatives thereof and derivatives obtained by ring-opening polymerization of ε-caprolactone initiated with one of the above polyols, and combinations thereof.

[0303] According to some embodiments, L1 can be a residue of a polyepoxide (i.e., a residue obtained by removing the epoxy groups of a polyepoxide). Examples of suitable polyepoxides include 1,2,3,4-diepoxybutane, 1,2,4,5-diepoxypentane, 1,2,5,6-diepoxyhexane, 1,2,7,8-diepoxyoctane, 1,2,9,10-diepoxydecane, epoxidized vegetable oils (such as epoxidized soybean oil and epoxidized linseed oil), epoxidized polybutadiene, triglycidyl isocyanurate, epoxy-functionalized polyorganosiloxanes (e.g., Silmer EP C50, Silmer EPC C50, Silmer EP J10, Silmer EP Di-50, Silmer EP Di-100, Silmer EPC Di-50, Silmer EP D208, Silmer EPCF418-F available from Siltech, or Silmer EPCF418-F available from Sinosil. EF1000 and EF1000) and their combinations.

[0304] In a preferred embodiment, L1 and L4 are independently the residue of a polyol selected from optionally alkoxylated trimethylolpropane, optionally alkoxylated di(trimethylolpropane), optionally alkoxylated pentaerythritol, optionally alkoxylated di(pentaerythritol), optionally alkoxylated tri(pentaerythritol), optionally alkoxylated glycerol, optionally alkoxylated diglycerol, optionally alkoxylated sorbitol, poly(ethylene glycol), poly(propylene glycol), poly(ethylene glycol-co-propylene glycol), poly(trimethylene glycol), poly(tetramethylene glycol), polyorganosiloxane polyols, and combinations thereof.

[0305] According to some embodiments, L2 may be a residue of a polythiol (i.e., a residue obtained by removing the SH group of a polythiol). Examples of suitable polythiols (also referred to herein as PSH) include ethane-1,2-dithiol, propane-1,3-dithiol, butane-1,4-dithiol, hexane-1,6-dithiol, octane-1,8-dithiol, decane-1,10-dithiol, 1,8-dimercapto-3,6-dioxaoctane (DMDO), di-, tri-, or polyethylene glycol di(ethanethiol), ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), 1,2-propanediol, 1,3-dithiol, 1,4-dithiol, ...thioglycolate), ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), 1 1,2-Propanediol bis(mercaptoacetate), 1,2-Propanediol bis(3-mercaptopropionate), 1,2-Propanediol bis(3-mercaptobutyrate), 1,3-Propanediol bis(mercaptoacetate), 1,3-Propanediol bis(3-mercaptopropionate), 1,3-Propanediol bis(3-mercaptobutyrate), 1,4-Butanediol bis(mercaptoacetate), 1,4-Butanediol bis(mercaptopropionate), 1,4-Butanediol bis(3-mercaptobutyrate), 1,6-Hexanediol bis(mercaptoacetate), 1,6-Hexanediol bis(3-mercaptopropionate) Ester), 1,6-hexanediol bis(3-mercaptobutyrate), di-, tri- or polyethylene glycol bis(thioglycolate), di-, tri- or polyethylene glycol bis(3-mercaptopropionate), di-, tri- or polyethylene glycol bis(3-mercaptobutyrate), di-, tri- or polypropylene glycol bis(thioglycolate), di-, tri- or polypropylene glycol bis(3-mercaptopropionate), di-, tri- or polypropylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(thioglycolate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(thioglycolate ...3-mercaptopropionate), trimethylolpropane tris Propane tris(3-mercaptobutyrate), pentaerythritol tris(thioglycolate), pentaerythritol tris(3-mercaptopropionate), pentaerythritol tris(3-mercaptobutyrate), pentaerythritol tetrakis(thioglycolate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tris[2-(3-mercaptobutyryloxy)ethyl]isocyanurate, thiol-terminated polymers (e.g. 3-800(BASF), GPM-800(Gabriel Performance Products), LOF (BASF), GPM-800LO (Gabriel Performance Products), KarenzMT PE-1 (ShowaDenko)), mercapto-functionalized polyorganosiloxanes (e.g., Silmer SH JO, Silmer SH Q20, and Silmer SH 208-30Q available from Siltech), and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof, and combinations thereof.

[0306] According to some embodiments, L3 can be a residue of a polyamine (ie, a residue obtained by removing the primary and secondary amine groups of a polyamine). Suitable polyamines (also referred to herein as P NH Examples of the amine group include 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 2-methylpentamethylenediamine, ethylenediamine, 1,2- or 1,3-propylenediamine, 2-methyl-1,2-propylenediamine, 2,2-dimethyl-1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,3- or 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexanediamine, 2,5-dimethyl-2,5-hexanediamine, 2,2,4- or 2,4,4-trimethyl-1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,8-octanediamine, 1,9-hexanediamine, 2,3-hexanediamine, 2,4-hexanediamine, 2,5-dimethyl-2,5-hexanediamine, 2,2,4- or 2,4,4-trimethyl-1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,8-hexanediamine, 2,3-hexanediamine, 2,3-hexanediamine, 2,4-hexanediamine, 2,5-hexanediamine, 2,2,4- or 2,4,4-trimethyl-1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,8-hexanediamine, 2,2-dimethyl-1,3-propanediamine, 1,8-hexanediamine, 2,2-di ,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 2,4- or 2,6-hexahydrotoluenediamine, 2,4'- or 4,4'-diamino-dicyclohexylmethane, 1,3- or 1,4-cyclohexanediamine, 1,3- or 1,4-bis(methylamino)cyclohexane, 1,8-p-menthanediamine, hydrazine, phenylenediamine, 2,3-2,4-3,4- or 2,6-toluenediamine, o-, m- or p-xylylenediamine, 2,4'- or 4,4'-diaminodiphenylmethane, benzidine, N-(2-aminoethyl)-1,3-propylenediamine, N,N'-bis-(2-aminoethyl)piperazine, polyetheramines (especially For example D-230, D-400, D-2000, D-2010, D-4000, ED-600, ED-900, ED-2003, EDR-148, EDR-176, THF-100, THF-170, T403, T3000, T5000, RFD-270), amino-functional polyorganosiloxanes (such as Silmer NH C50, Silmer NH Di-8, and Silmer NH Di-50 available from Siltech), and combinations thereof.

[0307] In one embodiment, the photoinitiator of the present invention may be according to formula (2), and Q3 and Q4 may form a polymer backbone. In this case, the photoinitiator of formula (2) preferably comprises:

[0308] - a plurality of units of formula (29):

[0309]

[0310] in

[0311] -B is *-O-[CH2-CH(OH)-Y] a -、-S- or -N(R 18 )-;

[0312] -Y, R 18 and A is as defined above;

[0313] - The symbol * represents the point of attachment to the C(=O) group;

[0314] and;

[0315] - a plurality of units according to one of the above formulae (20) to (28). Non-limiting examples of photoinitiators of formulae (1) and (2) are detailed below:

[0316]

[0317]

[0318]

[0319]

[0320]

[0321] and its isomers;

[0322] wherein each a, b, c, n, p, x, y and z independently represents an integer from 1 to 50, and each s independently represents an integer from 0 to 10. In the above formula, one or more oxyethylene units may be indiscriminately replaced by oxypropylene units and / or one or more oxypropylene units may be indiscriminately replaced by oxyethylene units.

[0323] The photoinitiators of formula (1) and (2) can be prepared by the method described in detail below.

[0324] Preparation method and precursor

[0325] All specific and preferred embodiments described above for the photoinitiators of formula (1) and (2) apply equally to the following methods and precursors.

[0326] Method n°1 and related precursors

[0327] The photoinitiator of formula (1) or (2) as described above can be prepared by a process comprising reacting at least one precursor of formula (30) or (31) with at least one product of formula (32):

[0328]

[0329] R'1-R'2 (32)

[0330] wherein Ar, R1, R2, R3, R'1, R'2, Q1, Q2 and Q3 are as defined above.

[0331] The wavy bonds shown in formulas (30) and (31) represent cis or trans isomers.

[0332] Preferably, the product of formula (32) can be selected from:

[0333] - amines, in particular secondary amines (e.g. sec-butylamine, isobutylamine, tert-butylamine, cyclohexylamine, 1,1,3,3-tetramethylbutylamine, morpholine, piperidine, pyrrolidine, N-methylpiperazine, oxazolidine, thiazolidine, thiomorpholine, azepane), more particularly secondary cyclic amines (e.g. morpholine, piperidine, pyrrolidine, N-methylpiperazine, oxazolidine, thiazolidine, thiomorpholine, azepane);

[0334] - alcohols, in particular primary alcohols (e.g. methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1-ol, 3-methylbutan-1-ol, 2,2-dimethylpropan-1-ol, hexan-1-ol, methylpentanol, 3-ethylbutan-1-ol, heptan-1-ol, octan-1-ol, 6-ethylhexan-1-ol, nonan-1-ol, decan-1-ol, dodecan-1-ol, tridecan-1-ol, isotridecan-1-ol, butoxyethanol, benzyl alcohol, methoxypolyethylene glycol);

[0335] - mercaptans, in particular primary mercaptans (for example 1-hexanethiol, 1-octanethiol, 1-decanethiol, 1-dodecanethiol, methyl thioglycolate, ethyl thioglycolate, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate);

[0336] - active methylene compounds, in particular β-diesters (for example dimethyl malonate, diethyl malonate, dipropyl malonate), β-ketoesters (for example ethyl acetoacetate), β-diketones (for example pentane-2,4-dione, cyclohexane-1,3-dione, 5,5-dimethylcyclohexane-1,3-dione), β-ketonitriles (for example 3-oxobutyronitrile), β-cyanoesters (for example methyl cyanoacetate, ethyl cyanoacetate), β-dinitriles (for example malononitrile).

[0337] The above reaction can be carried out in the presence of one or more compounds selected from the following:

[0338] a base, in particular a base selected from sodium hydroxide or potassium hydroxide, sodium carbonate or potassium carbonate or an amine base, for example a tertiary amine base, for example triethylamine, N,N-diisopropylethylamine, picoline, pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 4-dimethylaminopyridine (DMAP);

[0339] - solvents such as toluene, xylene, 2-butanone, methanol, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane and mixtures thereof.

[0340] The reaction can be carried out at a temperature of 10 to 120° C., preferably 50 to 100° C. The reaction can be carried out for a duration of 30 minutes to 24 hours, preferably 1 to 10 hours. Once the reaction is complete, the reaction medium can be washed one or more times with an aqueous solution, such as an aqueous hydrochloric acid solution, an aqueous sodium bicarbonate solution, and / or an aqueous sodium chloride solution. The solvent can be evaporated from the resulting organic phase.

[0341] The present invention also relates to precursors of formula (30) or (31):

[0342]

[0343] wherein Ar, R1, R2, R3, Q1, Q2 and Q3 are as defined above.

[0344] Examples of suitable precursors of formula (30) and (31) are listed below:

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351]

[0352] and its isomers;

[0353] wherein each a, b, c, n, p, x, y and z independently represents an integer from 1 to 50, and each s independently represents an integer from 0 to 10. In the above formula, one or more oxyethylene units may be indiscriminately replaced by oxypropylene units and / or one or more oxypropylene units may be indiscriminately replaced by oxyethylene units.

[0354] The precursor of formula (30) or (31) can be prepared by a process comprising reacting at least one precursor of formula (33) or (34) with at least one compound of formulae (35) to (42):

[0355]

[0356] in:

[0357] -Ar, R1, R2, R3, Q1, Y1 and Y2 are as defined above;

[0358] -G is OH, a halogen atom or -OC(=O)-J;

[0359] -J is alkyl or aryl, especially tert-butyl;

[0360] -R 14 As defined above;

[0361] -R 15 As defined above;

[0362] -R 16 and R 17 As defined above;

[0363] -Z 1a It is the hydroxyl-containing part;

[0364] -Z 1b is the epoxide-containing portion;

[0365] -Z 2 It is a thiol-containing moiety;

[0366] -Z 3 It is an amine-containing moiety;

[0367] -Z 4 It is the epoxide-containing portion.

[0368] The wavy bonds shown in formulas (33) and (34) represent cis or trans isomers.

[0369] The above reaction can be carried out in the presence of one or more compounds selected from the following:

[0370] a catalyst, in particular a catalyst selected from the group consisting of zirconium catalysts, titanium catalysts and quaternary ammonium salts, preferably selected from the group consisting of zirconium(IV) catalysts, titanium(IV) catalysts and tetraalkylammonium salts, more preferably selected from the group consisting of zirconium(IV) acetylacetonate, titanium(IV) isopropoxide, titanium(IV) oxyacetylacetonate, tetrabutylammonium bromide and tetrabutylammonium chloride;

[0371] - a solvent, in particular a solvent selected from toluene, xylene, acetonitrile, acetone, tetrahydrofuran and mixtures thereof;

[0372] - cosolvents, such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane and mixtures thereof.

[0373] Stabilizers / inhibitors, in particular inhibitors selected from hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ, 4-methoxyphenol), 4-tert-butylcatechol (TBC) and 3,5-di-tert-butyl-4-hydroxytoluene (BHT), phenothiazine (PTZ) and mixtures thereof.

[0374] When the reaction corresponds to esterification, amidation or thioesterification, the reaction can be carried out in the presence of a zirconium catalyst or a titanium catalyst. When the reaction corresponds to the ring-opening of an epoxy ring, the reaction can be carried out in the presence of a quaternary ammonium salt as a catalyst. The reaction can be carried out at a temperature of 70 to 140 ° C and preferably 90 to 130 ° C. The reaction can be carried out for a duration of 1 to 72 hours and preferably 4 to 24 hours. The reaction can be carried out to eliminate the water formed during the reaction. For example, the reaction can be carried out in a reactor equipped with a condenser (i.e., Dean-Stark), and the reaction medium can be heated at a temperature sufficient to evaporate water (optionally as an azeotropic mixture with a solvent). Once the reaction is complete, the reaction medium can be washed once or repeatedly with an aqueous solution (e.g., sodium chloride aqueous solution). The solvent can be evaporated from the resulting organic phase.

[0375] In one embodiment, the precursor of formula (30) or (31) can be prepared by a process comprising reacting at least one precursor of formula (33) or (34) with at least one compound of formula (38), and Z 1a Corresponding to formula (43):

[0376]

[0377] wherein L1 and b are as defined above.

[0378] Preferably, the compound of formula (38) is as described above for P OH Polyols listed.

[0379] Alternatively, the precursor of formula (30) or (31) can be prepared by a process comprising reacting at least one precursor of formula (33) or (34) with at least one compound of formula (39), and Z 1b Corresponding to formula (44):

[0380]

[0381] in:

[0382] -Y1 is as defined above;

[0383] - L1 and b are as defined above.

[0384] Preferably, the compound of formula (39) is a polyepoxide, also referred to herein as P EPOX, selected from 1,2,3,4-diepoxybutane; 1,2,4,5-diepoxypentane; 1,2,5,6-diepoxyhexane; 1,2,7,8-diepoxyoctane; 1,2,9,10-diepoxydecane; glycidyl ethers or esters of polyols (such as the POH polyols listed above), including ethylene glycol diglycidyl ether, 1,2- or 1,3-propylene glycol diglycidyl ether, 1,2-, 1,3- or 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,7-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 2-methyl-1,3-propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 2,2-diethyl-1,3-propylene glycol diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, 3,3-dimethyl-1,5-pentanediol diglycidyl ether, 2,4-diethyl-1,5-pentanediol diglycidyl ether, 3,3-butylethyl-1,5-pentanediol diglycidyl ether, di-, tri- or tetra(ethylene glycol) diglycidyl ether, di-, tri- or tetra(1,2-propylene glycol) diglycidyl ether, di-, tri- or tetra(1,3-propylene glycol) diglycidyl ether, di-, tri- - or tetrakis(1,4-butanediol) diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly(trimethylene glycol) diglycidyl ether, poly(tetramethylene glycol) diglycidyl ether, poly(ethylene glycol-co-propylene glycol) diglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, di(trimethylolpropane) tetraglycidyl ether, pentaerythritol tetraglycidyl ether, cyclohexanedicarboxylic acid diglycidyl ester, cyclohexane diglycidyl ether, cyclohexane-1,4-dimethanol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether triglycidyl ether, tris(hydroxyphenyl)methane triglycidyl ether, tris(hydroxyphenyl)ethane triglycidyl ether, bisphenol A, B, F or S diglycidyl ether, hydrogenated bisphenol A, B, F or S diglycidyl ether, diglycidyl phthalate, diglycidyl terephthalate, diglycidyl isophthalate; epoxidized vegetable oils (such as epoxidized soybean oil and epoxidized linseed oil); epoxidized polybutadiene; triglycidyl isocyanurate; epoxy-functionalized polyorganosiloxanes and combinations thereof.

[0385] Alternatively, the precursor of formula (30) or (31) can be prepared by a process comprising reacting at least one precursor of formula (33) or (34) with at least one compound of formula (40), and Z 2 Corresponding to formula (45):

[0386]

[0387] wherein L2 and b' are as defined above.

[0388] Preferably, the compound of formula (40) is as described above for P SH Polythiols listed.

[0389] Alternatively, the precursor of formula (30) or (31) may be prepared by a process comprising reacting at least one precursor of formula (33) or (34) with at least one compound of formula (41), and Z 3 Corresponding to formula (46):

[0390]

[0391] in:

[0392] -R 18 As defined above;

[0393] - L3 and b" are as defined above.

[0394] Preferably, the compound of formula (41) is as described above for P NH Polyamines listed.

[0395] Alternatively, the precursor of formula (30) or (31) can be prepared by a process comprising reacting at least one precursor of formula (33) or (34) with at least one compound of formula (42), and Z 4 Corresponding to formula (47):

[0396]

[0397] in:

[0398] -Y2 is as defined above;

[0399] - L4 and b'' are as defined above.

[0400] Preferably, the compound of formula (42) is an alicyclic polyepoxide, also known as P CYCLO.EPOX, selected from 7-oxabicyclo[4.1.0]hept-3-ylmethyl 7-oxabicyclo[4.1.0]heptane-3-carboxylate (UviCure S105), bis((3,4-epoxycyclohexyl)methyl)adipate (UviCure S128), 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, compounds of formula (47a), (47b) or (47c), polyorganosiloxanes functionalized with alicyclic epoxides (e.g., Silmer EPC C50, Silmer EPC Di-50 and Silmer EPC F418-F available from Siltech), and combinations thereof:

[0401]

[0402] The present invention also relates to precursors of formula (33) or (34):

[0403]

[0404]

[0405] in:

[0406] -Ar, R1, R2, R3, Q1 are as defined above;

[0407] -G is OH, a halogen atom or -OC(=O)-J;

[0408] -J is alkyl or aryl, especially tert-butyl.

[0409] Examples of suitable precursors of formula (33) and (34) are listed below:

[0410]

[0411] The precursor of formula (33) or (34) can be prepared by a process comprising reacting at least one phosphine oxide of formula (48) or (49) with at least one cyclic anhydride of formula (50) to provide a precursor according to formula (33) or (34) wherein G is OH:

[0412]

[0413] wherein Ar, R1, R2, R3, and Q1 are as defined above;

[0414] The method optionally comprises the following additional steps:

[0415] - reacting a precursor according to formula (33) or (34) wherein G is OH with an acyl halide of formula (51) to provide a precursor according to formula (33) or (34) wherein G is -OC(=O)-J

[0416] Hal-C(=O)-J (51)

[0417] wherein Hal is a halogen atom and J is an alkyl or aryl group, in particular a tert-butyl group; or

[0418] - reacting a precursor according to formula (33) or (34) wherein G is OH with a halogenating agent, in particular thionyl chloride, to provide a precursor according to formula (33) or (34) wherein G is a halogen atom.

[0419] The reaction of at least one phosphine oxide of formula (48) or (49) with at least one cyclic anhydride of formula (50) may be carried out using maleic anhydride as the cyclic anhydride of formula (50). The reaction may be carried out in the presence of one or more compounds selected from the group consisting of:

[0420] - Lewis acids, in particular metal halides, such as ferric chloride, aluminum chloride or aluminum bromide;

[0421] - a solvent, in particular a solvent selected from the group consisting of toluene, xylene, dichloromethane, chloroform, 1,2-dichloroethane and mixtures thereof and mixtures thereof.

[0422] The reaction can be carried out at a temperature of 15 to 50° C., in particular 20 to 40° C. The reaction can be carried out for a duration of 1 to 72 hours, preferably 8 to 36 hours. Once the reaction is complete, the reaction medium can be washed one or more times with an aqueous solution (e.g., an aqueous sodium chloride solution). The solvent can be evaporated from the resulting organic phase.

[0423] The reaction of the precursor according to formula (33) or (34) (wherein G is OH) with the acid halide of formula (51) can be carried out using trimethylacetyl chloride as the acid chloride of formula (51). The reaction can be carried out in the presence of one or more compounds selected from the group consisting of:

[0424] a base, in particular a base selected from sodium hydroxide or potassium hydroxide, sodium carbonate or potassium carbonate or an amine base, for example a tertiary amine base, for example triethylamine, N,N-diisopropylethylamine, picoline, pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 4-dimethylaminopyridine (DMAP);

[0425] - solvents such as xylene, toluene, tetrahydrofuran, dichloromethane and mixtures thereof.

[0426] The reaction can be carried out at a temperature of -10 to 10°C, preferably 0 to 5°C. The reaction can be carried out for a duration of 1 to 120 minutes, preferably 15 to 45 minutes. The anhydride obtained can be used in pure form in the next step of the process (i.e., reacted with a compound of at least one of formulae (35) to (42) to provide a precursor of formula (30) or (31)).

[0427] Method n°2 and related precursors

[0428] The photoinitiator of formula (1) or (2) as described above can be prepared by a process comprising reacting at least one precursor of formula (52) or (53) with at least one compound of formulae (35) to (42):

[0429]

[0430]

[0431] in:

[0432] -Ar, R1, R2, R3, R'1, R'2, Q1, Y1 and Y2 are as defined above;

[0433] -G is OH, a halogen atom or -OC(=O)-J;

[0434] -J is alkyl or aryl, especially tert-butyl;

[0435] -R 14 As defined above;

[0436] -R 15 As defined above;

[0437] -R 16 and R 17 As defined above;

[0438] -Z 1a It is the hydroxyl-containing part;

[0439] -Z 1b is the epoxide-containing portion;

[0440] -Z 2 It is a thiol-containing moiety;

[0441] -Z 3 It is an amine-containing moiety;

[0442] -Z 4 It is the epoxide-containing portion.

[0443] The above reaction can be carried out as defined above for the preparation of the precursor of formula (30) or (31).

[0444] In one embodiment, the photoinitiator of formula (1) or (2) can be prepared by a process comprising reacting at least one precursor of formula (52) or (53) with at least one compound of formula (38), and Z 1a Corresponding to formula (43):

[0445]

[0446] wherein L1 and b are as defined above.

[0447] Preferably, the compound of formula (38) is as described above for P OH Polyols listed.

[0448] Alternatively, the photoinitiator of formula (1) or (2) may be prepared by a process comprising reacting at least one precursor of formula (52) or (53) with at least one compound of formula (39), and Z 1b Corresponding to formula (44):

[0449]

[0450] in:

[0451] -Y1 is as defined above;

[0452] - L1 and b are as defined above;

[0453] Preferably, the compound of formula (39) is as above for P EPOX Polyepoxides listed.

[0454] Alternatively, the photoinitiator of formula (1) or (2) may be prepared by a process comprising reacting at least one precursor of formula (52) or (53) with at least one compound of formula (40), and Z 2 Corresponding to formula (45):

[0455]

[0456] wherein L2 and b' are as defined above.

[0457] Preferably, the compound of formula (40) is as described above for P SH Polythiols listed.

[0458] Alternatively, the photoinitiator of formula (1) or (2) may be prepared by a process comprising reacting at least one precursor of formula (52) or (53) with at least one compound of formula (41), and Z 3 Corresponding to formula (46):

[0459]

[0460] in:

[0461] -R 18 As defined above;

[0462] - L3 and b" are as defined above.

[0463] Preferably, the compound of formula (41) is as described above for P NH The polyamines listed.

[0464] Alternatively, the photoinitiator of formula (1) or (2) may be prepared by a process comprising reacting at least one precursor of formula (52) or (53) with at least one compound of formula (42), and Z 4 Corresponding to formula (47):

[0465]

[0466] in:

[0467] -Y2 is as defined above;

[0468] - L4 and b'' are as defined above.

[0469] Preferably, the compound of formula (42) is as above for P CYCLO List of cycloaliphatic polyepoxides. Epoxy resins

[0470] The present invention also relates to precursors of formula (52) or (53):

[0471]

[0472] in:

[0473] -Ar, R1, R2, R3, R'1, R'2 and Q1 are as defined above; -G is OH, a halogen atom or -OC(=O)-J;

[0474] -J is alkyl or aryl, especially tert-butyl.

[0475] Non-limiting examples of precursors of formula (52) and (53) are listed below:

[0476]

[0477] wherein G is OH, a halogen atom or -OC(=O)-J.

[0478] The precursor of formula (52) or (53) can be prepared by a process comprising reacting at least one precursor of formula (33) or (34) with at least one product of formula (32) to provide a precursor of formula (52) or (53) wherein G is OH:

[0479]

[0480] R'1-R'2 (32)

[0481] in

[0482] -Ar, R1, R2, R3, R'1, R'2 and Q1 are as defined herein;

[0483] -G is OH;

[0484] The method optionally comprises the following additional steps:

[0485] - reacting a precursor according to formula (52) or (53) wherein G is OH with an acyl halide of formula (51) to provide a precursor according to formula (52) or (53) wherein G is -OC(=O)-J

[0486] Hal-C(=O)-J (51)

[0487] wherein Hal is a halogen atom and J is an alkyl or aryl group, in particular a tert-butyl group; or

[0488] - reacting a precursor according to formula (52) or (53) wherein G is OH with a halogenating agent, in particular thionyl chloride, to provide a precursor according to formula (52) or (53) wherein G is a halogen atom.

[0489] The reaction of at least one precursor of formula (33) or (34) with at least one product of formula (32) can be carried out in the presence of one or more compounds selected from the group consisting of:

[0490] a base, in particular a base selected from sodium hydroxide or potassium hydroxide, sodium carbonate or potassium carbonate or an amine base, for example a tertiary amine base, for example triethylamine, N,N-diisopropylethylamine, picoline, pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 4-dimethylaminopyridine (DMAP);

[0491] - solvents such as toluene, xylene, 2-butanone, methanol, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane and mixtures thereof.

[0492] The reaction can be carried out at a temperature of 10 to 120° C. and preferably 50 to 80° C. The reaction can be carried out for a duration of 30 minutes to 24 hours and preferably 1 to 10 hours. Once the reaction is complete, the reaction medium can be washed one or more times with an aqueous solution, such as an aqueous hydrochloric acid solution, an aqueous sodium bicarbonate solution and / or an aqueous sodium chloride solution. The solvent can be evaporated from the resulting organic phase.

[0493] The product of formula (32) used in the process for the preparation of the precursor of formula (52) or (53) may be selected from amines, alcohols, thiols and active methylene compounds and is as defined above in process n° 1 and the related precursors.

[0494] The reaction of the precursor according to formula (52) or (53) (wherein G is OH) with the acid halide of formula (51) can be carried out using trimethylacetyl chloride as the acid chloride of formula (51). The reaction can be carried out in the presence of one or more compounds selected from the group consisting of:

[0495] a base, in particular a base selected from sodium hydroxide or potassium hydroxide, sodium carbonate or potassium carbonate or an amine base, for example a tertiary amine base, for example triethylamine, N,N-diisopropylethylamine, picoline, pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 4-dimethylaminopyridine (DMAP);

[0496] - solvents such as xylene, toluene, tetrahydrofuran, dichloromethane and mixtures thereof.

[0497] The reaction can be carried out at a temperature of -10 to 10°C, preferably 0 to 5°C. The reaction can be carried out for a duration of 1 to 120 minutes, preferably 15 to 45 minutes. The anhydride obtained can be used in pure form in the next step of the process (i.e., reacting with a compound of at least one of formulae (35) to (42) to provide a photoinitiator of formula (1) or (2)).

[0498] Method n°3 and related precursors

[0499] The photoinitiator of formula (5) or (6) as described above can be prepared by a process comprising reacting at least one precursor of formula (33) or (34) with at least one product of formula (54):

[0500]

[0501]

[0502] HX-L0-X'H (54)

[0503] in:

[0504] -Ar, R1, R2, R3, Q1 are as defined above;

[0505] -X and X' are independently selected from O, S and NR 19 ;

[0506] -R 19 is H or optionally substituted alkyl;

[0507] -L0 is an optionally substituted C1-C4 alkylene

[0508] -G is OH, a halogen atom or -OC(=O)-J;

[0509] -J is alkyl or aryl, especially tert-butyl;

[0510] Preferably, the product of formula (54) used in the process for preparing the photoinitiator of formula (5) or (6) is a compound bearing two functional groups independently selected from hydroxyl, amino and thiol. More preferably, the product of formula (54) is an amino alcohol (e.g., 2-aminoethanol, 2-(methylamino)ethanol, 2-(ethylamino)ethanol, 3-methylamino-1-propanol), an aminothiol (e.g., 2-aminoethanethiol), a mercaptoalcohol (e.g., 2-hydroxyethanethiol), a diol (e.g., ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,4-butanediol), a diamine (e.g., ethylenediamine, 1,2'-dimethylethylenediamine, 1,2'-diethylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, 1,2-diaminopropane, diethylenetriamine), an amino ester containing an amine group and an alcohol or thiol group, or an amino acid (e.g., D / L-serine, D / L-cysteine, D / L-threonine, and esters thereof, in particular, their methyl or ethyl esters).

[0511] Precursors of formula (33) and (34) can be prepared according to the method described in process n° 1 and the related precursors.

[0512] The reaction of at least one precursor of formula (33) or (34) with at least one product of formula (54) can be carried out in the presence of one or more compounds selected from the group consisting of:

[0513] a base, in particular a base selected from sodium hydroxide or potassium hydroxide, sodium carbonate or potassium carbonate or an amine base, for example a tertiary amine base, for example triethylamine, N,N-diisopropylethylamine, picoline, pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 4-dimethylaminopyridine (DMAP);

[0514] - solvents such as toluene, xylene, 2-butanone, methanol, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane and mixtures thereof.

[0515] The reaction can be carried out at a temperature of 10 to 100° C. and preferably 20 to 50° C. The reaction can be carried out for a duration of 30 minutes to 24 hours and preferably 3 to 20 hours. Once the reaction is complete, the reaction medium can be washed one or more times with an aqueous solution, such as an aqueous hydrochloric acid solution, an aqueous sodium bicarbonate solution and / or an aqueous sodium chloride solution. The solvent can be evaporated from the resulting organic phase.

[0516] Photoinitiator composition

[0517] The present disclosure also relates to a photoinitiator composition comprising:

[0518] - a mixture of at least two photoinitiators of formula (1) according to the invention;

[0519] - a mixture of at least two photoinitiators of formula (2) according to the invention;

[0520] a mixture of at least one photoinitiator of formula (1) according to the invention and at least one precursor of formula (30) according to the invention; or

[0521] A mixture of at least one photoinitiator of formula (2) according to the invention and at least one precursor of formula (31) according to the invention.

[0522] Advantageously, the photoinitiator composition comprising a mixture of such photoinitiators may be liquid at 20°C.

[0523] Furthermore, the present disclosure relates to a photoinitiator composition comprising the photoinitiator of formula (1) or (2) according to the present invention and a photoinitiator other than the photoinitiator of formula (1) or (2).

[0524] The photoinitiator other than the photoinitiator of formula (1) or (2) may be a photoinitiator having Norrish type I activity and / or Norrish type II activity, more particularly a free radical photoinitiator having Norrish type I activity.

[0525] Non-limiting types of additional photoinitiators suitable for use in the photoinitiator compositions of the present invention include, for example, benzoin, benzoin ethers, acetophenones, α-hydroxyacetophenones, benzil, benzil ketals, anthraquinones, phosphine oxides, acylphosphine oxides, α-hydroxyketones, phenylglyoxylates, α-aminoketones, benzophenones, thioxanthones, xanthones, acridine derivatives, phenazine derivatives, quinoxaline derivatives, triazine compounds, benzoylformates, aromatic oximes, metallocenes, acylsilyl or acylgermanyl compounds, camphorquinone, polymeric derivatives thereof, and mixtures thereof.

[0526] Examples of suitable additional photoinitiators include, but are not limited to, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzylanthraquinone, 2-tert-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, benzoin ether, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, Michler's ketone, acetophenones such as 2,2-dialkoxybenzophenone and 1-hydroxyphenyl ketone, benzophenone, 4,4'-bis-(diethylamino)benzophenone, acetophenone, 2,2-diethoxyacetophenone, 2-isopropylthioxanthone, thioxanthone, diethylthioxanthone, 1,5-Acenaphthylene, benzil, α-hydroxy ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 2-hydroxy-2-methyl-1-phenyl-propanone, oligomeric α-hydroxy ketone, benzoylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, anisole, anthraquinone, anthraquinone-2-sulfonic acid sodium salt monohydrate, (benzene)tricarbonylchromium , benzoin isobutyl ether, benzophenone / 1-hydroxycyclohexyl phenyl ketone 50 / 50 blend, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4-benzoylbiphenyl, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyl benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, camphorquinone, 2-chlorothioxanthene-9-one, dibenzocycloheptadienone, 4,4'-dihydroxybenzophenone, 4,4'-dimethyldibenzoyl, 2,5-dimethyldiphenylbenzophenone, 3,4-dimethylbenzophenone, diphenyl(2, 4,6-trimethylbenzoyl)phosphine oxide / 2-hydroxy-2-methylpropiophenone 50 / 50 blend, 4'-ethoxyacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 3'-hydroxyacetophenone, 4'-hydroxyphenylphenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, methylbenzoylformate, phenanthrenequinone, 4'-phenoxyacetophenone, (cumene)cyclopentadienyliron(ii) hexafluorophosphate, 9,10-diethoxy and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, and combinations thereof.

[0527] In particular, the additional photoinitiator may be selected from benzophenones, e.g. BP (benzophenone), 7005 (polymerized benzophenone), 7006 (polymerized benzophenone), EMK (4,4'-bis(diethylamino)benzophenone) or BMS (4-benzoyl-4'-methyldiphenyl sulfide); thioxanthone such as 7010 (polymerized thioxanthone), ITX (isopropylthioxanthone), DETX (2,4-diethylthioxanthone) or CPTX (1-chloro-4-propoxythioxanthone); α-hydroxyacetophenone, such as 73 (2-Hydroxy-2-methyl-1-phenylpropanone); acylphosphine oxides such as BPO (phenyl bis (2,4,6-trimethylbenzoyl) -phosphine oxide), TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) or TPO-L (ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate); phenylglyoxylates, e.g. MBF (methylbenzoyl formate); and mixtures thereof.

[0528] More particularly, the additional photoinitiator may be a phenylglyoxylate, in particular MBF (methylbenzoyl formate). Alternatively, the additional photoinitiator may be an α-hydroxyacetophenone, in particular 73 (2-hydroxy-2-methyl-1-phenylpropanone). Alternatively, the additional photoinitiator may be a benzophenone, in particular 7005 (polymerized benzophenone).

[0529] Photopolymerization method

[0530] The photoinitiator of formula (1) or (2) as defined above or the photoinitiator composition as defined above may be used in a photopolymerization process, ie a process for photopolymerizing (eg curing) one or more ethylenically unsaturated compounds.

[0531] The process for photopolymerizing one or more ethylenically unsaturated compounds comprises contacting the one or more ethylenically unsaturated compounds with a photoinitiator of formula (1) or (2) according to the invention or a photoinitiator composition according to the invention and irradiating the mixture, in particular with UV, near-UV, visible, infrared and / or near-infrared radiation.

[0532] The ethylenically unsaturated compounds may be defined as follows.

[0533] Curable composition

[0534] The curable (or polymerizable) composition of the present invention comprises a photoinitiator of formula (1) or (2) according to the present invention or a photoinitiator composition according to the present invention, referred to as component A). The curable composition of the present invention further comprises an ethylenically unsaturated compound (or a mixture of ethylenically unsaturated compounds), referred to as component b).

[0535] The curable composition of the present invention may comprise:

[0536] - 0.05 to 30%, preferably 0.1 to 20%, more preferably 0.2 to 15%, more preferably 0.5 to 10%, and even more preferably 1 to 5% of component a);

[0537] - 70-99.95%, preferably 80-99.9%, more preferably 85-99.8%, more preferably 90-99.5%, and even more preferably 95-99% of component b);

[0538] % are wt% based on the total weight of components a) and b).

[0539] The curable composition of the present invention may further comprise one or more compounds selected from the group consisting of:

[0540] - cationically polymerizable compounds;

[0541] - polyols and / or polythiols;

[0542] - additives; and

[0543] -Solvent.

[0544] Ethylenically unsaturated compounds

[0545] As used herein, the term "ethylenically unsaturated compound" means a compound containing a polymerizable carbon-carbon double bond. A polymerizable carbon-carbon double bond is a carbon-carbon double bond that can react with another carbon-carbon double bond in a polymerization reaction. The polymerizable carbon-carbon double bond is typically contained in a group selected from acrylates (including cyanoacrylates), methacrylates, acrylamides, methacrylamides, styrenes, maleates, fumarates, itaconates, allyls, propenyls, vinyls, and combinations thereof, preferably in a group selected from acrylates, methacrylates, allyls, and vinyls, more preferably in a group selected from acrylates and methacrylates. The carbon-carbon double bonds of benzene rings are not considered polymerizable carbon-carbon double bonds.

[0546] According to some preferred embodiments, the ethylenically unsaturated compound can be selected from (meth)acrylate functional monomers, (meth)acrylate functional oligomers and mixtures thereof. In particular, the ethylenically unsaturated compound comprises (meth)acrylate functional oligomers and (meth)acrylate functional monomers.

[0547] As used herein, the term "(meth)acrylate functional monomer" means a monomer comprising a (meth)acrylate group, particularly an acrylate group. The term "(meth)acrylate functional oligomer" means an oligomer comprising a (meth)acrylate group, particularly an acrylate group. The term "(meth)acrylate group" encompasses both an acrylate group (-O-CO-CH=CH2) and a methacrylate group (-O-CO-C(CH3)=CH2).

[0548] According to some embodiments, the ethylenically unsaturated compound comprises a (meth)acrylate functional monomer.The ethylenically unsaturated compound may comprise a mixture of (meth)acrylate functional monomers.

[0549] The (meth)acrylate functional monomer may have a molecular weight of less than 600 g / mol, specifically 100-550 g / mol, more specifically 200-500 g / mol.

[0550] The (meth)acrylate functional monomer may have 1 to 6 (meth)acrylate groups, specifically 1 to 3 (meth)acrylate groups.

[0551] The (meth)acrylate functional monomer may comprise a mixture of (meth)acrylate functional monomers having different functionalities. For example, the (meth)acrylate functional monomer may comprise a mixture of (meth)acrylate functional monomers containing a single acrylate or methacrylate group per molecule (referred to herein as a "mono (meth)acrylate functional compound") and (meth)acrylate functional monomers containing two or more, preferably two or three, acrylate and / or methacrylate groups per molecule.

[0552] In one embodiment, the (meth)acrylate functional monomer comprises a mono(meth)acrylate functional monomer.The mono(meth)acrylate functional monomer can advantageously serve as a reactive diluent and reduce the viscosity of the composition.

[0553] Examples of suitable mono(meth)acrylate functional monomers include, but are not limited to, mono(meth)acrylates of aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched, or cycloaliphatic and may be a monool, diol, or polyol, provided that only one hydroxyl group is (meth)acrylated); mono(meth)acrylates of aromatic alcohols (such as phenols, including alkylated phenols); mono(meth)acrylates of alkylaryl alcohols (such as benzyl alcohol); mono(meth)acrylates of oligomeric and polymeric glycols (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol); Acrylic acid esters; mono(meth)acrylates of monoalkyl ethers of diols and oligomeric diols; mono(meth)acrylates of alkoxylated (e.g., ethoxylated and / or propoxylated) aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched or cycloaliphatic and may be a monohydric alcohol, a dihydric alcohol or a polyhydric alcohol, provided that only one hydroxyl group of the alkoxylated aliphatic alcohol is (meth)acrylated); mono(meth)acrylates of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (e.g., alkoxylated phenols); caprolactone mono(meth)acrylate; and the like.

[0554] The following compounds are specific examples of mono(meth)acrylate-functional monomers suitable for component 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-hydroxypropyl(meth)acrylate and 3-hydroxypropyl(meth)acrylate; 2-methoxyethyl(meth)acrylate; 2-ethoxyethyl(meth)acrylate; 2-ethoxypropyl(meth)acrylate and 3-ethoxypropyl(meth)acrylate; tetrahydrofurfuryl(meth)acrylate; alkoxylated tetrahydrofurfuryl(meth)acrylate; (meth)acrylate 2-(2-ethoxyethoxy)ethyl acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate; lauryl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; alkoxylated phenol (meth)acrylate; alkoxylated nonylphenol (meth)acrylate; cyclic trimethylolpropane formal (meth)acrylate; isobornyl (meth)acrylate; tricyclodecanemethanol (meth)acrylate; tert-butylcyclohexanol (meth)acrylate acrylate; trimethylcyclohexanol (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; diethylene glycol monoethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; ethoxylated lauryl (meth)acrylate; methoxy polyethylene glycol (meth)acrylate; hydroxyethyl-butyl carbamate (meth)acrylate; 3-(2-hydroxyalkyl) oxazolidinone (meth)acrylate; and combinations thereof.

[0555] In one embodiment, the (meth)acrylate functional monomer may comprise a (meth)acrylate functional monomer containing two or more (meth)acrylate groups per molecule.

[0556] Examples of suitable (meth)acrylate functional monomers containing two or more (meth)acrylate groups per molecule include acrylate and methacrylate esters of polyols. Examples of suitable polyols are described above for P OH Such polyols may be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.), provided that they contain at least two (meth)acrylate functional groups per molecule.

[0557] Exemplary (meth)acrylate functional monomers containing two or more (meth)acryloyloxy groups per molecule may include bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate. Acrylates; 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)acrylates; 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; glycerol di(meth)acrylate; glycerol tri(meth)acrylate; trimethylolethane tri(meth)acrylate; trimethylolethane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane di(meth)acrylate; quaternary Pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) diacrylate; di(trimethylolpropane) triacrylate; di(trimethylolpropane) tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol) tetraacrylate; di(pentaerythritol) pentaacrylate; di(pentaerythritol) hexa(meth)acrylate; tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate; and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and combinations thereof.

[0558] Component A) may comprise 0 to 99.5% by weight, in particular 5 to 90% by weight, more in particular 10 to 80% by weight, even more in particular 15 to 75% by weight, and still more in particular 20 to 70% by weight of (meth)acrylate-functional monomers, based on the total weight of component A). In particular, component A) may comprise 5 to 50% by weight, or 10 to 50% by weight, or 15 to 50% by weight, or 20 to 50% by weight, or 25 to 50% by weight, or 30 to 50% by weight of (meth)acrylate-functional monomers, based on the total weight of component A). Alternatively, component A) may comprise 50 to 99.5% by weight, or 55 to 99.5% by weight, or 60 to 99.5% by weight, or 65 to 99.5% by weight, or 70 to 99.5% by weight of (meth)acrylate-functional monomers, based on the total weight of component A).

[0559] In one embodiment, the ethylenically unsaturated compound comprises a (meth)acrylate functional oligomer.The ethylenically unsaturated compound may comprise a mixture of (meth)acrylate functional oligomers.

[0560] The (meth)acrylate functional oligomer may be selected to enhance the flexibility, strength, and / or modulus of the cured polymer prepared using composition A, among other properties.

[0561] The (meth)acrylate functional oligomer may have 1 to 18 (meth)acrylate groups, specifically 2 to 6 (meth)acrylate groups, more specifically 2 to 6 acrylate groups.

[0562] The (meth)acrylate functional oligomer can have a number average molecular weight equal to or greater than 600 g / mol, specifically 800 to 15,000 g / mol, more specifically 1,000 to 5,000 g / mol.

[0563] In particular, the (meth)acrylate functionalized oligomer may be selected from (meth)acrylate functionalized urethane oligomers (sometimes also referred to as "urethane (meth)acrylate oligomers", "polyurethane (meth)acrylate oligomers" or "urethane (meth)acrylate oligomers"), (meth)acrylate functionalized epoxy oligomers (sometimes also referred to as "epoxy (meth)acrylate oligomers"), (meth)acrylate functionalized polyether oligomers (sometimes also referred to as "polyether (meth)acrylate oligomers"), (meth)acrylate functionalized polydiene oligomers (sometimes also referred to as "polydiene (meth)acrylate oligomers"), (meth)acrylate functionalized polycarbonate oligomers (sometimes also referred to as "polycarbonate (meth)acrylate oligomers") and (meth)acrylate polyester oligomers (sometimes also referred to as "polyester (meth)acrylate oligomers"), and mixtures thereof.

[0564] Preferably, the (meth)acrylate functional oligomer comprises a (meth)acrylate functional urethane oligomer, more preferably an acrylate functional urethane oligomer.

[0565] Advantageously, the (meth)acrylate functional oligomer comprises a (meth)acrylate functional urethane oligomer having two (meth)acrylate groups, more preferably an acrylate functional urethane oligomer having two acrylate groups.

[0566] Exemplary polyester (meth)acrylate oligomers include the reaction products of acrylic acid or methacrylic acid, or mixtures thereof, or synthetic equivalents thereof, with hydroxyl-terminated polyester polyols. The reaction process can be carried out so that all or substantially all of the hydroxyl groups of the polyester polyol are (meth)acrylated, particularly where the polyester polyol is difunctional. The polyester polyol can be prepared by the polycondensation reaction of a polyol (particularly a diol) and a polycarboxylic acid functional compound (particularly a dicarboxylic acid and anhydride). The polyol and the polycarboxylic acid functional compound can each have a linear, branched, alicyclic, or aromatic structure and can be used alone or as a mixture.

[0567] Examples of suitable epoxy (meth)acrylates include reaction products of acrylic acid or methacrylic acid, or mixtures thereof, with epoxy resins (polyglycidyl ethers or esters). The epoxy resin may be particularly selected from bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4 -Epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, dicyclopentadiene diepoxide, 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 ether of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyols such as ethylene glycol, propylene glycol and glycerol, diglycidyl esters of aliphatic C6-C22 dibasic acids, glycidyl esters of C30-36 dimers of fatty acids, epoxidized vegetable oils (such as epoxidized soybean oil and epoxidized linseed oil), epoxidized polybutadiene, and the like.

[0568] Suitable polyether (meth) acrylate oligomers include, but are not limited to, condensation products of acrylic acid or methacrylic acid or their synthetic equivalents or mixtures thereof with polyether alcohols, which are polyether polyols (e.g., polyethylene glycol, polypropylene glycol, or polytetramethylene glycol). Suitable polyether alcohols can be straight-chain or branched substances containing ether linkages and terminal hydroxyl groups. Polyether alcohols 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 initiator molecules. Suitable initiator molecules include water, polyhydroxy-functional materials, polyester polyols, and amines.

[0569] Suitable polyurethane (meth)acrylate oligomers for use in composition A (sometimes also referred to as "urethane (meth)acrylate oligomers") include urethane-based, aliphatic, cycloaliphatic, and / or aromatic polyester diisocyanates and polyether diisocyanates terminated with (meth)acrylate end groups in combination with aliphatic, cycloaliphatic, and / or aromatic polyester polyols and polyether polyols. Suitable polyurethane (meth)acrylate oligomers include, for example, polyester-based aliphatic urethane diacrylate and tetraacrylate oligomers, polyether-based aliphatic urethane diacrylate and tetraacrylate oligomers, and polyester / polyether-based aliphatic urethane diacrylate and tetraacrylate oligomers.

[0570] Polyurethane (meth) acrylate oligomers can be prepared by reacting aliphatic, alicyclic and / or aromatic polyisocyanates (e.g., diisocyanates, triisocyanates) with OH-terminated polyester polyols, polyether polyols, polycarbonate polyols, polycaprolactone polyols, polyorganosiloxane polyols (e.g., polydimethylsiloxane polyols) or polydiene polyols (e.g., polybutadiene polyols) or combinations thereof to form isocyanate-functionalized oligomers, which are then reacted with hydroxyl-functionalized (meth) acrylates (e.g., 2-hydroxyethyl (meth) acrylate or 3-hydroxypropyl (meth) acrylate) to provide terminal (meth) acrylate groups. For example, the polyurethane (meth) acrylate oligomers can contain two, three, four or more (meth) acrylate functional groups per molecule. As is known in the art, other addition sequences can also be implemented to prepare polyurethane (meth) acrylates. For example, a hydroxyl-functionalized (meth)acrylate can first be 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 first be 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 produce a polyurethane (meth)acrylate. Alternatively, all components can be combined and reacted simultaneously.

[0571] Suitable acrylic (meth)acrylate oligomers (sometimes also referred to in the art as "acrylic oligomers") include oligomers that can be described as having an oligomeric acrylic backbone functionalized with one or more (meth)acrylate groups (which can be at the end of the oligomer or pendant to the acrylic backbone). The acrylic backbone can be a homopolymer, random copolymer, or block copolymer comprising repeating units of acrylic acid monomers. The acrylic monomers can be any monomeric (meth)acrylate, such as C1-C6 alkyl (meth)acrylates, as well as functionalized (meth)acrylates, such as (meth)acrylates bearing hydroxyl, carboxylic acid, and / or epoxy groups. Acrylic (meth)acrylate oligomers can be prepared using any procedure known in the art, for example, by functionalizing an oligomer, at least a portion of which is functionalized with hydroxyl, carboxylic acid, and / or epoxy groups (e.g., hydroxyalkyl (meth)acrylates, (meth)acrylic acid, glycidyl (meth)acrylate) to obtain a functionalized oligomer intermediate, which is then reacted with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functionality.

[0572] The curable composition of the present invention may comprise 0 to 99.5 wt %, in particular 5 to 90 wt %, more in particular 10 to 80 wt %, even more in particular 15 to 75 wt %, still more in particular 20 to 70 wt % of (meth)acrylate functional oligomer, based on the total weight of the curable composition. In particular, the curable composition of the present invention may comprise 5 wt % to 50 wt % or 10 wt % to 50 wt % or 15 wt % to 50 wt % or 20 wt % to 50 wt % or 25 wt % to 50 wt % or 30 wt % to 50 wt % of (meth)acrylate functional oligomer, based on the total weight of the curable composition. Alternatively, the curable composition of the present invention may comprise 50 wt % to 99.5 wt % or 55 wt % to 99.5 wt % or 60 wt % to 99.5 wt % or 65 wt % to 99.5 wt % or 70 wt % to 99.5 wt % of (meth)acrylate functional oligomer, based on the total weight of the curable composition.

[0573] The composition may comprise one or more ethylenically unsaturated compounds in addition to the (meth)acrylate functional monomer or oligomer. Examples of such ethylenically unsaturated compounds include:

[0574] - polyvinyl and / or polyallyl monomers (in particular divinylbenzene, 1,4-butanediol divinyl ether, triethylene glycol divinyl ether, diallyl ether, glycerol diallyl ether, glycerol triallyl ether, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, diallyl phthalate, triallyl isocyanurate, 2,4,6-triallyloxy-1,3,5-triazine, glyoxal bis(diallyl acetal) and mixtures thereof);

[0575] - vinyl esters of carboxylic acids (in particular vinyl acetate, vinyl propionate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl octanoate, vinyl nonanoate, vinyl laurate, vinyl stearate, vinyl esters of versatic acid and mixtures thereof);

[0576] - vinyl ethers (in particular vinyl methyl ether, vinyl ethyl ether, vinyl n-butyl ether, vinyl isobutyl ether and mixtures thereof, ethylene glycol divinyl ether, triethylene glycol divinyl ether and trimethylolpropane trivinyl ether);

[0577] - cycloaliphatic vinyl monomers (especially vinylcyclohexane);

[0578] - olefins (especially ethylene, propylene, 1-butene, isobutene, diisobutene, 1-nonene, 1-decene and mixtures thereof);

[0579] - conjugated dienes (especially butadiene, isoprene, pentadiene, chlorodienes and mixtures thereof);

[0580] - vinylaromatic monomers (in particular styrene, α-methylstyrene, tert-butylstyrene, o-, m- and p-methylstyrene, o-, m- and p-ethylstyrene, o-methyl-p-isopropylstyrene, p-chlorostyrene, p-bromostyrene, o- and p-dichlorostyrene, o- and p-dibromostyrene, o-, m- and p-methoxystyrene, optionally substituted indenes, optionally substituted vinylnaphthalenes, acenaphthene, diphenylethylene, vinylanthracene and mixtures thereof);

[0581] - monocarboxylic or dicarboxylic acid monomers, cyclic anhydride monomers and their salts (in particular 3-butenoic acid, crotonic acid, vinylacetic acid, fumaric acid, maleic acid, maleic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, itaconic acid, mesaconic acid, citraconic acid, glutaconic acid, muconic acid and mixtures thereof);

[0582] - unsaturated polymers such as polybutadiene;

[0583] - and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof

[0584] - and mixtures thereof.

[0585] Cationic polymerizable compounds

[0586] The curable composition of the present invention may further comprise a cationically polymerizable compound.The curable composition may comprise a mixture of cationically polymerizable compounds.

[0587] The term "cationically polymerizable compound" means a compound (other than an ethylenically unsaturated compound) that contains at least one polymerizable functional group (e.g., a heterocyclic group) that polymerizes via a cationic mechanism. In the cationic polymerization mechanism, a cationic initiator forms a Bronsted or Lewis acid species that combines with the cationically polymerizable compound, which then becomes reactive and causes chain growth by reaction with another cationically polymerizable compound.

[0588] The cationically polymerizable compound may be selected from the group consisting of epoxides, oxetanes, oxolanes, cyclic acetals, cyclic lactones, thiirane, thietane, spiroorthoesters, and mixtures thereof.

[0589] In a preferred embodiment, the cationically polymerizable compound may be selected from epoxides, oxetanes, and mixtures thereof.

[0590] Examples of suitable polyepoxides are those described above for P EPOX Examples of suitable alicyclic polyepoxides are listed above for PCycloEpox listed.

[0591] Examples of suitable oxetanes include trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-ethyl-3-phenoxymethyloxetane and bis(3-ethyl-3-methyloxy)butane, 3-ethyl-3-oxetanemethanol.

[0592] Examples of suitable oxolanes include tetrahydrofuran and 2,3-dimethyltetrahydrofuran.

[0593] Examples of suitable cyclic acetals include trioxane, 1,3-dioxolane, and 1,3,6-trioxanecyclooctane.

[0594] Examples of suitable cyclic lactones include β-propiolactone and ε-caprolactone.

[0595] Examples of suitable thiirane include ethylene sulfide, 1,2-epithelial and thiochlorohydrin.

[0596] Examples of suitable thioethanes capable of cationically polymerizing include trimethylene sulfide, 2-propylthiethane, and 3,3-dimethylthiethane.

[0597] Examples of suitable spiroorthoesters capable of cationic polymerization are compounds obtained by reaction of epoxides and lactones.

[0598] When the composition of the present invention comprises a cationically polymerizable compound, it may further comprise a polyol. Suitable polyols are as described above for P OH listed.

[0599] The curable composition of the present invention may comprise 10 to 80 wt %, specifically 15 to 75 wt %, more specifically 20 to 70 wt % of the cationically polymerizable compound, based on the total weight of the curable composition.

[0600] Polyols and thiols

[0601] When the composition of the present invention comprises a cationically polymerizable compound, it may further comprise a polyol and / or a polythiol. Suitable polyols and polythiols are as described above for P OH and P SH listed.

[0602] Polyols can be particularly useful when the compositions of the present invention comprise cationically polymerizable compounds.

[0603] Polythiols may be particularly useful when the compositions of the present invention comprise ethylenically unsaturated compounds other than (meth)acrylate functional monomers or oligomers, particularly polyvinyl and / or polyallyl monomers.

[0604] The amount of polyol and polythiol in the curable composition will vary depending on the type of compound used. However, typically, the curable composition is formulated to contain 0 to 10 weight %, 0.5 to 8 weight %, 1 to 5 weight % or 1.5 to 4 weight % polyol and / or polythiol, based on the weight of the curable composition.

[0605] additive

[0606] The curable composition of the present invention may further comprise additives.The curable composition may comprise a mixture of additives.

[0607] In particular, the additives may be chosen from sensitizers, amine synergists, stabilizers, antioxidants, light barriers, polymerization inhibitors, foam inhibitors, flow or leveling agents, colorants, pigments, dispersants (wetting agents, surfactants), slip additives, fillers, thixotropic agents, matting agents, impact modifiers, waxes and mixtures thereof; and any other additives conventionally used in the field of coatings, sealants, adhesives, molding, 3D printing or inks.

[0608] According to some embodiments, the curable composition may include a stabilizer.

[0609] Stabilizer can be introduced into curable composition of the present invention to provide enough storage stability and shelf life. In addition, stabilizer can be used during the preparation of curable composition, to prevent undesirable reaction from occurring in the processing of the ethylenically unsaturated components of curable composition. Stabilizer can be a compound or material that delays or prevents the reaction or solidification of the photopolymerizable functional groups present in the composition in the absence of actinic radiation. However, it is advantageous to select the amount and type of stabilizer so that the composition keeps being able to solidify (that is, stabilizer does not prevent the radiation-curing of composition) when exposed to actinic radiation. Stabilizer can particularly be a free radical stabilizer (i.e., a stabilizer that works by suppressing free radical reaction).

[0610] Any stabilizer associated with (meth)acrylate functionalized compounds known in the art can be used in the present invention. Quinones represent a particularly preferred type of stabilizer that can be used in the context of the present invention. As used herein, the term "quinone" includes quinone and hydroquinone and their ethers, such as monoalkyl ethers, monoaryl ethers, monoarylalkyl ethers and bis(hydroxyalkyl) ethers of hydroquinone. Hydroquinone monomethyl ether is an example of a suitable stabilizer that can be used. Other stabilizers known in the art are hydroquinone (HQ), 4-tert-butylcatechol (TBC), 3,5-di-tert-butyl-4-hydroxytoluene (BHT), phenothiazine (PTZ), pyrogallol, phosphite compounds, triphenyl antimony and tin (II) salts.

[0611] In the curable composition, the concentration of the stabilizer will vary according to the specific stabilizer selected for use or the combination of stabilizer and the required stability and the sensitivity of the component to degradation in the absence of stabilizer. However, conventionally the curable composition is mixed with a stabilizer comprising 5 to 5000ppm. According to some embodiments of the present invention, during each stage of the method for the preparation of the curable composition, the reaction mixture contains at least some stabilizers, for example at least 10ppm stabilizer.

[0612] The curable composition may contain a colorant. The colorant may be a dye, a pigment, and mixtures thereof. As used herein, the term "dye" refers to a colorant having a solubility of 10 mg / L or greater in the medium into which the colorant is introduced at 25°C. The term "pigment" is defined in DIN 55943 as a colorant that is practically insoluble in the application medium under relevant ambient conditions and therefore has a solubility therein of less than 10 mg / L at 25°C. The term "CI" is used as an abbreviation for color index.

[0613] The colorant can be a pigment. Organic and / or inorganic pigments can be used. If the colorant is not a self-dispersing pigment, the inkjet ink preferably also contains a dispersant, more preferably a polymeric dispersant. The pigment can be black, cyan, magenta, yellow, red, orange, violet, blue, green, brown, and mixtures thereof. The pigment can be selected from those disclosed in HERBST, Willy et al., 3rd edition, Wiley-VCH, 2004. ISBN 3527305769.

[0614] Specific pigments include:

[0615] - carbon black;

[0616] - CI Pigment White 1, 3, 4, 5, 6, 7, 10, 11, 12, 14, 17, 18, 19, 21, 24, 25, 27, 28 and 32;

[0617] - CI Pigment Yellow 1, 3, 10, 12, 13, 14, 17, 55, 65, 73, 74, 75, 83, 93, 97, 109, 111, 120, 128, 138, 139, 150, 151, 154, 155, 180, 185 and 213;

[0618] - CI Pigment Red 17, 22, 23, 41, 48:1, 48:2, 49:1, 49:2, 52:1, 57:1, 81:1, 81:3, 88, 112, 122, 144, 146, 149, 169, 170, 175, 176, 184, 185, 188, 202, 206, 207, 210, 216, 221, 248, 251, 254, 255, 264, 270 and 272;

[0619] - CI Pigment Violet 1, 2, 19, 23, 32, 37 and 3;

[0620] - CI Pigment Blue 15:1, 15:2, 15:3, 15:4, 15:6, 16, 56, 61 and (bridged) aluminum phthalocyanine pigments;

[0621] - CI Pigment Orange 5, 13, 16, 34, 40, 43, 59, 66, 67, 69, 71 and 73;

[0622] -CI Pigment Green 7 and 36;

[0623] -CI Pigment Brown 6 and 7;

[0624] and mixtures thereof.

[0625] The curable composition of the present invention may include a dispersant. A dispersant can be used to disperse insoluble materials such as pigments or fillers in the curable composition.

[0626] The dispersant may be a polymeric dispersant, a surfactant, or a mixture thereof.

[0627] Typical polymeric dispersants are copolymers of two, three, four, five or even more monomers. The properties of polymeric dispersants depend on the properties of the monomers and their distribution in the polymer. Copolymeric dispersants preferably have the following polymer composition:

[0628] - random copolymers (e.g. ABBAABAB);

[0629] - alternating copolymers (e.g. ABABABAB);

[0630] - gradient copolymers (e.g. AAABAABBABBB);

[0631] - block copolymers (e.g. AAAAABBBBBB);

[0632] - Graft copolymers (polymeric main chain with polymeric side chains attached to the main chain

[0633] chain);

[0634] and mixed forms of these copolymers.

[0635] The polymeric dispersant may have a number average molecular weight Mn of 500 to 30,000 g / mol, more preferably 1,500 to 10,000 g / mol.

[0636] Commercial examples of polymeric dispersants include:

[0637] - Dispersants available from BYK CHEMIE GMBH;

[0638] - Dispersants, available from LUBRIZOL;

[0639] -From EVONIK Dispersant;

[0640] - from BASF and dispersants;

[0641] -From ELEMENTIS Dispersant.

[0642] solvent

[0643] The curable compositions of the present invention may contain a solvent. As used herein, the term "solvent" means a non-reactive organic solvent, ie, a solvent containing carbon and hydrogen atoms that does not react when exposed to actinic radiation used to cure the curable compositions described herein.

[0644] Advantageously, the curable compositions of the present invention can be formulated to be solvent-free. For example, the curable compositions of the present invention can contain little or no solvent, such as less than 10 wt %, or less than 5 wt %, or less than 1 wt %, or even 0 wt % solvent, based on the total weight of the curable composition.

[0645] According to some embodiments, the curable composition is liquid at 25° C. In various embodiments of the present invention, the curable composition described herein is 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 even less than 100 mPa.s, as measured at 25° C. using a Brookfield viscometer, Model DV-II, using a No. 27 spindle (wherein the spindle speed typically varies between 20 rpm and 200 rpm, depending on the viscosity). In advantageous embodiments of the present invention, the viscosity of the curable composition at 25° C. 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.

[0646] preparation

[0647] The curable compositions described herein can be compositions to be cured by free radical polymerization. In certain embodiments, the curable compositions can be photocured (i.e., cured by exposure to actinic radiation, particularly UV, near UV, visible, infrared, and / or near infrared radiation).

[0648] The curable composition of the present invention may be an ink composition, a coating composition, an adhesive composition, a sealant composition, a molding composition, a dental composition, a nail polish composition, or a 3D printing composition.

[0649] End-use applications of the curable compositions include, but are not limited to, inks, coatings, adhesives, additive manufacturing resins (e.g., 3D printing resins), molding resins, sealants, composite materials, antistatic layers, electronic applications, recyclable materials, smart materials capable of detecting and responding to stimuli, packaging materials, personal care products, nail polishes, products for agriculture, water or food processing, or animal husbandry, and biomedical materials. Thus, applications of the curable compositions of the present invention are found in the production of biocompatible articles. Such articles can, for example, exhibit high biocompatibility, low cytotoxicity, and / or low extractables.

[0650] The composition according to the invention can be used in particular to obtain a cured product according to the following method.

[0651] Method for preparing cured product

[0652] The method for preparing a cured product according to the present invention comprises curing the curable composition of the present invention. In particular, the curable composition can be cured by exposing the composition to radiation. More particularly, the curable composition can be cured by exposing the composition to UV, near UV, visible, infrared and / or near infrared radiation. The curable composition can advantageously be cured by exposing the composition to an LED light source.

[0653] Curing can be accelerated or promoted by supplying energy to the curable composition, for example, by heating the curable composition. Thus, a cured product can be considered a reaction product formed by curing the curable composition. The curable composition can be partially cured by exposure to actinic radiation, wherein further curing is achieved by heating the partially cured article. For example, a product formed from the curable composition can be heated at a temperature of 40°C to 120°C for a period of 5 minutes to 12 hours.

[0654] Prior to curing, the curable composition can be applied to the substrate surface in any known conventional manner, such as by spraying, spraying, knife coating, roller coating, casting (casting), drum coating, dipping, etc. and combinations thereof. Indirect application using a transfer process can also be used.

[0655] The base material that applies and solidifies curable composition can be the base material of any kind.Suitable base material is described in detail below.When being used as adhesive, curable composition can be placed between two base materials, solidifies then, thereby the composition of solidification combines base material together to provide the goods of adhesion.Curable composition according to the present invention can also form or solidify (for example, curable composition can be cast in suitable mould, solidifies then) in body mode.

[0656] The substrate can be a ceramic, metal, mineral, cellulose, animal-based or polymeric substrate. The substrate can also be a part of the human body, such as a tooth or nail.

[0657] The substrate may be porous or substantially non-porous.The substrate may be transparent, translucent or opaque.

[0658] Examples of the ceramic substrate include alumina-based ceramics and zirconia-based ceramics.

[0659] Examples of metal substrates include titanium, gold, silver, copper, brass, steel, and bronze.

[0660] Examples of mineral substrates include glass, asbestos, and basalt.

[0661] Examples of cellulosic substrates include plain paper or resin-coated paper (e.g., polyethylene or polypropylene coated paper). There is no practical limitation on the type of paper and it includes newsprint, magazine paper, office paper, wallpaper, but also includes heavier weight papers, commonly known as paperboard, such as white lined cardboard, corrugated board, and packaging board. Other examples of cellulosic substrates include bamboo, cotton, flax, hemp, jute, lyocell, modal, rayon, raffia, ramie, and sisal.

[0662] Examples of cellulosic substrates include wool, fur, silk, and leather.

[0663] Examples of polymeric substrates include polyethylene, polypropylene, polycarbonate, polyvinyl chloride, polyethylene terephthalate, polyethylene naphthalate, polylactide, polyamide, polyimide, polyacrylonitrile, polyurethane, acrylonitrile butadiene styrene.

[0664] There is no limitation on the shape of the substrate. It can be a sheet, a film, a nonwoven or woven fiber mat or a three-dimensional object.

[0665] 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.

[0666] The cured product obtained by the method of the present invention may be an ink, a coating (paint), an adhesive, a sealant, a molded article, a dental material, a nail polish or a 3D-printed article.

[0667] 3D printing methods

[0668] In particular, a 3D printed article can be obtained using a 3D printing method comprising printing a 3D article using the composition of the present invention. In particular, the method can include printing the 3D article layer by layer or continuously.

[0669] Three-dimensional (3D) printing (also known as additive manufacturing) is a method of fabricating 3D digital models through the accumulation of build materials. 3D printed objects are created by sequentially constructing two-dimensional (2D) layers or slices corresponding to cross-sections of the 3D object using computer-aided design (CAD) data of the object. The radiation can be in the form of electromagnetic waves or electron beams. The most commonly used energy sources are UV, near-UV, visible, infrared, and / or near-infrared radiation.

[0670] Multiple layers of the curable composition according to the present invention may be applied to a substrate surface; multiple layers may be cured simultaneously (e.g., by exposure to a single dose of radiation), or each layer may be cured sequentially before additional layers of curable composition are applied.

[0671] Non-limiting examples of suitable 3D printing methods include stereolithography (SLA); digital light processing (DLP); liquid crystal device (LCD); inkjet (or multi-jet) printing; continuous liquid interface production (CLIP); extrusion-based processes such as continuous fiber 3D printing and motion casting 3D printing; and volumetric 3D printing. The build method can be "layer-by-layer" or continuous. The liquid can be deposited in a vat or, for example, using inkjet or gel deposition.

[0672] Stereolithography and other photocurable 3D printing methods typically use a low-intensity light source to irradiate each layer of a photocurable resin to form the desired article. Therefore, if a particular photocurable resin will fully polymerize (cure) upon irradiation and have sufficient green strength to maintain its integrity throughout the 3D printing process and post-processing, the photocurable resin polymerization kinetics and the green strength of the printed article are important criteria.

[0673] Curable composition of the present invention can be used as 3D printing resin formulation, i.e., is intended to be used for the composition of three-dimensional products using 3D printing technology. Such three-dimensional products can be free-standing / self-supporting, and can be basically composed of or composed of the composition according to the present invention having solidified. Three-dimensional products can also be composite materials, which comprise at least one component basically composed of or composed of the component and comprising at least one other component (for example, metal component or thermoplastic component or inorganic filler or fiber-reinforced material) composed of the material except this curing composition. Curable composition of the present invention is particularly useful for digital light printing (DLP), although it is also possible to use the curable composition of the present invention to implement other types of three-dimensional (3D) printing methods (for example, SLA, inkjet, multi-jet printing, piezoelectric printing, photochemical curing extrusion and gel deposition printing). Curable composition of the present invention can be used for three-dimensional printing operation together with other material, and the other material is used as the support or the support member of the product formed by the curable composition of the present invention.

[0674] Thus, the curable compositions of the present invention can be used to practice various types of three-dimensional manufacturing or printing techniques, including methods in which the construction of a three-dimensional object is carried out in a step-by-step or layer-by-layer manner. In such methods, layer formation can be carried out by solidifying (curing) the curable composition under exposure to radiation (e.g., visible, UV or other actinic radiation). For example, a new layer can be formed at the top surface of a growing object or at the bottom surface of a growing object. The curable compositions of the present invention can also be advantageously used in methods for producing three-dimensional objects by additive manufacturing, wherein the method is carried out continuously. For example, an object can be produced by a liquid interface. 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).

[0675] The curable composition can be supplied by ejecting it from the print head instead of supplying it from a barrel. This type of method is generally referred to as inkjet or multi-jet 3D printing. One or more UV curing sources mounted just behind the inkjet print head cure the curable composition immediately after the curable composition is applied to the build surface substrate or a previously applied layer. Two or more print heads can be used in this method, which allow different compositions to be applied 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 different compositions. In typical use, support material (which is later removed during post-processing) is deposited simultaneously with the composition for producing the desired 3D printed part. The print head can operate at a temperature of about 25°C to a maximum of about 100°C. The viscosity of the curable composition is less than 30mPa.s at the operating temperature of the print head.

[0676] The method for preparing a 3D printed article may include the following steps:

[0677] a) providing (e.g. applying) a first layer of a curable composition according to the present invention onto a surface;

[0678] b) at least partially curing the first layer to provide a cured first layer;

[0679] c) providing (e.g., coating) a second layer of the curable composition onto the cured first layer;

[0680] d) at least partially curing the second layer to provide a cured second layer adhered to the cured first layer; and

[0681] e) Repeating steps c) and d) a desired number of times to build a three-dimensional article.

[0682] Alternatively, the method for preparing a 3D printed article may include the following steps:

[0683] a) providing a carrier and an optically transparent member having a building surface, said carrier and said building surface defining a building area therebetween;

[0684] b) filling the build area with a composition as defined above;

[0685] c) continuously or intermittently curing a portion of the composition in the build area according to the method defined above to form a cured composition; and

[0686] d) continuously or intermittently advancing the carrier away from a build surface to form the 3D printed article from the cured composition.

[0687] After printing a 3D article, it can be subjected to one or more post-processing steps. Post-processing steps can be selected from one or more of the following: removal of any printed support structures, washing with water and / or an organic solvent to remove residual resin, and post-curing using heat treatment and / or actinic radiation, either simultaneously or sequentially. Post-processing steps can be used to transform the freshly printed article into a finished, functional article ready for its intended application.

[0688] Inkjet printing method

[0689] The inkjet printing method according to the present invention comprises jetting the curable composition of the present invention onto a substrate.

[0690] The substrate onto which the curable composition is sprayed may be any kind of substrate. Suitable substrates are as detailed above.

[0691] The curable composition may be jetted by one or more print heads, ejecting small droplets through nozzles in a controlled manner onto a substrate that is moving relative to the print heads.

[0692] The print head can be a piezoelectric head or a continuous type print head.

[0693] The inkjet printing process can be performed in single-pass or multi-pass printing mode.

[0694] The inkjet printing method may further comprise a UV curing step. In inkjet printing, a UV curing device may be arranged in combination with the print head of the inkjet printer, travelling therewith, so that the liquid UV curable inkjet ink is exposed to curing radiation very shortly after being ejected.

[0695] In a particularly preferred embodiment, the UV curing step is performed using a UV LED light source.

[0696] To facilitate curing, the inkjet printer may include one or more oxygen depletion cells that place a blanket of nitrogen or other relatively inert gas (e.g., CO2) at an adjustable position and adjustable inert gas concentration to reduce the oxygen concentration in the curing environment.

[0697] How to paint your nails

[0698] The method of coating nails according to the present invention comprises applying the curable composition of the present invention to the nails, and curing the composition on the nails.

[0699] use

[0700] The compounds of formula (1) or (2) according to the invention or the photoinitiator compositions according to the invention can be used as photoinitiators or photoinitiating systems in radiation-curable compositions, in particular in UV- or LED-curable compositions.

[0701] As used herein, "UV-curable composition" means a composition that is cured by exposure to UV light emitted by a mercury light source, particularly a mercury vapor lamp, and "LED-curable composition" means a composition that is 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 nm to 420 nm.

[0702] The compounds of formula (1) or (2) according to the invention or the photoinitiator compositions according to the invention can be used for photopolymerization reactions. The photopolymerization reactions can be used for curing one or more ethylenically unsaturated compounds as defined above.

[0703] The compound of formula (1) or (2) of the present invention or the photoinitiator composition of the present invention can be used to obtain a cured product with a reduced amount of extractables. In particular, the cured product can be an ink, an overprint varnish, a coating (paint), an adhesive, a sealant, a molded article, a dental material, a nail polish, or a 3D-printed article.

[0704] The reduction in the amount of extractables can be evaluated by comparison with cured products obtained with conventional photoinitiators.

[0705] Extractables may be any component that migrates from the cured product. In particular, the extractables may be a photoinitiator or its residues.

[0706] Migration in inkjet inks can occur in different ways:

[0707] - Penetrant migration - through the substrate to the reverse side of the print;

[0708] - Set-off Migration - from the printed side of the substrate to the opposite side of the substrate when stacked or stored on a roll;

[0709] - Vapor phase migration - evaporation of volatile compounds when heated;

[0710] -Condensation extraction - condensation of key compounds during cooking or sterilization.

[0711] The amount of extractables can be quantitatively determined using a suitable analytical method such as liquid chromatography mass spectrometry (LC-MS). For example, the curable composition can be applied to a glass substrate as a 12 μm thick film and cross-linked 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 extractable portion is weighed, thereby allowing the amount of uncured (not trapped in the photocurable network) product to be determined.

[0712] 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 refine their respective contents.

[0713] In particular, the cured product can have less than 5 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.25 wt%, or less than 0.1 wt% extractables based on the weight of the cured product.

[0714] The curable composition of the present invention can be used to obtain inks, overprint varnishes, coatings, adhesives, sealants, molded articles, dental materials or 3D-printed articles, in particular inks.

[0715] In this specification, embodiments have been described in a manner that enables a clear and concise description to be written, but it is intended and will be understood that the embodiments can be combined or separated in various ways without departing from the present invention. For example, it should be understood that all preferred features described herein apply to all aspects of the invention described herein.

[0716] While the invention is illustrated and described herein with reference to particular embodiments, the invention is not intended to be limited to the details shown. Rather, various modifications may be made to the details within the scope and range of equivalents of the claims and without departing from the invention.

[0717] Example

[0718] The following examples illustrate the present invention without limiting it.

[0719] Example 1: Synthesis of Precursor 1

[0720]

[0721] 2,4,6-trimethylbenzoyldiphenylphosphine oxide (from Arkema) was added within 1 hour. To an ice-cold solution of TPO (85.0 g, 244 mmol) and maleic anhydride (28.7 g, 293 mmol) in dichloromethane (850 mL) was added aluminum chloride (129 g, 968 mmol) in portions while maintaining the reaction temperature at 5-10° C. The resulting deep red solution was heated at 30-32° C. for 48 h. The mixture was cooled to 20° C. and then poured into ice water (about 1 L) under stirring. The dichloromethane was removed from the two-phase mixture by concentrating under reduced pressure, and the resulting aqueous slurry was filtered to obtain a crude solid product. The product was repeatedly washed with water, then suspended in toluene (500 mL) and filtered. The obtained solid was thoroughly dried in a vacuum oven at 60° C. to give precursor 1 as a light yellow powder (97 g, 89%).

[0722] Example 2: Synthesis of Precursor 2

[0723]

[0724] To an ice-cold solution of Precursor 1 (10.0 g, 22.4 mmol) and triethylamine (9.4 mL, 67.2 mmol) in toluene (150 mL) was added trimethylacetyl chloride (3.0 mL, 24.6 mmol) over 20 minutes and the resulting mixture was stirred at 5-10° C. for 30 minutes. Methanol (9.1 mL, 224 mmol) was added in one portion and the solution was stirred for an additional 30 minutes. The volatiles were removed under reduced pressure and the residue was dissolved in ethyl acetate (100 mL). The organic solution was washed with 1M HCl (3×75 mL), saturated NaHCO 3 solution (3×75 mL) and brine (75 mL), then dried (MgSO 4 ), filtered and concentrated under reduced pressure to give Precursor 2 as a light yellow solid (8.50 g, 82%).

[0725] Example 3: Synthesis of Photoinitiator 1

[0726]

[0727] To a stirred solution of precursor 2 (4.0 g, 8.69 mmol) in methanol (45 mL) was added morpholine (1.5 mL, 17.4 mmol), and the resulting solution was stirred for 30 minutes at 20° C. The volatiles were removed under reduced pressure, and the resulting residue was redissolved in ethyl acetate (40 mL) and washed with deionized water (3×30 mL) and brine (40 mL), then the organic phase was dried (MgSO 4 ), filtered, and concentrated under reduced pressure to afford photoinitiator 1 as a light orange solid (3.48 g, 73%).

[0728] Example 4: Synthesis of Photoinitiator 2

[0729]

[0730] To a stirred solution of precursor 2 (4.45 g, 9.66 mmol) in methanol (50 mL) was added 1-methylpiperazine (2.2 ml, 19.3 mmol), and the resulting solution was stirred for 30 minutes at 20° C. The volatiles were removed under reduced pressure and the resulting residue was redissolved in ethyl acetate (40 mL) and washed with deionized water (3×30 mL) and brine (40 mL), then the organic phase was dried (MgSO 4 ), filtered, and concentrated under reduced pressure to give photoinitiator 2 as an orange solid (3.20 g, 59%, single isomer).

[0731] Example 5: Synthesis of Precursor 3

[0732]

[0733] To an ice-cold solution of Precursor 1 (14.0 g, 31.4 mmol) and triethylamine (13.1 mL, 94.1 mmol) in toluene (250 mL) was added trimethylacetyl chloride (4.2 mL, 34.5 mmol) over 20 minutes and the resulting mixture was stirred at 5-10°C for 30 minutes. n-Butylamine (3.4 mL, 34.5 mmol) was added in one portion and the solution was stirred for an additional 30 minutes. The volatiles were removed under reduced pressure and the residue was dissolved in ethyl acetate (150 mL). The organic solution was washed with 1 M HCl (3 x 100 mL), saturated NaHCO3 solution (3 x 100 mL) and brine (120 mL), then dried (MgSO4), filtered and concentrated under reduced pressure to give Precursor 3 as a colorless solid (15.1 g, 96%).

[0734] Example 6: Synthesis of Photoinitiator 3

[0735]

[0736] To a stirred solution of precursor 3 (4.0 g, 7.98 mmol) in methanol (60 mL) was added morpholine (1.4 ml, 16.0 mmol), and the resulting solution was stirred at 20° C. for 30 minutes. The volatiles were removed under reduced pressure and the resulting residue was redissolved in ethyl acetate (40 mL) and washed with deionized water (3×30 mL) and brine (40 mL). The organic phase was then dried (MgSO 4 ), filtered, and concentrated under reduced pressure to afford photoinitiator 3 as an off-white solid (3.55 g, 76%, single isomer).

[0737] Example 7: Synthesis of Photoinitiator 4

[0738]

[0739] To a stirred solution of precursor 3 (4.50 g, 8.97 mmol) in methanol (60 mL) was added N-methylpiperazine (2.0 mL, 17.9 mmol), and the resulting solution was stirred at 20° C. for 30 minutes. The volatiles were removed under reduced pressure and the resulting residue was redissolved in ethyl acetate (40 mL) and washed with deionized water (3×30 mL) and brine (40 mL). The organic phase was then dried (MgSO 4 ), filtered, and concentrated under reduced pressure to afford photoinitiator 4 as a glassy solid (3.70 g, 69%, single isomer).

[0740] Example 8: Synthesis of Photoinitiator 5

[0741]

[0742] To an ice-cold suspension of precursor 1 (10.0 g, 22.4 mmol) and triethylamine (12.0 mL, 86.1 mmol) in toluene (100 mL) was added trimethylacetyl chloride (3.0 mL, 24.5 mmol) at 0-5° C., and the resulting solution was stirred at 0-5° C. for 30 minutes. Methanol (60 mL) was added, and the mixture was stirred at 30-35° C. for 1 hour. The mixture was cooled to 20° C., then ethylenediamine (1.80 g, 28.0 mmol) was added, and the solution was stirred at 20° C. for 16 hours. The methanol was removed by concentration under reduced pressure, and the resulting residue was dissolved in ethyl acetate (100 mL), and the organic solution was washed with water (100 mL), 10 wt% aqueous sodium carbonate solution (100 mL) and brine (50 mL), then dried (MgSO4), filtered and concentrated under reduced pressure to give the crude product, which was washed with cold tert-butyl methyl ether to give pure photoinitiator 5 as a light yellow solid (10.0 g, 91%).

[0743] Example 9: Synthesis of Precursor 4

[0744]

[0745] To a stirred ice-cold suspension of precursor 1 (105 g, 235 mmol) and triethylamine (120 mL, 861 mmol) in toluene (1.2 L) was added trimethylacetyl chloride (28.8 mL, 235 mmol) at 5-10° C. over 10 minutes and the resulting suspension was stirred at 5-10° C. for 35 minutes. A trifunctional primary amine having repeating oxypropylene units and an average molecular weight of 440 g / mol (from Hunstman) was added at 5-10° C.

[0148] T403-34.2 g, 77.7 mmol) was added and the mixture was warmed to 20°C and then stirred for an additional 16 h. Water (1 L) was added and the layers were separated. The organic phase was washed with 2M hydrochloric acid (500 mL), 10% w / w aqueous sodium carbonate solution (250 mL), and brine (200 mL), then dried (MgSO4), filtered, and concentrated under reduced pressure to afford Precursor 4 as a light cream solid (124 g, 92%).

[0746] Example 10: Synthesis of Photoinitiator 6

[0747]

[0748] To a solution of precursor 4 (5.30 g, 3.08 mmol) in methanol (60 mL) was added morpholine (5.0 mL, 57.4 mmol), and the resulting solution was stirred for 4 h at 20° C. The mixture was concentrated under reduced pressure to remove methanol, and the resulting residue was redissolved in ethyl acetate (100 mL), and the organic solution was washed with water (2×100 mL) and brine (50 mL), then dried (MgSO 4 ), filtered, and concentrated under reduced pressure to afford photoinitiator 6 as a colorless solid (5.6 g, 92%).

[0749] Example 11: Synthesis of Photoinitiator 7

[0750]

[0751] To a solution of precursor 2 (1.00 g, 2.17 mmol) and diethyl malonate (0.42 g, 2.60 mmol) in N,N-dimethylformamide (10 mL) was added potassium carbonate (1.00 g, 7.24 mmol) and the resulting suspension was heated at 60° C. for 1 h. The mixture was allowed to cool to 20° C. before ethyl acetate (100 mL) and water (50 mL) were added, followed by 1 M hydrochloric acid (20 mL), and the biphasic mixture was vigorously shaken and separated. The organic phase was washed with saturated sodium bicarbonate solution (50 mL) and brine (50 mL), then dried (MgSO 4 ), filtered, and concentrated under reduced pressure to give the crude product. Column chromatography (eluting with 1:1 petrol-ethyl acetate) gave pure photoinitiator 7 as a light yellow liquid (1.20 g, 89%).

[0752] Example 12: Synthesis of Precursor 5

[0753]

[0754] To a suspension of Precursor 1 (15.0 g, 33.6 mmol) and poly(tetrahydrofuran) having a number average molecular weight of 250 g / mol (4.20 g, 16.8 mmol) in toluene (90 mL) was added methanesulfonic acid (1.5 mL, 23.1 mmol) and the resulting mixture was heated at reflux temperature for 8 h while continuously removing water using a Dean-Stark apparatus. The mixture was allowed to cool to 20° C., then 5 wt % aqueous sodium carbonate solution (100 mL) was added and the layers were separated. The organic phase was washed with brine (50 mL), dried (MgSO ), filtered and concentrated under reduced pressure to give Precursor 5 as a yellow glassy solid (17.2 g, 92%).

[0755] Example 13: Synthesis of Photoinitiator 8

[0756]

[0757] To a solution of precursor 5 (3.00 g, 2.71 mmol) and diethyl malonate (0.92 g, 5.69 mmol) in 2-butanone (40 mL) was added potassium carbonate (1.87 g, 13.5 mmol) and the resulting suspension was heated to 85° C. for 3 h. The mixture was cooled to 40° C. and the solvent was removed by distillation under reduced pressure. Toluene (30 mL) was added to the residue and 1 M hydrochloric acid (50 mL) was slowly added as gas evolved. More toluene (50 mL) was added and the layers separated. The organic layer was washed with water (50 mL) and brine (20 mL), then dried (MgSO ), filtered and concentrated under reduced pressure to give photoinitiator 8 as a light yellow glassy solid (3.5 g, 91%).

[0758] Example 14: Synthesis of Photoinitiator 9

[0759]

[0760] To a solution of precursor 5 (14.8 g, 13.4 mmol) and dimethyl malonate (3.71 g, 28.1 mmol) in 2-butanone (85 mL) was added potassium carbonate (6.47 g, 46.8 mmol) and the resulting suspension was heated to 85° C. for 3 h. The mixture was cooled to 40° C. and the solvent was removed by distillation under reduced pressure. Toluene (50 mL) was added to the residue and 1 M hydrochloric acid (100 mL) was slowly added as gas evolved. More toluene (80 mL) was added and the layers separated. The organic layer was washed with water (50 mL) and brine (30 mL), then dried (MgSO ), filtered and concentrated under reduced pressure to give photoinitiator 9 as a light yellow glassy solid (17.2 g, 94%).

[0761] Example 15: Synthesis of Precursor 6

[0762]

[0763] To a suspension of Precursor 1 (15.0 g, 33.6 mmol) and poly(tetrahydrofuran) having a number average molecular weight of 650 g / mol (410.9 g, 16.8 mmol) in toluene (90 mL) was added methanesulfonic acid (1.5 mL, 23.1 mmol), and the resulting mixture was heated at reflux temperature for 8 h while continuously removing water using a Dean-Stark apparatus. The mixture was allowed to cool to 20° C., then 5 wt % aqueous sodium carbonate solution (100 mL) was added and the layers were separated. The organic phase was washed with brine (50 mL), dried (MgSO ), filtered, and concentrated under reduced pressure to afford Precursor 5 as a yellow liquid (22.0 g, 87%).

[0764] Example 16: Synthesis of Photoinitiator 10

[0765]

[0766] To a solution of precursor 6 (17.5 g, 11.6 mmol) and dimethyl malonate (3.22 g, 24.4 mmol) in 2-butanone (100 mL) was added potassium carbonate (5.61 g, 40.6 mmol) and the resulting suspension was heated to 85°C for 3 h. The mixture was cooled to 40°C and the solvent was removed by distillation under reduced pressure. Toluene (60 mL) was added to the residue and 1 M hydrochloric acid (150 mL) was slowly added as gas evolved. More toluene (140 mL) was added and the layers were separated. The organic layer was washed with water (30 mL) and brine (50 mL), then dried (MgSO4), filtered and concentrated under reduced pressure to give photoinitiator 10 as a light yellow liquid (19.5 g, 95%).

[0767] Example 17: Synthesis of Precursor 7

[0768]

[0769] Precursor 1 (240 g, 538 mmol) and 1,3-polypropylene glycol (from WeylChem) with a number average molecular weight of 200-300 g / mol were added. To a suspension of 1,2-dimethyl-2-oxo-1,2-dihydro ...

[0770] Example 18: Synthesis of Photoinitiator 11

[0771]

[0772] To a solution of precursor 7 (186 g, 168 mmol) in toluene (1 L) was added dimethyl malonate (46.4 g, 352 mmol) and potassium carbonate (81.0 g, 586 mmol), and the resulting suspension was heated at 90° C. for 2.5 h. The mixture was cooled to 20° C., then 2 M hydrochloric acid (1 L) was slowly added while evolving carbon dioxide. When gas evolution ceased, the layers were thoroughly mixed and separated, and the organic phase was then washed with water (400 mL) and brine (250 mL). The organic phase was then dried (MgSO ), filtered, and concentrated under reduced pressure to afford photoinitiator 11 as a glassy, light yellow solid (223 g, 97%).

[0773] Example 19: Curing Experiment

[0774] The following examples illustrate that the photoinitiators disclosed herein have high cure speeds compared to previously disclosed photoinitiators.

[0775] Testing protocol: Formulations were prepared by combining all materials in the given proportions and then stirring at 30-40°C until the sample was completely homogeneous; the formulations were then allowed to cool to 20°C. All components remained completely dissolved in the resin formulation throughout these experiments. For all experiments, the formulations were cured at a film thickness of 50 μm on Leneta Form 3N-31 glossy topcoat paper using a belt curing apparatus; films were prepared using a K-bar. All films were then cured under a 395 nm LED lamp at a belt speed of 10 m / min. The cure speed for each formulation was calculated from the number of passes under each lamp and the belt speed required to achieve a complete surface cure (determined when a light scratch on the film surface no longer leaves a mark) and a deep cure (determined using a "thumb twist" test, where a thumb is pressed firmly down on the coating with a twisting motion and no visible mark is produced). The calculated cure speed (in m / min) is given in Tables 1A-1B as the average of three runs. Results were recorded as "uncured" when the cure speed was less than 0.3 m / min.

[0776] Table 1A: Curing of Phosphine Oxide in Formulations of Equal Weight %

[0777] Formulations containing 8% w / w of each phosphine oxide photoinitiator in a 7:3 w / w mixture of bisphenol A ethoxylate diacrylate and tripropylene glycol diacrylate were prepared.

[0778]

[0779] These results demonstrate that the phosphine oxides disclosed herein are effective photoinitiators for deep curing of acrylate resin films under LED lighting conditions. While they are slightly slower than the commercially available photoinitiator SpeedCure TPO, this is to be expected given their higher molecular weight and lower active content at this concentration. Furthermore, the photoinitiators disclosed herein promote faster curing than the previously disclosed photoinitiators, Photoinitiator B and Photoinitiator C.

[0780] Table 1B: Curing of phosphine oxide at the same active concentration

[0781] Formulations were prepared containing a given weight percent of phosphine oxide photoinitiator in a 7:3 w / w mixture of bisphenol A ethoxylate diacrylate and tripropylene glycol diacrylate. The amount of phosphine oxide was chosen to ensure the same approximate concentration of active phosphine oxide was present in each formulation, based on the proportion of each molecule containing an active phosphine oxide moiety.

[0782]

[0783]

[0784] From these results, it can be seen that the phosphine oxide disclosed in the present invention is an effective photoinitiator for deep and surface cure of acrylate resin films under LED lamp conditions and is comparable to commercially available SpeedCure TPO when the same active phosphine oxide content is present. The disclosed phosphine oxide also promotes surface cure of acrylate resin films under these conditions.

[0785] Example 20: Nail Gel Coating

[0786] Typical UV-curable nail gel topcoat formulations are shown in Table 2A below. CN9066 is a urethane methacrylate oligomer with a good balance of adhesion, optical clarity, and tensile properties. The formulations were diluted with difunctional monomers SR239 (HDDMA) and SR170 (2-hydroxyethyl methacrylate). Formulations containing 2 wt% and 4 wt% loadings of Speedcure TPO (Comps 1 and 3) and Speedcure TPO-L (Comps 2 and 4), based on the weight of the ethylenically unsaturated compound, were compared to formulations containing 2 wt% and 4 wt% of Photoinitiator 9, prepared in accordance with the present invention in Example 14 (Invs 1 and 2).

[0787] Table 2A

[0788] Comp 1 Comp 2 Inv 1 Comp 3 Comp 4 Inv 2 CN9066 13 13 13 12.73 12.73 12.73 SR239 4.6 4.6 4.6 4.51 4.51 4.51 SR170 2 2 2 1.96 1.96 1.96 Speedcure TPO 0.4 0.8 Speedcure TPO-L 0.4 0.8 Photoinitiator 9 0.4 0.8

[0789] The formulation was mixed at 1500 RPM for two minutes using a Flacktek DAC 400 high-speed mixer until uniform. The composition was scraped onto a glass plate using a 3MIL scraping rod and cured for 60 seconds in an LED nail lamp (Gelish 18G, λ-395-405nm). The color, haze, and yellowness of the composition were measured using a HunterLab Ultrascan VIS spectrophotometer. Surface tack was qualitatively measured by applying the comparative composition and the present composition to a plastic nail spoon and curing them for 60 seconds using an LED nail lamp. Tack was assessed on a scale of 0-5, with 0 = no tack and 5 = very tack. Hardness was measured on the coating surface using a Konig pendulum (ASTM D4366) before and after IPA wiping. Due to oxygen inhibition, the LED-curable composition will have a tack layer on the surface. The tack layer was removed with IPA to determine the hardness of the coating. Removability was measured using a methyl ethyl ketone (MEK) double rub test (ASTM D5402). The performance properties of the UV-curable nail gel top coats are shown below in Table 2B.

[0790] Table 2B

[0791]

[0792] The color and yellowness values of the films containing photoinitiator 9 were slightly higher compared to TPO and TPO-L. The Konig hardness of the formulations containing photoinitiator 9 was slightly lower before and after IPA rub. After IPA rub, the hardness values of all formulations increased. The formulations containing photoinitiator 9 ranged from 35-46, compared to 42-52 for the formulations containing TPO and 45-46 for the formulations containing TPO-L. All compositions had the same surface tack after curing in the LED lamp for up to 60 seconds. A tack-free surface was not achieved with either the comparative formulation or the formulations of the present invention. All formulations were able to withstand over 200 double rubs with MEK, indicating that the cured coatings had good chemical resistance.

[0793] The cure speed, heat generation during cure, and heat flow measurements of the UV-curable top coating compositions containing TPO, TPO-L, and photoinitiator 9 were measured using photodifferential scanning calorimetry (PhotoDSC), as shown in Table 2C below. PhotoDSC was measured using a TA Instruments Q2000DSC equipped with an EFOSA4000 Acticure UV / Visible light curing system (containing a 100W mercury lamp light source). Prior to the experiment, the UV light intensity outside the sample window was measured using an EIT UV power puck II radiometer. Sample preparation for PhotoDSC was performed as follows: a Tzero aluminum reference pan and a Tzero aluminum sample pan were weighed. A drop of formulation (approximately 5-15 mg) was placed in the center of the sample pan and the mass was recorded. Both pans were placed in the DSC apparatus. Under a continuous stream of nitrogen, the system was stabilized at 25°C for 30 seconds. An isothermal experiment was started and the UV / visible light (320 to 450 nm, 190-210 mJ / cm 2 ) were submerged in the sample and reference pan for two minutes. The exothermic peak due to crosslinking was recorded during the experiment. The cure rate was measured by measuring the time it took to reach the peak maximum when the lamp was on. The area under the peak was recorded as the heat flow value (J / g). The maximum temperature during the cure was recorded as the temperature indicated by the maximum peak during the cure period.

[0794] Table 2C

[0795]

[0796] Inv 1 and Comps 1 and 2 are direct comparisons of compositions containing 2 wt% photoinitiator, while Inv 2 and Comps 3 and 4 are direct comparisons of compositions containing 4 wt% photoinitiator. The cure speeds of Inv 1 and 2 are similar to those of Comps 1-4. For the composition containing 2 wt% photoinitiator, the time to peak maximum was 0.5 min for TPO, and 0.06 min for TPO-1 and Photoinitiator 9 for the composition containing 2 wt% photoinitiator. For TPO, TPO-L, and Photoinitiator 9, the time to peak maximum was 0.06 min for the composition containing 4 wt% photoinitiator.

[0797] Next, the formulations were tested for cure speed using a 405nm LED device. Previous data utilized broad spectrum UV light. A typical nail gel lamp contains 18 x 2W LED bulbs with 30-50mJ / cm2 of 395-405nm light. 2 To understand the difference in curing speed, the dose of light from the 405nm LED device was set to 40mJ / cm 2 To simulate curing in a nail lamp. The PhotoDSC results using a 405 nm LED device can be found in Table 2D below.

[0798] Table 2D

[0799]

[0800] Comps 1 and 2 had slightly faster cure speeds (0.10 min and 0.11 min) compared to Inv 1 (0.13 min). Furthermore, Comps 3 and 4 had slightly faster cure speeds (both 0.10 min) compared to Inv 2 (0.12 min). Heat flux during cure was similar for all samples and ranged from 165-180 J / g. For the nail gel compositions, the differences in cure speed between the compositions do not indicate the superiority of one photoinitiator over the others, as in a nail salon setting, where a consumer places their hand under a nail lamp for 60 seconds, all samples would achieve full cure within this time.

[0801] Example 21: 3D printing experiment

[0802] Material

[0803] The following materials were used in Example 21:

[0804]

[0805]

[0806] Curable composition Curable compositions were prepared using the compounds listed in Tables 3A and 3B (amounts are expressed in parts by weight).

[0807] Table 3A

[0808]

[0809]

[0810] The maximum heat flux and peak time were determined using the following test conditions: 405 nm, 50 mW / cm 2 LED lasted 18 s, 50 mL / min N2 flow rate, 40 °C.

[0811] The acrylate conversion was determined using the following test conditions: 405 nm, 10 mW / cm 2 LED on for 20s, 20℃.

[0812] Table 3B. Summary of formulations and their properties

[0813]

[0814]

[0815] The following test conditions were used to determine the acrylate conversion: 405 nm, 10 mW / cm2 at (1+5) s. 2 LED, 3mil film, 10LPM dry air, 20℃.

[0816] Preparation of the formulations in Tables 3A and 3B

[0817] In a white max 50 can from FlackTek Inc., the photoinitiator was loaded first, followed by SR494, CN991, and SR531. A mixture of 51-55.66 g of each sample was mixed at 3000 RPM for 3 minutes in a Speed Mixer from FlackTec Inc. The sample cans were then placed in a 60°C oven for approximately 2 hours and mixed for an additional 2 minutes until the solution became clear.

[0818] Viscosity

[0819] The viscosity of each blend in Table 3B was measured at 20°C using a Brookfield DV-III+ viscometer with an SC-27 spindle. Each sample was measured at a specific RPM required to achieve 50% torque range. The viscosity was measured after the temperature and sample reached stability (10 minutes).

[0820] The results show that photoinitiator 9 according to the invention increases the viscosity of the formulation only moderately compared to the same equivalent amount of phosphine oxide TPO.

[0821] UV-visible spectroscopy measurements

[0822] UV-Vis spectra of each sample were obtained using a Shimadzu UV1800 spectrophotometer according to ASTM E169-04 using a quartz cuvette with a 1.0 cm optical path and scanning the spectrum over the wavelength range of 450 to 200 nm. The measurement cell was filled with a 500 ppm solution of photoinitiator in acetonitrile to ensure that the observed absorbance did not exceed 1.0 within the spectral range of the expected absorbance value. The normalized comparative data are overlaid on Figure 1 middle.

[0823] The results show that the UV spectrum of photoinitiator 9 at 2.16 times the weight percent matches that of TPO very well.

[0824] LED-DSC test

[0825] Differential Scanning Calorimetry (DSC) was performed using a custom 405 nm LED lamp setup. All photopolymerization rate measurements were performed using a Q2000 DSC unit from TA Instruments. The lamp holder for the DSC unit can be supplied by Arkema The engineered resin N3D-TOUGH784 was custom made and printed to ensure an exact fit with the AccuCure ULM-2-405, a 405nm lamp from DigitalLight Labs. The LED light was automatically triggered by connecting the "Event" outlet of the DSC cell to the Accure Photo Rheometer Ultraviolet Illumination & Measurement System. The LED light exposure can be programmed by turning it on or off using the "Event" from the Photo DSC software, but the intensity of the light can be preset by the Accure Photo Rheometer Ultraviolet Illumination & Measurement System. For measurement, approximately 10 mg of liquid sample was placed in the center of the T130522DSC Tzero pan by exposing it to 50 mW / cm at a 50 mL / min N2 flow rate and 40°C. 2 The resulting heat flow (W / g) curves were collected to analyze the maximum heat flow peak and maximum peak time, and are listed in Table 3A.

[0826] The results show that at the same equivalent amount of phosphine oxide, the curing speed precursors in the formulation are 4 < photoinitiator 6 < TPO. Although the photoinitiator according to the present invention has a slower curing speed than TPO, it advantageously does not produce low molecular weight photo-products. The curing speed is within the desired range.

[0827] FTIR testing

[0828] Fourier Transform Infrared (FTIR) with an Attenuated Total Reflection (ATR) device was used. All polymerization rate measurements were carried out using a Nicolet iS50 FT-IR spectrometer from Thermo Scientific equipped with a standard DLaTGS detector. The lamp holder of the ART platform of the FTIR unit can be customized and printed by Arkema engineering resin N3D-TOUGH784 to ensure an exact fit for the 405 nm lamp AccuCure ULM-2-405 from Digital Light Labs. On the bottom of this lamp holder, a dry air channel is built in to allow air to blow evenly over the sample surface, and the gas flow rate can be controlled on a rotameter. The LED lamp is manually triggered by an Ultraviolet illumination & Measurement System. The LED light exposure can be programmed through AccuCure software. For measurement, a drop of liquid sample is placed at the center of the ATR crystal. A 3 mil film is coated by a customized coating applicator (3 mil WFM, G1046 from BYK). The LED lamp with a gripper is placed on the top of the ART platform. Then the FTIR scan is started to first collect the liquid IR spectrum. Then the respective IR spectra at total exposure times of 10 s, 20 s, 50 s, and 100 s at 10 mW of LED light under ambient conditions are collected, as shown in Table 3A and Figure 2A as shown. Alternatively, the respective IR spectra at total exposure times of 1 s, 6 s, 16 s, 66 s, and 166 s at 10 mW of LED light in 10 LPM of dry air are collected, as shown in Table 3B or Figure 2B as shown. The measurement of acrylate conversion is carried out at the height under the reference peak near 1720 cm -1 ; the acrylate peak at about 1407 cm -1 is also measured. The peak height is determined using the baseline technique, where the baseline is selected as the two lowest points between 600 cm -1 and 1800 cm -1 . Then the height under the peak and above the baseline is determined. The integration limits for the liquid and cured samples are not the same but similar, especially for the reference peak.

[0829] Measure the ratio of the acrylate height of the liquid and cured samples to the reference peak height. The degree of cure or conversion, expressed as a percentage of the acrylate reacted, is calculated by the following equation:

[0830] Conversion (%) = [(R liq - R c ) × 100] / R liq

[0831] Where R liq is the height ratio of the liquid sample and R c is the height ratio of the LED-cured sample. The resulting acrylate conversion is shown in Figure 2A and Figure 2B and the acrylate conversions at 20 s exposure are listed in Tables 3A and 3B.

[0832] Figure 2A Shows that at the same equivalent of phosphine oxide, the curing speed precursor 4 < photoinitiator 6 < TPO in the formulation. Although the photoinitiator according to the present invention has a slower curing speed than TPO, it advantageously does not produce low molecular weight photoproducts. The curing speed is within the desired range.

[0833] Figure 2B Shows the curing speed of photoinitiator 9 in a formulation that very well matches TPO at the same equivalent of phosphine oxide.

[0834] 3D printing working curve

[0835] The following method is used to measure the working curve to find Ec (critical energy) and Dp (penetration depth), which are key features for determining the printability and printer settings for successful 3D printing. Ec represents the amount of energy that needs to be applied to cure the formulation to the "green state", and Dp is the depth that UV photons penetrate the formulation, which determines the thickness of the layer that can be printed.

[0836] The working curve and 3D printing are completed on an EnvisionOne 3D printer from EnvisionTec using a 385 nm light source.

[0837] Preparing your file for printing

[0838] 1. Import an STL file that has a measurable square with varying thickness (the increment is the same as the layer thickness to be printed).

[0839] 2. For the following STL file, use a 50 μm layer thickness in the slicing software. This will ensure a linear increase in the energy dose received by each printed square.

[0840] 3. Import the STL file into the printer slicing software.

[0841] 4. Place the part in a known build area, such as in the center.

[0842] 5. Place the part on a surface without using any support structure, raft, or substrate.

[0843] 6. Set the burn-in exposure and the standard exposure equal to each other.

[0844] 7. Minimize other settings, such as lift waiting time, to make the procedure fast and efficient.

[0845] Prepare the printer

[0846] 1. Remove the build platform.

[0847] 2. Load the barrel

[0848] 3. Place resin in bucket - only a small amount is needed to cover the bottom of the bucket -0.6 cm.

[0849] Printing working curve parts

[0850] 1. Start the working curve printing file. According to the preparation, each layer is 6.05mW / cm 2 Printing time 1s to 4s

[0851] 2. Once printing is complete, carefully peel the part from the bottom of the barrel surface.

[0852] 3. Gently clean the parts with IPA (isopropyl alcohol), TPM (tripropylene glycol monomethyl ether), acetone or other solvents.

[0853] 4. Print 2-3 working curves for each formulation.

[0854] Measure the cure depth corresponding to the energy dose

[0855] 1. Use a caliper Measure the depth of cure for all squares using the 3671. Generally speaking, as the energy dose increases, the depth of cure thickness should increase.

[0856] 2. Energy dose is determined as follows:

[0857] a. Energy dose (mJ / cm 2 ) = irradiance (mW / cm 2 )*time(seconds)

[0858] b. Note: Energy dose can also be measured using a radiometer

[0859]

[0860] Determine critical exposure, penetration depth, and printing parameters

[0861] 1. Determine the critical exposure Ec (mJ / cm) using the Jacobs working curve equation described in PF Jacobs, Fundamentals of stereolithography, Proc. Solid Free. Fabr. Symp. (1992) 87-89. 2 ) and penetration depth Dp (mils).

[0862] a.

[0863] b. Among them,

[0864] iC d = Measured cure depth (mils)

[0865] ii.E max =Energy dose (mJ / cm 2 )

[0866] c. Draw C d (mils) vs.ln(E max The slope of the curve corresponds to the penetration depth, and corresponds to C d =0 max The point is the critical exposure.

[0867] 2. The measured cure depth and corresponding exposure time are used to determine the optimal printing parameters. The goal is to achieve an exposure time that achieves a cure depth of 2-4x the thickness of the printed layer.

[0868] 3. Examples : For the above energy dose and cure depth measurements, Dp = 2.4 mils and Ec = 0.6 mJ / cm 2 .

[0869] The results are listed in Table 3B. The results show that at the same equivalent amount of phosphine oxide, the Ec and Dp of the photoinitiator 9 according to the present invention in the formulation are lower than those of TPO. The higher the concentration, the lower the Ec and Dp.

[0870] Tensile and DMA sample preparation:

[0871] 1. Prepare 400 g of each formulation as shown in Table 3B.

[0872] 2. Verify the break-in range and standard range exposure times of the EnvisionOne cDLP Mechanical (385nm) from Envision Tec.

[0873] 3. Set up the printer with the following parameters:

[0874] Printer irradiance: ~6.05mW / cm 2

[0875] Printing thickness: 50 microns / layer

[0876] Elevator settings: Default

[0877] Part printing orientation: XY plane

[0878] 3.5 seconds / layer

[0879] 4. Printing dog bone shaped tensile rods

[0880] Specimen type: ASTM D638 Type IV

[0881] Number of samples printed: 5

[0882] Dimensions: Approximately 115mm x 19mm x 3.2mm (LxWxH).

[0883] 5.DMA flexural mode specimen

[0884] Specimen type: ASTM D4065

[0885] Number of samples printed: 2

[0886] 6. Place a set of 5 tensile bars and a set of 2 DMA parts into a Dymax Model 5000 Flood Cure Unit for UVA / UVV flood curing for 60 seconds per side.

[0887] 7. The tensile bars and DMA bars were stored in a controlled room at 23°C and 50% RH for 40-80 hours before testing.

[0888] Tensile Tester (ASTM D618) : Instron 5966w / 2630-109 static axial clamp-on extensometer.

[0889] Test speed: 5mm / min

[0890] Preload: 5N

[0891] Preload pulling rate: 0.1mm / min

[0892] Specimen protection: yes

[0893] Specimen protection load: 4.448N

[0894] Extensometer: Yes

[0895] Extensometer type: Instron 2630-109 (ASTM E83 B-1 type extensometer)

[0896] Extensometer gauge length: 1"

[0897] All five bars were tested and the average tensile data was calculated and reported in Table 3B.

[0898] The results show that at the same phosphine oxide equivalent, the elongation at break and tensile toughness of the photoinitiator 9 according to the present invention in the formulation are both higher than those of TPO, with a slightly lower tensile modulus. The higher the concentration, the better the elongation at break and tensile toughness.

[0899] DMA test

[0900] A ThermoScientific Q800 from TA Instrument was used to observe the changes in mechanical properties of each cured DMA part at a frequency of 1 Hz and 5° C. / min over the entire temperature range of −150° C. to 250° C. The resulting tan (δ) peaks are listed in Table 3B to understand the changes in polymer behavior.

[0901] The results show that when 4.08 wt% is used, at the same equivalent amount of phosphine oxide, the glass transition temperature of the photoinitiator 9 according to the present invention in the formulation is 5.8°C higher than that of TPO. When 8.16 wt% is used, at the same equivalent amount of phosphine oxide, the glass transition temperature of the photoinitiator 9 according to the present invention in the formulation is 14.7°C lower than that of TPO.

[0902] Example 22: Experiment with Photoinitiator 11

[0903] Compatibility of Photoinitiator 11 in Common (Meth)acrylate Functional Monomers and Oligomers

[0904] Photoinitiator 11 was added in small portions to the monomer at 50°C and 250 rpm and to the oligomer at 60°C and 300 rpm until maximum solubility was achieved. Oligomers required higher temperatures due to their more viscous nature. Overall dissolution of the solids in the resin and oligomer was assessed visually. The maximum weight percent of photoinitiator 11 dissolved in each monomer or oligomer was reported in Figure 3SR531 is cyclic trimethylolpropane formal acrylate. SR339C is 2-phenoxyethyl acrylate. SR508E is dipropylene glycol diacrylate. SR238 is 1,6-hexanediol diacrylate. SR341 is 3-methyl-1,5-pentanediol diacrylate. SR595 is 1,10-decanediol diacrylate. SR506E is isobornyl acrylate. SR9003 is propoxylated neopentyl glycol diacrylate. SR9035 is ethoxylated trimethylolpropane triacrylate. CN3755 is an acrylated amine synergist. CN991E is a difunctional aliphatic urethane acrylate oligomer. CN964A85 is a difunctional aliphatic urethane acrylate oligomer diluted with tripropylene glycol diacrylate. CN963B80 is a difunctional aliphatic urethane acrylate oligomer diluted with 1,6-hexanediol diacrylate. CN965 is a difunctional aliphatic urethane acrylate oligomer. SR395 is isodecyl acrylate. All of these monomers and oligomers are commercially available from Arkema.

[0905] Photoinitiator 11 exhibits high compatibility and solubility with common (meth)acrylate-functional monomers and oligomers, which benefits formulators in graphics and other applications.

[0906] Cure Speed - Hg on Tape

[0907] The monomers and photoinitiator were added in the target weight ratios and then gently stirred at 30-40°C for 3 hours using a magnetic stirrer. Solubility was visually inspected to confirm complete dissolution. The components used in each formulation are shown in Table 4 below (amounts are expressed in weight % based on the total weight of the formulation).

[0908] Table 4

[0909] Preparation 1 Preparation 2 Preparation 3 Preparation 4 Preparation 5 SR306:SR349(30:70) 85 85 85 80.3 82.9 Speedcure TPO 5 Speedcure TPO-L 5 Speedcure BPO 5 Photoinitiator 11 9.7 Omnipol TP 7.1 Speedcure 73 2 2 2 2 2 CN3715 8 8 8 8 8

[0910] SR306 is tripropylene glycol diacrylate, SR349 is ethoxylated bisphenol A diacrylate, and CN3715 is a monofunctional acrylated amine synergist.

[0911] Mercury curing was performed on a Jenton International Limited Conveyor unit model 101808-T201-A001. The lamp head power supply unit model was JA2000VPXI-0000. The intensity setting was 50%, the belt speed was 10 m / min, and the film weight was 12 μm.

[0912] LED curing was performed on an Integration Technology Limited Conveyor unit model VZero. The lamp head unit was a water-cooled dual-band (365nm and 395nm) LED lamp model Solidcure 2 1.2kW.

[0913] The cure results at the target film weight were checked by lightly scraping for surface cure and by compressing the thumb twist for depth cure. The average cure speed was calculated by dividing the belt speed by the number of passes recorded when a complete cure of the resin was achieved. For practical purposes, cure speeds of less than 0.3 m / min were classified as "uncured". Repeat cures were performed on the same formulation and the average cure speed was used for the final comparison. The cure speeds required to obtain surface cure and depth cure were as follows: Figure 4 Under a mercury lamp, photoinitiator 11 matches the curing performance of BPO at the same phosphine oxide w / w %.

[0914] Yellowing

[0915] Each phosphine oxide was evaluated for its ability to photobleach after exposure to a mercury lamp and in 24 μm films. Mercury curing was performed at a belt speed of 10 m / min and each sample was passed through 5 times. The yellowness index (YI) was measured immediately after curing at T=0 and again after 24 hours. The change in yellowness index (ΔH) over 24 hours is plotted below. The results are shown in Figure 5A and 5B middle.

[0916] Formulation Information: Speedcure TPO, Speedcure BPO, and Speedcure TPO-L (all from Arkema) were added at 4 wt%, inventive photoinitiator 11 at 8 wt%, and Omnipol TP at 5 wt% to a mixture of 30 wt% SR306 (from Arkema) and 70 wt% SR349 (from Arkema). The formulations were prepared by dissolving the photoinitiators in the monomers at 50°C and 250 rpm for 3 hours, and complete dissolution was assessed visually.

[0917] The formulation containing BPO yellowed the most at T = 0. The formulation containing photoinitiator 11 showed a YI similar to TPO-L and TPO.

[0918] Stability - Accelerated Aging of Photoinitiators vs. Accelerated Aging of Formulations

[0919] Stability of photoinitiator 11 was analyzed by LED-FTIR at 405 nm.

[0920] LED-FTIR analysis was used to obtain cure speed comparisons of aged samples containing photoinitiator 11 relative to Speedcure TPO in an experimental formulation. The photoinitiator was aged at 60°C for one week before formulation and compared directly to the photoinitiator aged in the formulation at 60°C for one week.

[0921] Preparation details (amounts are expressed in parts by weight):

[0922]

[0923] Curing conditions: 405nm, 10mW, 10L / min dry air

[0924] LED FT-IR analysis was performed on a ThermoScientific Nicolet iS50 FT-IR spectrometer with a standard DLaTGS detector 2. The applied sample was spread into a 3 mil thick film using a film applicator. For analysis, the 1727 cm -1 All spectra were normalized using the (-C=O stretching) peak as a reference. For acrylic acid monomers, 1407 cm -1 The conversion rate was measured as a function of time by measuring the decrease in the peak height of the C=C peak at . The degree of monomer conversion was calculated by measuring the peak height. The stability results of the formulation containing Speedcure TPO are shown in Figure 6A The stability results of the formulation containing photoinitiator 11 are shown in Figure 6B middle.

[0925] This study demonstrates that Photoinitiator 11 is stable in the experimental formulations as both the individual photoinitiators age and the formulation as a whole ages. Cure speed is not affected by accelerated aging like Speedcure TPO, which exhibits a greater decrease in cure speed than Photoinitiator 11.

[0926] Stability in inkjet formulations

[0927] Formulators often experience a reduction in the shelf life of inkjet formulations containing phosphine oxides. We have seen that photoinitiator 11 remains reactive when formulated into cyan inks and degrades less than other phosphine oxides promoted on the market.

[0928] For surface cure, check the cure result at the target film weight by gently scratching and for deep cure, by compressing the thumb to twist. The average cure speed is calculated by dividing the belt speed by the number of passes recorded when a fully cured resin is achieved. For practical purposes, a cure speed of less than 0.3 m / min is classified as "uncured." Repeat the cure for the same formulation and use the average cure speed for the final comparison.

[0929] The cure speed of the sample was checked at T=0, then the sample was aged in an oven at 60°C for 2 weeks and the cure speed was re-evaluated. The initial cure speed was directly compared to the cure speed of the aged sample. Lamp system: Mercury lamp with 50% intensity and belt speed of 10m / min

[0930] The LED light was set at 395nm, the light intensity was 70%, and the belt speed was 20m / min

[0931] Formulation information (amounts expressed in wt % based on the total weight of the formulation):

[0932] The film weight was 6 μm.

[0933]

[0934] The results under mercury solidification are shown in Figure 7A At the same phosphine oxide w / w %, photoinitiator 11 showed the best initial cure performance under a mercury lamp, closely followed by Speedcure BPO. Omnipol TP gave the same cure performance as Speedcure TPO. After two weeks in a 60°C oven, all cure performances decreased, with monomeric phosphine oxide decreasing by half, Omnipol TP by one-third, and photoinitiator 11's performance decreasing only slightly.

[0935] The results of LED curing are as follows Figure 7B As shown. Initial curing with Speedcure BPO gave the best results under a 395nm LED, followed by Speedcure TPO. Photoinitiator 11 gave similar cure speeds to Speedcure-L. Omnipol TP performed the worst under LED. After the samples had been stored in a 60°C oven for two weeks, little difference in cure performance was seen, with most showing slight improvement.

[0936] Extractables

[0937] The cured paper is first dried by passing it 5 times under a mercury lamp at 5.0 m / min, with the lamp at 50% intensity. The weight of the paper is recorded. A 50 μm film is cured under mercury (lamp 50% intensity, belt speed 5.0 m / min) and the weight of the paper is re-recorded. The film is placed in a thick-walled pressure vessel with 15 mL of solvent (acetonitrile and ethanol) and placed in an oven at 60° C. for 10 days. After cooling to room temperature, the vial is opened and the extract is filtered through a 0.45 μm filter and then analyzed. The migrating substances are quantified using an HPLC method suitable for MS, which has been developed for analysis using a calibration curve for all migrating substances. The target is a 5% active content of phosphine oxide.

[0938] The extractables of concern are centered around mesitylene-3-methylbenzaldehyde, previously identified by Scarsella et al. as a photolytic decomposition product of TPO, TPO-L, and BPO (Molecules 2019, 24, 3592). It was found to migrate at high concentrations, and its in vivo safety in the presence of food or contact has not yet been evaluated.

[0939] preparation:

[0940]

[0941] LM5302 is an ethoxylated trimethylolpropane triacrylate available from Arkema.

[0942] result:

[0943]

[0944]

Claims

1. A photoinitiator according to formula (1) or (2): in: - each Ar is independently an optionally substituted arylene; - R1 and R2 are independently H or an optionally substituted group selected from alkyl and aryl; or R1 and R2 together with the carbon atoms to which they are attached form a ring; - one of R'1 and R'2 is H and the other of R'1 and R'2 is selected from -OR 4 、-SR 5 、-NR 6 R 7 、-C(R 8 )(CO-W 1 -R 9 )(CO-W 2 -R 10 )、-C(R 11 )(CO-W 3 -R 12 )(CN) and -C(R 13 )(CN)2; or R'2 is H and R'1 and Q2 together with the atoms to which they are attached form a 5-7 membered ring; or R'2 is H and R'1 and Q3 together with the atoms to which they are attached form a 5-8 membered ring; - each R3 is independently an optionally substituted group selected from alkyl, aryl and alkoxy; -R 4 、R 5 、R 6 and R 7 is independently H or an optionally substituted group selected from alkyl, polyoxyalkylene, cycloalkyl, heterocycloalkyl, aryl and heteroaryl; or R 6 and R 7 Together with the nitrogen atom to which they are attached, they form a 5-7 membered ring; -R 8 、R 11 and R 13 are independently H or optionally substituted alkyl, preferably H; -R 9 、R 10 and R 12 is independently an optionally substituted group selected from alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl, or R 9 and R 10 Together with the atoms to which they are attached, they form a 5-7 membered ring, -W 1 、W 2 and W 3 are independently selected from a bond or an oxygen atom; -Q1 is an optionally substituted aryl group or a group of formula (3): in: -Each R a are independently optionally substituted groups selected from alkyl, aryl, alkoxy, aryloxy, thioalkyl, and thioaryl; and -y is a number selected from 0 to 5; -Q2 and Q3 are independently -OR 14 、-SR 15 、-NR 16 R 17 、-O-[CH2-CH(OH)-Y1] a -Z 1 、-SZ 2 、-N(R 18 )-Z 3 or -O-Cyhex-Y2-Z 4 ; or Q2 and R'1 together with the atoms to which they are attached form a 5-7 membered ring; or Q3 and R'1 together with the atoms to which they are attached form a 5-7 membered ring; -R 14 and R 15 are independently H or an optionally substituted group selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl; -R 16 、R 17 and R 18 is independently H or an optionally substituted group selected from alkyl and aryl; or R 16 and R 17 Together with the nitrogen atom to which they are attached, they form a 5-7 membered ring; -Cyhex is a cyclohexylene group substituted by a hydroxyl group, preferably represented by the following formula: -Y1 is a bond, -CH2-O-* or -CH2-C(=O)-O-*; -Y2 is a bond, -CH2-OC(=O))-# or -C(=O)-O-#; -a is 0 or 1; -Z 1 , Z 2 , Z 3 and Z 4 are independently phosphine oxide-containing moieties; - The symbol * represents the part Z 1 connection points; - The symbol # represents the part Z 4 connection point.

2. The photoinitiator according to claim 1, wherein each Ar is independently an optionally substituted phenylene, preferably a meta-phenylene substituted with one or more optionally substituted groups selected from alkyl, aryl, alkoxy, aryloxy, thioalkyl and thioaryl groups; and more preferably, Ar is a group of formula (4):

3. The photoinitiator according to claim 1 or 2, wherein R1 and R2 are both H, or R1 and R2 together with the carbon atoms to which they are attached form a six-membered ring, preferably a six-membered alicyclic ring, and wherein preferably R1 and R2 are both H.

4. The photoinitiator according to any one of claims 1 to 3, wherein one of R'1 and R'2 is H, and the other of R'1 and R'2 is -OR 4 , and preferably R 4 is an optionally substituted alkyl group.

5. The photoinitiator according to any one of claims 1 to 3, wherein one of R'1 and R'2 is H, and the other of R'1 and R'2 is -SR 5 , and preferably R 5 is an optionally substituted alkyl group.

6. The photoinitiator according to any one of claims 1 to 3, wherein one of R'1 and R'2 is H, and the other of R'1 and R'2 is -NR 6 R 7 , and wherein preferably R 6 and R 7 Together with the nitrogen atom to which they are attached they form a 5- to 7-membered ring; in particular an optionally substituted ring selected from morpholine, piperidine, pyrrolidine, oxazolidine, piperazine, thiazolidine, thiomorpholine and azepane.

7. The photoinitiator according to any one of claims 1 to 3, wherein one of R'1 and R'2 is H, and the other of R'1 and R'2 is -C(R 8 )(CO-W 1 -R 9 )(CO-W 2 -R 10 ), and wherein preferably, -R 8 It is H; -W 1 and W 2 are independently a bond or an oxygen atom; and -R 9 and R 10 is independently optionally substituted alkyl.

8. The photoinitiator according to any one of claims 1 to 3, wherein R'2 is H and R'1 forms a 5-8 membered ring with Q2 or Q3, and wherein preferably, the photoinitiator is according to formula (5) or (6) in -X and X' are independently selected from O, S and NR 19 ; -R 19 is H or optionally substituted alkyl; -L0 is an optionally substituted C1-C4 alkylene group.

9. The photoinitiator according to any one of claims 1 to 8, wherein each R3 is independently an optionally substituted phenyl group, a methoxy group or an ethoxy group; preferably, each R3 is independently a phenyl group or an ethoxy group.

10. The photoinitiator according to any one of claims 1 to 9, wherein Q1 is a phenyl group or a group of formula (3a):

11. The photoinitiator according to any one of claims 1 to 7 and 9 to 10, wherein -Q2 and Q3 are independently -OR 14 ; -R 14 is an optionally substituted alkyl group, preferably a methyl group or an ethyl group.

12. The photoinitiator according to any one of claims 1 to 7 and 9 to 10, wherein -Q2 and Q3 are independently -O-[CH2-CH(OH)-Y1] a -Z 1 ; -Z 1 is a group of formula (7); in: - Ar, Y1, R1, R2, R'1, R'2, R3, Q1 and a are as defined in any one of claims 1 to 7 and 9 to 10; - L1 is the connecting part; and -b is a number selected from 1 to 15. The photoinitiator according to claim 12 , wherein a is equal to 0.

14. The photoinitiator according to claim 12, wherein a is equal to 1 and Y1 is a bond or -CH2-O-*, preferably -CH2-O-*.

15. The photoinitiator according to any one of claims 1 to 7 and 9 to 10, wherein -Q2 and Q3 are independently -SR 15 ; -R 15 is an optionally substituted alkyl group.

16. The photoinitiator according to any one of claims 1 to 7 and 9 to 10, wherein -Q2 and Q3 are independently -SZ 2 ; -Z 2 is a group of formula (8): in: - Ar, R1, R2, R'1, R'2, R3 and Q1 are as defined in any one of claims 1 to 7 and 9 to 10; - L2 is the connecting part; and -b' is a number selected from 1 to 15.

17. The photoinitiator according to any one of claims 1 to 7 and 9 to 10, wherein -Q2 and Q3 are independently -NR 16 R 17 ; -R 16 and R 17 is independently H or an optionally substituted group selected from alkyl and aryl; or R 16 and R 17 Together with the nitrogen atom to which they are attached, they form a 5-7 membered ring.

18. The photoinitiator according to any one of claims 1 to 7 and 9 to 10, wherein -Q2 and Q3 are independently -N(R 18 )-Z 3 ; -R 18 is H or an optionally substituted group selected from alkyl and aryl; -Z 3 is a group of formula (9): in: -Ar, R1, R2, R'1, R'2, R3, R 18 and Q1 is as defined in any one of claims 1 to 7 and 9 to 10; - L3 is the connecting part; and -b" is a number selected from 1 to 15.

19. The photoinitiator according to any one of claims 1 to 7 and 9 to 10, wherein -Q2 and Q3 are independently -O-Cyhex-Y2-Z 4 ; -Z 4 is a group of formula (7) or a group of formula (10) as defined in claim 12; in: -Ar, Y2, R1, R2, R'1, R'2, R3, Q1 are as defined in any one of claims 1 to 7 and 9 to 10; - L4 is the connecting part; and -b'' is a number selected from 1 to 15.

20. The photoinitiator according to any one of claims 12, 16, 18 and 19, wherein each linking moiety L1, L2, L3 and L4 is independently selected from an aromatic linking moiety, an aliphatic linking moiety, an alicyclic linking moiety, a polyether linking moiety, a polythioether linking moiety, a polyalkyleneimine linking moiety, a polyester linking moiety, a polycarbonate linking moiety, a polycaprolactone linking moiety, a polyurethane linking moiety, a polyorganosiloxane linking moiety, a polybutadiene linking moiety and combinations thereof; Preferably, each linking moiety L1, L2, L3 and L4 is independently selected from aromatic linking moieties, aliphatic linking moieties, alicyclic linking moieties, polyether linking moieties, polythioether linking moieties, polyalkyleneimine linking moieties, polyester linking moieties, polyorganosiloxane linking moieties and combinations thereof.

21. The photoinitiator according to any one of claims 12, 16, 18 and 19, wherein each linking portion L1, L2, L3 and L4 is independently selected from: - a trivalent moiety corresponding to formula (11): in: -R 20 and R 21 are independently straight or branched chain alkylene groups; -a' is an integer equal to 0 or 1; - a trivalent moiety corresponding to formula (12): in: - R4 and R'4 are independently H or methyl; - R5 is H, alkyl or alkoxy, preferably R5 is alkyl; - each c is independently an integer from 0 to 2, provided that no more than one c is equal to 0, preferably each c is equal to 1 or one c is equal to 0 and the other two c are equal to 1; - each d is independently an integer from 2 to 4, in particular 2; - each e is independently an integer from 0 to 10, in particular from 1 to 6; - a trivalent moiety corresponding to formula (13): in: -R'5 is H, alkyl or alkoxy, preferably R'5 is alkyl; - Each R6 is independently a linear or branched alkylene group; - each c' is independently an integer from 0 to 2, provided that no more than one c' is equal to 0, preferably each c' is equal to 1 or one c' is equal to 0 and the other two c' are equal to 1; - a trivalent moiety corresponding to formula (14a), (14b) or (14c): where R f is H or methyl; - a tetravalent moiety corresponding to formula (15a) or (15b): in: - Each R7 is independently a linear or branched alkylene group; - R8 and R'8 are independently H or methyl; - each f is independently an integer from 0 to 2, provided that no more than one f is equal to 0, preferably each f is equal to 1; - each g is independently an integer from 2 to 4, in particular 2; - each h is independently an integer from 0 to 10, in particular from 1 to 6; - a tetravalent moiety corresponding to formula (16): in - R9 and R'9 are independently H or methyl; -Each R 10 are independently H, alkyl or alkoxy, preferably R 10 is an alkyl group; - each i is independently an integer from 2 to 4, in particular 2; - each j is independently an integer from 0 to 10, in particular from 1 to 6; - a tetravalent, pentavalent or hexavalent moiety corresponding to formula (17): in: -R 24 and R' 24 are independently H or methyl; - each i* is independently an integer from 2 to 4, in particular 2; - each j* is independently an integer from 0 to 10, in particular from 1 to 6; -k' is an integer from 1 to 3; - corresponding to the hexavalent moiety of formula (18): in -R 11 and R' 11 are independently H or methyl; - each k is independently an integer from 2 to 4, in particular 2; - each l is independently an integer from 0 to 10, in particular from 1 to 6 - corresponding to the hexavalent moiety of formula (19): in: -R 25 and R' 25 are independently H or methyl; - each l* is independently an integer from 2 to 4, in particular 2; - each m* is independently an integer from 0 to 10, in particular from 1 to 6; - a divalent moiety according to one of the formulae (20) to (28): -(CR 12 R' 12 ) m -(20) -[(CR 13 R' 13 ) n -O] o -(CR 13 R' 13 ) n -(21) -[(CR 14 R' 14 ) p -O] q -(CR 15 R' 15 ) r -[O-(CR 14 R' 14 ) p ] q -(22) -[(CR 16 R' 16 ) s -C(=O)O] t -(CR 17 R' 17 ) u -(23a) -(CR 17 R' 17 ) u -[(CR 16 R' 16 ) s -C(=O)O] t -(23b) -[(CR 18 R' 18 ) v -O-C(=O)-(CR 19 R' 19 )w-C(=O)-O] x -(CR 18 R' 18 ) v -(24) -[(CR 20 R' 20 ) y -S] z -(CR 20 R' 20 ) y -(25) -(CR 21 R' 21 ) m '-C(=O)-O-(CR 22 R' 22 ) n '-O-C(=O)-(CR 21 R' 21 ) m '-(26) -(CR 23 R' 23 )m”-Cy-[L-Cy]n”-(CR 23 R' 23 )m”-(27) in: -R 12 , R' 12 、R 15 , R' 15 、R 17 , R' 17 、R 18 , R' 18 、R 19 , R' 19 、R 21 , R' 21 、R 22 , R' 22 、R 23 and R' 23 are independently H or alkyl; -R 13 , R' 13 、R 14 , R' 14 、R 16 , R' 16 、R 20 , R' 20 、R 26 and R' 26 are independently H or methyl; -Cy is an optionally substituted ring, in particular an optionally substituted cyclohexylene or phenylene; -L is a bond or linking moiety, such as Alk, -C(=O)-, -C(=O)-O-Alk-O- C(=O)-, -SO-, -SO2-, -C(=CCl2)- and -Alk-Ph-Alk-; -Alk is an optionally substituted alkylene group; -Ph is optionally substituted phenylene; - m, n', r, v, u, w are independently integers from 2 to 20; - each m" is independently an integer from 0 to 20; - n, n*, p and y are independently integers from 2 to 4; -n" is an integer equal to 0 or 1; - m', o, t, x and z are independently an integer from 1 to 20; - each o* is independently an integer from 0 to 10, in particular from 1 to 6; - each q is independently an integer from 0 to 20, provided that at least one q is not 0; -s is an integer from 3 to 12; - a divalent moiety according to formula (S1): in: -Each R 27 are independently alkyl, haloalkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkaryl, alkoxy, or aryloxy; - each L5 is independently a bond or a hydrocarbon linker, which is optionally interrupted by one or more functional groups selected from ethers and esters; -p* is 0 to 100; - a tetravalent moiety according to formula (S2): in: -Each R 28 are independently alkyl, haloalkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkaryl, alkoxy, or aryloxy; - Each L6 is independently a hydrocarbon linking moiety, which is optionally replaced by one or more selected from ether, Ester and amino functional groups are interrupted; -q* is 0 to 100; - a polyvalent moiety according to formula (S3) or (S4): in: -Each R 29 and R 30 are independently alkyl, haloalkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkaryl, alkoxy, or aryloxy; - each L7 and L8 is independently a hydrocarbon linking moiety, which is optionally interrupted by one or more functional groups selected from ether, ester and amino groups; - r* and t* are independently 0 to 100; -s* is 2-18; -u* is 1 to 9.

22. The photoinitiator according to any one of claims 12, 16, 18 and 19, wherein L1, L2, L3 and L4 are independently selected from: Preferably, each linking moiety L1, L2, L3 and L4 is independently a divalent linking moiety selected from the group consisting of alkylene groups such as 1,3-propylene, 1,3- or 1,4-butylene, 1,5-pentanediyl, 1,6-hexanediyl, 1,8-octanediyl, 1,9-nonanediyl, 1,10-decanediyl, 1,12-decanediyl, 2-methyl-1,3-propylenediyl, 2,2-diethyl-1,3-propylenediyl, 3-methyl-1,5-pentanediyl, 3,3-dimethyl-1,5-pentanediyl, 2,2-dimethyl-1,3-propylenediyl, 2,2-diethyl-1,3-propylenediyl, 2,2-dimethyl ... alkyl-1,3-propanediyl, 2,4-diethyl-1,5-pentanediyl; alkoxylated derivatives of the aforementioned alkylene groups, preferably ethoxylated and / or propoxylated derivatives of the aforementioned alkylene groups; derivatives of the aforementioned alkylene groups, preferably esterified by ring-opening polymerization of lactones such as ε-caprolactone; residues of di-, tri-, tetra- or polyoxyalkylene groups containing no hydroxyl groups, for example di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol, di-, tri- or tetrabutylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, poly(ethylene glycol-co-propylene glycol).

23. The photoinitiator according to any one of claims 1 to 7 and 9, wherein the photoinitiator is according to formula (2) and the Q3 moiety forms the polymer backbone; Preferably, the photoinitiator of formula (2) comprises: - a plurality of units of formula (29): in -B is *-O-[CH2-CH(OH)-Y] a -、-S- or -N(R 18 )-; -Y, R 18 and a as defined in claim 1; - The symbol * represents the point of attachment to the C(=O) group; and; - a plurality of units according to one of the formulae (20) to (28) as defined in claim 21.

24. A process for preparing a photoinitiator of formula (1) or (2) according to any one of claims 1 to 7 and 9 to 23, wherein the process comprises reacting at least one precursor of formula (30) or (31) with at least one product of formula (32): wherein Ar, R1, R2, R3, R'1, R'2, Q1, Q2 and Q3 are as defined in any one of claims 1 to 23; Preferably, the product of formula (32) is selected from: - amines, in particular secondary amines (e.g. sec-butylamine, isobutylamine, tert-butylamine, cyclohexylamine, 1,1,3,3-tetramethylbutylamine, morpholine, piperidine, pyrrolidine, N-methylpiperazine, oxazolidine, thiazolidine, thiomorpholine, azepane), more particularly secondary cyclic amines (e.g. morpholine, piperidine, pyrrolidine, N-methylpiperazine, oxazolidine, thiazolidine, thiomorpholine, azepane); - alcohols, in particular primary alcohols (e.g. methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1-ol, 3-methylbutan-1-ol, 2,2-dimethylpropan-1-ol, hexan-1-ol, methylpentanol, 3-ethylbutan-1-ol, heptan-1-ol, octan-1-ol, 6-ethylhexan-1-ol, nonan-1-ol, decan-1-ol, dodecan-1-ol, tridecan-1-ol, isotridecan-1-ol, butoxyethanol, benzyl alcohol, methoxypolyethylene glycol); - mercaptans, in particular primary mercaptans (for example 1-hexanethiol, 1-octanethiol, 1-decanethiol, 1-dodecanethiol, methyl thioglycolate, ethyl thioglycolate, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate); - active methylene compounds, in particular β-diesters (for example dimethyl malonate, diethyl malonate, dipropyl malonate), β-ketoesters (for example ethyl acetoacetate), β-diketones (for example pentane-2,4-dione, cyclohexane-1,3-dione, 5,5-dimethylcyclohexane-1,3-dione), β-ketonitriles (for example 3-oxobutyronitrile), β-cyanoesters (for example methyl cyanoacetate, ethyl cyanoacetate), β-dinitriles (for example malononitrile).

25. Precursors of formula (30) or (31): wherein Ar, R1, R2, R3, Q1, Q2 and Q3 are as defined in any one of claims 1 to 23.

26. A process for preparing a precursor of formula (30) or (31) according to claim 25, wherein the process comprises reacting at least one precursor of formula (33) or (34) with a compound of at least one of formulae (35) to (42): R 14 -OH(35)R 15 -SH(36)NHR 16 R 17 (37) Z 1a -OH(38) Z 2 -SH(40)Z 3 -NH(R 18 )(41) in: - Ar, R1, R2, R3, Q1, Y1 and Y2 are as defined in any one of claims 1 to 3 and 9 to 10; -G is OH, a halogen atom or -OC(=O)-J; -J is alkyl or aryl, especially tert-butyl; -R 14 As defined in claim 1 or 11; -R 15 As defined in claim 1 or 15; -R 16 and R 17 As defined in claim 1 or 17; -Z 1a It is the hydroxyl-containing part; -Z 1b is the epoxide-containing portion; -Z 2 is a thiol-containing moiety; -Z 3 It is an amine-containing moiety; -Z 4 It is the epoxide-containing portion.

27. The method of claim 26, wherein the method comprises reacting at least one precursor of formula (33) or (34) with at least one compound of formula (38), and Z 1a Corresponding to formula (43): wherein L1 and b are as defined in any one of claims 12 and 20 to 22; Preferably, the compound of formula (38) is a polyol selected from the group consisting of ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 1,3- or 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol , 3,3-dimethyl-1,5-pentanediol, neopentyl glycol, 2,4-diethyl-1,5-pentanediol, 3,3-butylethyl-1,5-pentanediol, cyclohexanediol, cyclohexane-1,4-dimethanol, norbornene dimethanol, norbornane dimethanol, tricyclodecanediol, tricyclodecane dimethanol, dicyclopentadiene diol, hydroquinone bis(2-hydroxyethyl) ether, catechol, resorcinol, cashew diol, phloroglucinol, pyrogallol, tris(hydroxyphenyl)methane , tris(hydroxyphenyl)ethane, bisphenol A, B, F or S, hydrogenated bisphenol A, B, F or S, trimethylolmethane, trimethylolethane, trimethylolpropane, di(trimethylolpropane), triethylolpropane, pentaerythritol, di(pentaerythritol), tri(pentaerythritol), glycerol, di-, tri- or tetraglycerol, polyglycerol, di-, tri- or tetra(ethylene glycol), di-, tri- or tetra(1,2-propylene glycol), di-, tri- or tetra(1,3-propylene glycol), di-, Tri- or tetra-(1,4-butanediol), poly(ethylene glycol), poly(propylene glycol), poly(trimethylene glycol), poly(tetramethylene glycol), poly(ethylene glycol-co-propylene glycol), sugar alcohols, i.e., erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, lactitol, fucitol, or iditol), dianhydrohexanols (i.e., isosorbide, isomannite, isoiditol), tris(2-hydroxyethyl)isocyanurate, hydroxylated vegetable oils, C 36 - dimer diols, polybutadiene polyols, polyester polyols, polyether polyols, polyorganosiloxane polyols, polycarbonate polyols, and alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof and derivatives obtained by ring-opening polymerization of ε-caprolactone initiated with one of the aforementioned polyols, and combinations thereof.

28. The method of claim 26, wherein the method comprises reacting at least one precursor of formula (33) or (34) with at least one compound of formula (39), and Z 1b Corresponding to formula (44): in: -Y1 as defined in claim 1; - L1 and b are as defined in any one of claims 12 and 20 to 22; Preferably, the compound of formula (39) is a polyepoxide selected from the group consisting of 1,2,3,4-diepoxybutane, 1,2,4,5-diepoxypentane, 1,2,5,6-diepoxyhexane, 1,2,7,8-diepoxyoctane, 1,2,9,10-diepoxydecane, ethylene glycol diglycidyl ether, 1,2- or 1,3-propylene glycol diglycidyl ether, 1,2-, 1,3- or 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,7-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether. Glycerol ether, 1,12-dodecanediol diglycidyl ether, 2-methyl-1,3-propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 2,2-diethyl-1,3-propylene glycol diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, 3,3-dimethyl-1,5-pentanediol diglycidyl ether, 2,4-diethyl-1,5-pentanediol diglycidyl ether, 3,3-butylethyl-1,5-pentanediol diglycidyl ether, di-, tri- or tetra(ethylene glycol) diglycidyl ether, di-, tri- or tetra(1,2-propylene glycol) diglycidyl ether, di-, tri- or tetra(1,3-propylene glycol) diglycidyl ether, di-, tri- or tetra( (1,4-Butanediol) diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly(trimethylene glycol) diglycidyl ether, poly(tetramethylene glycol) diglycidyl ether, poly(ethylene glycol-co-propylene glycol) diglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, di(trimethylolpropane) tetraglycidyl ether, pentaerythritol tetraglycidyl ether, cyclohexanedicarboxylic acid diglycidyl ester, cyclohexane diglycidyl ether, cyclohexane-1,4-dimethanol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether ethers, isosorbide diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, cashew diglycidyl ether, phloroglucinol triglycidyl ether, pyroglucinol triglycidyl ether, tris(hydroxyphenyl)methane triglycidyl ether, tris(hydroxyphenyl)ethane triglycidyl ether, bisphenol A, B, F or S diglycidyl ether, hydrogenated bisphenol A, B, F or S diglycidyl ether, diglycidyl phthalate, diglycidyl terephthalate, diglycidyl isophthalate, limonene dioxide (4-vinyl-1-cyclohexene diepoxide), epoxidized vegetable oils, triglycidyl isocyanurate, epoxy-functionalized polyorganosiloxanes, and combinations thereof.

29. The method of claim 26, wherein the method comprises reacting at least one precursor of formula (33) or (34) with at least one compound of formula (40), and Z 2 Corresponding to formula (45): wherein L2 and b' are as defined in any one of claims 16 and 20 to 22; Preferably, the compound of formula (40) is a polythiol selected from the group consisting of ethane-1,2-dithiol, propane-1,3-dithiol, butane-1,4-dithiol, hexane-1,6-dithiol, octane-1,8-dithiol, decane-1,10-dithiol, 1,8-dimercapto-3,6-dioxaoctane (DMDO), di-, tri- or polyethylene glycol di(ethanethiol), ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), 1,2- Propylene glycol bis(thioglycolate), 1,2-propylene glycol bis(3-mercaptopropionate), 1,2-propylene glycol bis(3-mercaptobutyrate), 1,3-propylene glycol bis(thioglycolate), 1,3-propylene glycol bis(3-mercaptopropionate), 1,3-propylene glycol bis(3-mercaptobutyrate), 1,4-butanediol bis(thioglycolate), 1,4-butanediol bis(thiopropionate), 1,4-butanediol bis(3-mercaptobutyrate), 1,6-hexanediol bis(thioglycolate), 1,6-hexanediol bis(3-mercaptopropionate), esters), 1,6-hexanediol bis(3-mercaptobutyrate), di-, tri- or polyethylene glycol bis(thioglycolate), di-, tri- or polyethylene glycol bis(3-mercaptopropionate), di-, tri- or polyethylene glycol bis(3-mercaptobutyrate), di-, tri- or polypropylene glycol bis(thioglycolate), di-, tri- or polypropylene glycol bis(3-mercaptopropionate), di-, tri- or polypropylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(thioglycolate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tris[2-(3-mercaptobutyryloxy)ethyl]isocyanurate, thiol-terminated polymers, mercapto-functionalized polyorganosiloxanes, and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof, and combinations thereof.

30. The method of claim 26, wherein the method comprises reacting at least one precursor of formula (33) or (34) with at least one compound of formula (41), and Z 3 Corresponding to formula (46): in: -R 18 As defined in claim 1; - L3 and b" as defined in any one of claims 18 and 20 to 22; Preferably, the compound of formula (41) is a polyamine selected from the group consisting of 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 2-methylpentamethylenediamine, ethylenediamine, 1,2- or 1,3-propylenediamine, 2-methyl-1,2-propylenediamine, 2,2-dimethyl-1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,3- or 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexanediamine, 2,5-dimethyl-2,5-hexanediamine, 2,2,4- or 2,4,4-trimethyl-1,6-hexanediamine, 1,7-heptanediamine, 1 ,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 2,4- or 2,6-hexahydrotoluenediamine, 2,4'- or 4,4'-diamino-dicyclohexylmethane, 1,3- or 1,4-cyclohexanediamine, 1,3- or 1,4-bis(methylamino)cyclohexane, 1,8-p-menthanediamine, hydrazine, phenylenediamine, 2,3-2,4-3,4- or 2,6-toluenediamine, o-, m- or p-xylylenediamine, 2,4'- or 4,4'-diaminodiphenylmethane, benzidine, N-(2-aminoethyl)-1,3-propylenediamine, N,N'-bis-(2-aminoethyl)piperazine, polyetheramines (especially For example D-230, D-400, D-2000, D-2010, D-4000, ED-600, ED-900, ED-2003, EDR-148, EDR-176, THF-100, THF-170, T403, T3000, T5000, RFD-270), amino-functional polyorganosiloxanes, and combinations thereof.

31. The method of claim 26, wherein the method comprises reacting at least one precursor of formula (33) or (34) with at least one compound of formula (42), and Z 4 Corresponding to formula (47): in: -Y2 as defined in claim 1; - L4 and b'' are as defined in any one of claims 19 to 22; Preferably, the compound of formula (42) is an alicyclic polyepoxide selected from 7-oxabicyclo[4.1.0]hept-3-ylmethyl 7-oxabicyclo[4.1.0]heptane-3-carboxylate (UviCure S105), bis((3,4-epoxycyclohexyl)methyl)adipate (UviCure S128), compounds of formula (47a), (47b) or (47c), and combinations thereof 32. Precursors of formula (33) or (34) in: -Ar, R1, R2, R3, Q1 are as defined in any one of claims 1 to 7 and 9 to 10; -G is OH, a halogen atom or -OC(=O)-J; -J is alkyl or aryl, especially tert-butyl.

33. A process for preparing a precursor of formula (33) or (34) according to claim 32, wherein the process comprises reacting a phosphine oxide of at least one of formula (48) or (49) with at least one cyclic anhydride of formula (50) to provide a precursor according to formula (33) or (34), wherein G is OH: wherein Ar, R1, R2, R3, Q1 are as defined in any one of claims 1 to 7 and 9 to 10; The method optionally comprises the following additional steps: - reacting a precursor according to formula (33) or (34) wherein G is OH with an acyl halide of formula (51) to provide a precursor according to formula (33) or (34) wherein G is -OC(=O)-J Hal-C(=O)-J (51) wherein Hal is a halogen atom and J is an alkyl or aryl group, in particular a tert-butyl group; or - reacting a precursor according to formula (33) or (34) wherein G is OH with a halogenating agent, in particular thionyl chloride, to provide a precursor according to formula (33) or (34) wherein G is a halogen atom.

34. A process for preparing a photoinitiator of formula (1) or (2) according to any one of claims 1 to 7 and 9 to 23, wherein the process comprises reacting at least one precursor of formula (52) or (53) with a compound of at least one of formulae (35) to (42): R 14 -OH(35)R 15 -SH(36)NHR 16 R 17 (37) Z 1a -OH(38) Z 2 -SH(40)Z 3 -NH(R 18 )(41) in: - Ar, R1, R2, R3, R'1, R'2, Q1, Y1 and Y2 are as defined in any one of claims 1 to 7 and 9 to 10; -G is OH, a halogen atom or -OC(=O)-J; -J is alkyl or aryl, especially tert-butyl; -R 14 As defined in claim 1 or 11; -R 15 As defined in claim 1 or 15; -R 16 and R 17 As defined in claim 1 or 17; -Z 1a It is the hydroxyl-containing part; -Z 1b is the epoxide-containing portion; -Z 2 It is a thiol-containing moiety; -Z 3 It is an amine-containing moiety; -Z 4 It is the epoxide-containing portion.

35. The method of claim 34, wherein the method comprises reacting at least one precursor of formula (52) or (53) with at least one compound of formula (38), and Z 1a Corresponding to formula (43): wherein L1 and b are as defined in any one of claims 12 and 20 to 22; Preferably, the compound of formula (38) is a polyol selected from the group consisting of: Ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 1,3- or 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol Alcohol, neopentyl glycol, 2,4-diethyl-1,5-pentanediol, 3,3-butylethyl-1,5-pentanediol, cyclohexanediol, cyclohexane-1,4-dimethanol, norbornene dimethanol, norbornane dimethanol, tricyclodecanediol, tricyclodecane dimethanol, dicyclopentadiene glycol, hydroquinone bis(2-hydroxyethyl) ether, catechol, resorcinol, cashew diol, phloroglucinol, pyrogallol, tris(hydroxyphenyl)methane, tris(hydroxyphenyl) )ethane, bisphenol A, B, F or S, hydrogenated bisphenol A, B, F or S, trimethylolmethane, trimethylolethane, trimethylolpropane, di(trimethylolpropane), triethylolpropane, pentaerythritol, di(pentaerythritol), glycerol, di-, tri- or tetraglycerol, polyglycerol, di-, tri- or tetra(ethylene glycol), di-, tri- or tetra(1,2-propylene glycol), di-, tri- or tetra(1,3-propylene glycol), di-, tri- or tetra(1,4 -butylene glycol), poly(ethylene glycol), poly(propylene glycol), poly(trimethylene glycol), poly(tetramethylene glycol), poly(ethylene glycol-co-propylene glycol), sugar alcohols, i.e., erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, lactitol, fucitol, or iditol), dianhydrohexanols (i.e., isosorbide, isomannite, isoiditol), tris(2-hydroxyethyl)isocyanurate, hydroxylated vegetable oils, C 36 - dimer diols, polybutadiene polyols, polyester polyols, polyether polyols, polyorganosiloxane polyols, polycarbonate polyols, and alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof and derivatives obtained by ring-opening polymerization of ε-caprolactone initiated with one of the aforementioned polyols, and combinations thereof.

36. The method of claim 34, wherein the method comprises reacting at least one precursor of formula (52) or (53) with at least one compound of formula (39), and Z 1b Corresponding to formula (44): in: -Y1 as defined in claim 1; - L1 and b are as defined in any one of claims 12 and 20 to 22; Preferably, the compound of formula (39) is a polyepoxide selected from the group consisting of 1,2,3,4-diepoxybutane, 1,2,4,5-diepoxypentane, 1,2,5,6-diepoxyhexane, 1,2,7,8-diepoxyoctane, 1,2,9,10-diepoxydecane, ethylene glycol diglycidyl ether, 1,2- or 1,3-propylene glycol diglycidyl ether, 1,2-, 1,3- or 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,7-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether. Glycerol ether, 1,12-dodecanediol diglycidyl ether, 2-methyl-1,3-propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 2,2-diethyl-1,3-propylene glycol diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, 3,3-dimethyl-1,5-pentanediol diglycidyl ether, 2,4-diethyl-1,5-pentanediol diglycidyl ether, 3,3-butylethyl-1,5-pentanediol diglycidyl ether, di-, tri- or tetra(ethylene glycol) diglycidyl ether, di-, tri- or tetra(1,2-propylene glycol) diglycidyl ether, di-, tri- or tetra(1,3-propylene glycol) diglycidyl ether, di-, tri- or tetra( (1,4-Butanediol) diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly(trimethylene glycol) diglycidyl ether, poly(tetramethylene glycol) diglycidyl ether, poly(ethylene glycol-co-propylene glycol) diglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, di(trimethylolpropane) tetraglycidyl ether, pentaerythritol tetraglycidyl ether, cyclohexanedicarboxylic acid diglycidyl ester, cyclohexane diglycidyl ether, cyclohexane-1,4-dimethanol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether ethers, isosorbide diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, cashew diglycidyl ether, phloroglucinol triglycidyl ether, pyroglucinol triglycidyl ether, tris(hydroxyphenyl)methane triglycidyl ether, tris(hydroxyphenyl)ethane triglycidyl ether, bisphenol A, B, F or S diglycidyl ether, hydrogenated bisphenol A, B, F or S diglycidyl ether, diglycidyl phthalate, diglycidyl terephthalate, diglycidyl isophthalate, limonene dioxide (4-vinyl-1-cyclohexene diepoxide), epoxidized vegetable oils, triglycidyl isocyanurate, epoxy-functionalized polyorganosiloxanes, and combinations thereof.

37. The method of claim 34, wherein the method comprises reacting at least one precursor of formula (52) or (53) with at least one compound of formula (40), and Z 2 Corresponding to formula (45): wherein L2 and b' are as defined in any one of claims 16 and 20 to 22; Preferably, the compound of formula (40) is a polythiol selected from the group consisting of ethane-1,2-dithiol, propane-1,3-dithiol, butane-1,4-dithiol, hexane-1,6-dithiol, octane-1,8-dithiol, decane-1,10-dithiol, 1,8-dimercapto-3,6-dioxaoctane (DMDO), di-, tri- or polyethylene glycol di(ethanethiol), ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), 1,2- Propylene glycol bis(thioglycolate), 1,2-propylene glycol bis(3-mercaptopropionate), 1,2-propylene glycol bis(3-mercaptobutyrate), 1,3-propylene glycol bis(thioglycolate), 1,3-propylene glycol bis(3-mercaptopropionate), 1,3-propylene glycol bis(3-mercaptobutyrate), 1,4-butanediol bis(thioglycolate), 1,4-butanediol bis(thiopropionate), 1,4-butanediol bis(3-mercaptobutyrate), 1,6-hexanediol bis(thioglycolate), 1,6-hexanediol bis(3-mercapto esters), 1,6-hexanediol bis(3-mercaptobutyrate), di-, tri- or polyethylene glycol bis(thioglycolate), di-, tri- or polyethylene glycol bis(3-mercaptopropionate), di-, tri- or polyethylene glycol bis(3-mercaptobutyrate), di-, tri- or polypropylene glycol bis(thioglycolate), di-, tri- or polypropylene glycol bis(3-mercaptopropionate), di-, tri- or polypropylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(thioglycolate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(thioglycolate ... tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tris[2-(3-mercaptobutyryloxy)ethyl]isocyanurate, thiol-terminated polymers, mercapto-functionalized polyorganosiloxanes, and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof, and combinations thereof.

38. The method of claim 34, wherein the method comprises reacting at least one precursor of formula (52) or (53) with at least one compound of formula (41), and Z 3 Corresponding to formula (46): in: -R 18 As defined in claim 1; - L3 and b" as defined in any one of claims 18 and 20 to 22; Preferably, the compound of formula (41) is a polyamine selected from the group consisting of 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 2-methylpentamethylenediamine, ethylenediamine, 1,2- or 1,3-propylenediamine, 2-methyl-1,2-propylenediamine, 2,2-dimethyl-1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,3- or 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexanediamine, 2,5-dimethyl-2,5-hexanediamine, 2,2,4- or 2,4,4-trimethyl-1,6-hexanediamine, 1,7-heptanediamine, 1 ,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 2,4- or 2,6-hexahydrotoluenediamine, 2,4'- or 4,4'-diamino-dicyclohexylmethane, 1,3- or 1,4-cyclohexanediamine, 1,3- or 1,4-bis(methylamino)cyclohexane, 1,8-p-menthanediamine, hydrazine, phenylenediamine, 2,3-2,4-3,4- or 2,6-toluenediamine, o-, m- or p-xylylenediamine, 2,4'- or 4,4'-diaminodiphenylmethane, benzidine, N-(2-aminoethyl)-1,3-propylenediamine, N,N'-bis-(2-aminoethyl)piperazine, polyetheramines (especially For example D-230, D-400, D-2000, D-2010, D-4000, ED-600, ED-900, ED-2003, EDR-148, EDR-176, THF-100, THF-170, T403, T3000, T5000, RFD-270), amino-functional polyorganosiloxanes, and combinations thereof.

39. The method of claim 34, wherein the method comprises reacting at least one precursor of formula (52) or (53) with at least one compound of formula (42), and Z 4 Corresponding to formula (47): in: -Y2 as defined in claim 1; - L4 and b'' are as defined in any one of claims 19 to 22; Preferably, the compound of formula (42) is an alicyclic polyepoxide selected from 7-oxabicyclo[4.1.0]hept-3-ylmethyl 7-oxabicyclo[4.1.0]heptane-3-carboxylate (UviCure S105), bis((3,4-epoxycyclohexyl)methyl)adipate (UviCure S128), compounds of formula (47a), (47b) or (47c), and combinations thereof 40. Precursors of formula (52) or (53): in: - Ar, R1, R2, R3, R'1, R'2 and Q1 are as defined in any one of claims 1 to 7 and 9 to 10; -G is OH, a halogen atom or -OC(=O)-J; -J is alkyl or aryl, especially tert-butyl.

41. A process for preparing a precursor of formula (52) or (53) according to claim 40, wherein the process comprises reacting at least one precursor of formula (33) or (34) with at least one product of formula (32) to provide a precursor of formula (52) or (53), wherein G is OH: R'1-R'2 (32) in - Ar, R1, R2, R3, R'1, R'2 and Q1 are as defined in any one of claims 1 to 7 and 9 to 10; -G is OH; The method optionally comprises the following additional steps: - reacting a precursor according to formula (52) or (53) wherein G is OH with an acyl halide of formula (51) to provide a precursor according to formula (52) or (53) wherein G is -OC(=O)-J Hal-C(=O)-J (51) wherein Hal is a halogen atom and J is an alkyl or aryl group, in particular a tert-butyl group; or - reacting a precursor according to formula (52) or (53) wherein G is OH with a halogenating agent, in particular thionyl chloride, to provide a precursor according to formula (52) or (53) wherein G is a halogen atom.

42. The method of claim 41, wherein the product of formula (32) is selected from: - amines, in particular secondary amines (e.g. sec-butylamine, isobutylamine, tert-butylamine, cyclohexylamine, 1,1,3,3-tetramethylbutylamine, morpholine, piperidine, pyrrolidine, N-methylpiperazine, oxazolidine, thiazolidine, thiomorpholine, azepane), more particularly secondary cyclic amines (e.g. morpholine, piperidine, pyrrolidine, N-methylpiperazine, oxazolidine, thiazolidine, thiomorpholine, azepane); - alcohols, in particular primary alcohols (e.g. methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1-ol, 3-methylbutan-1-ol, 2,2-dimethylpropan-1-ol, hexan-1-ol, methylpentanol, 3-ethylbutan-1-ol, heptan-1-ol, octan-1-ol, 6-ethylhexan-1-ol, nonan-1-ol, decan-1-ol, dodecan-1-ol, tridecan-1-ol, isotridecan-1-ol, butoxyethanol, benzyl alcohol, methoxypolyethylene glycol); - mercaptans, in particular primary mercaptans (for example 1-hexanethiol, 1-octanethiol, 1-decanethiol, 1-dodecanethiol, methyl thioglycolate, ethyl thioglycolate, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate); - active methylene compounds, in particular β-diesters (for example dimethyl malonate, diethyl malonate, dipropyl malonate), β-ketoesters (for example ethyl acetoacetate), β-diketones (for example pentane-2,4-dione, cyclohexane-1,3-dione, 5,5-dimethylcyclohexane-1,3-dione), β-ketonitriles (for example 3-oxobutyronitrile), β-cyanoesters (for example methyl cyanoacetate, ethyl cyanoacetate), β-dinitriles (for example malononitrile).

43. A process for preparing a photoinitiator of formula (5) or (6) according to claim 8, wherein the process comprises reacting at least one precursor of formula (33) or (34) with at least one product of formula (54): HX-L0-X'H (54) in: -Ar, R1, R2, R3, Q1 are as defined in any one of claims 1 to 7 and 9 to 23; - X, X' and L0 as defined in claim 8, -G is OH, a halogen atom or -OC(=O)-J; -J is alkyl or aryl, especially tert-butyl; Preferably, the product of formula (54) is a compound having two functional groups independently selected from hydroxyl, amino and thiol, More preferably, the product of formula (54) is an amino alcohol (e.g., 2-aminoethanol, 2-(methylamino)ethanol, 2-(ethylamino)ethanol, 3-methylamino-1-propanol), an aminothiol (e.g., 2-aminoethanethiol), a mercaptoalcohol (e.g., 2-hydroxyethanethiol), a diol (e.g., ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,4-butanediol), a diamine (e.g., ethylenediamine, 1,2'-dimethylethylenediamine, 1,2'-diethylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, 1,2-diaminopropane, diethylenetriamine), an amino ester containing an amine group and an alcohol or mercapto group, or an amino acid (e.g., D / L-serine, D / L-cysteine, D / L-threonine, and esters thereof, in particular, their methyl or ethyl esters).

44. A photoinitiator composition comprising: - a mixture of at least two photoinitiators of formula (1) according to any one of claims 1 to 22; - a mixture of at least two photoinitiators of formula (2) according to any one of claims 1 to 23; a mixture of at least one photoinitiator of formula (1) according to any one of claims 1 to 22 and at least one precursor of formula (30) according to claim 25; or A mixture of at least one photoinitiator of formula (2) according to any one of claims 1 to 23 and at least one precursor of formula (31) according to claim 25.

45. A photoinitiator composition comprising a photoinitiator of formula (1) or (2) according to any one of claims 1 to 23 and a photoinitiator different from the photoinitiator of formula (1) or (2), in particular a photoinitiator selected from SpeedCure MBF (methyl benzoylformate), SpeedCure 73 (2-hydroxy-2-methyl-1-phenylpropanone), SpeedCure 7005 (polymeric benzophenone).

46. A method for photopolymerizing one or more ethylenically unsaturated compounds, the method comprising contacting the one or more ethylenically unsaturated compounds with a photoinitiator of formula (1) or (2) according to any one of claims 1 to 23 or a photoinitiator composition according to claim 44 or 45, and irradiating the mixture, in particular with UV, near-UV, visible light, infrared and / or near-infrared radiation.

47. A curable composition comprising: a) a photoinitiator of formula (1) or (2) according to any one of claims 1 to 23 or a photoinitiator composition according to claim 44 or 45; and b) Ethylenically unsaturated compounds.

48. The curable composition according to claim 47, wherein the composition further comprises a cationically polymerizable compound, in particular a cationically polymerizable compound selected from epoxides, oxetanes, oxolanes, cyclic acetals, cyclic lactones, thiirane, thietanes, spiroorthoesters, derivatives thereof and mixtures thereof.

49. The curable composition of claim 47 or 48, wherein the composition further comprises a polyol and / or a polythiol.

50. The curable composition according to any one of claims 47 to 49, wherein the composition further comprises additives, in particular additives selected from sensitizers, amine synergists, stabilizers, antioxidants, light barriers, polymerization inhibitors, foam inhibitors, flow or leveling agents, colorants, pigments, dispersants (wetting agents, surfactants), slip additives, fillers, thixotropic agents, matting agents, impact modifiers, waxes and mixtures thereof.

51. The curable composition of any one of claims 47 to 50, wherein the composition is an ink composition, a coating composition, an adhesive composition, a sealant composition, a molding composition, a dental composition, a nail polish composition, or a 3D printing composition.

52. A method for preparing a cured product, comprising curing the curable composition according to any one of claims 47 to 51, preferably by exposing the curable composition to radiation, such as UV, near UV, visible light, infrared and / or near infrared radiation.

53. A 3D printing method comprising printing a 3D article with the composition according to any one of claims 47 to 51, in particular printing layer by layer or continuously.

54. An inkjet printing method comprising jetting the curable composition according to any one of claims 47 to 51 onto a substrate.

55. A method of coating nails, wherein the method comprises applying a curable composition according to any one of claims 47 to 51 to the nail and curing the composition on the nail.

56. Use of a photoinitiator of formula (1) or (2) according to any one of claims 1 to 23 or a photoinitiator composition according to claim 44 or 45 as a photoinitiator or photoinitiating system in a radiation-curable composition, preferably a UV- or LED-curable composition.

57. Use of a photoinitiator of formula (1) or (2) according to any one of claims 1 to 23 or a photoinitiator composition according to claim 44 or 45 for curing one or more ethylenically unsaturated compounds.

58. Use of a photoinitiator of formula (1) or (2) according to any one of claims 1 to 23 or a photoinitiator composition according to claim 44 or 45 for obtaining a cured product with a reduced amount of extractables.

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