Photoinitiator combinations and uses thereof

Abstract

The present invention relates to a homogeneous liquid / fluid combination of photoinitiators with improved formability, reactivity, and surface cure properties, particularly a novel combination of an acylphosphine oxide and a ketocoumarin, optionally further combined with at least one co-initiator.

Description

[Technical Field]

[0001] The present invention relates to a homogeneous liquid / fluid combination of photoinitiators with improved compoundability, reactivity, and surface cure properties, particularly a novel combination of an acylphosphine oxide and a ketocoumarin, optionally further combined with at least one co-initiator. [Background technology]

[0002] Oxygen sensitivity is a major problem in the radical polymerization of acrylates, resulting in poor mechanical performance and sticky surfaces of the cured films.

[0003] Methods to improve oxygen inhibition can be divided into different strategies, as reported in Progress in Organic Coatings 77, (2014) 1789-1798: - Passivation of the coating by gaseous passivation (nitrogen, carbon dioxide). This is an expensive solution. - Use of high light irradiance lamps that generate a higher concentration of radicals. If the lamp's primary output coincides with the absorption maximum of the photoinitiator, this results in a faster curing process. The high energy consumption is an expensive solution. - Surface lamination with liquid or waxy additives to inhibit oxygen diffusion. After surface coating, excess products are produced. - Use of high concentrations of photoinitiators that exhibit high radical concentrations when the light is turned on. These radicals aid in the rapid consumption of oxygen. -Amines in the formulation participate in radical chain processes that consume oxygen. The trivalent phosphites (RO)P, (ArO)P, ArP, and RP (where R is a linear or branched alkyl group and Ar is an optionally substituted phenyl group) accelerate the cure rate in air. Unfortunately, the effectiveness of the trivalent phosphites is limited to 24 hours or less. -Addition of hydrogen donors to reduce oxygen inhibition. Typical hydrogen donors are thiols, silanes, stannanes, etc., which convert non-reactive peroxyl radicals into hydroperoxyls and new reactive radicals, as reported in Progress in Organic Chemistry 2014. Unfortunately, they have an unpleasant odor and are not easy to handle.

[0004] To overcome oxygen inhibition, another option has been to use a combination of two or more photoinitiators.

[0005] In the coatings industry, as reported by Liska in Progress in Organic Chemistry 77, (2014), 1789-1798 and WO 2005 / 035670, the problem is addressed by mixing a photoinitiator that absorbs light at >360 nm (MAPO (monoacylphosphine oxide) or BAPO (bisacylphosphine oxide)) with a lower wavelength photoinitiator (<350 nm) that matches the emission band of a mercury lamp. The anti-oxygen inhibition strategy combining an acylphosphine oxide and an α-hydroxyketone only works well with mercury lamps, and the mixture cannot cover the near-UV or visible LED emission spectrum.

[0006] Lalevee (Macromolecules 2018, 51, 4633-4641) proposed a mixture of 3-hydroperoxyflavone / N-phenylglycine that works under 405 nm LED.

[0007] Charge-transfer complexes are highly reactive in the radical polymerization of acrylates in air because the radical generation rate is fast enough to resist oxygen inhibition. Unfortunately, it is not fast enough to completely eliminate the onset of inhibition. Addition of iodonium salts improves the reaction, but results in the emission of unpleasant odors and post-cure yellowing.

[0008] Furthermore, as reported by W.A. Green in Industrial Photoinitiators, blends of photoinitiators without organic diluents or acrylic monomers (e.g., Irgacure® 1300 (BASF), Esacure® TZT (IGM Resins BV), Esacure KIP 100F (IGM Resins BV)) are commercially available for their ease of use. These liquid blends provide synergistic mixtures that improve surface cure, and blends of multiple photoinitiators are more effective than high concentrations of a single initiator. Unfortunately, the examples described in the literature do not work with visible LED lamps such as 395 nm, 400 nm, and 405 nm.

[0009] Molecular complex compounds comprising acylphosphine oxides and α-hydroxyketones have been proposed by Ciba Specialty Chemicals in U.S. Patent No. 5,942,290 for use with reactive photoinitiators. The crystalline molecular complexes contain very small amounts of impurities and are suitable for very sensitive applications when using Hg lamps.

[0010] Furthermore, as reported in the Journal Applied Polymer Science Vol. 112, 129-132, 2009, a mixture of acylphosphine oxide (MAPO (monoacylphosphine oxide) or BAPO (bisacylphosphine oxide)) and camphorquinone (CQ) was evaluated to determine possible synergistic effects. The results showed that when BAPO was mixed with CQ, the polymerization rate of the mixture was low, indicating antagonism. Summary of the Invention [Problem to be solved by the invention]

[0011] Therefore, there is a need for new photoinitiators that absorb energy over a broad wavelength range, are easy to handle, and have high performance. [Means for solving the problem]

[0012] The present invention provides a homogeneous liquid / fluid combination (hereinafter referred to as a "blend") of a photoinitiator that absorbs energy emitted from a near-UV or visible LED (the LED emits in the range of about 365 to about 420 nm) that, when combined with at least one ethylenically unsaturated compound that undergoes radical polymerization, is capable of curing a photopolymerizable composition. The homogeneous liquid / fluid combination according to the present invention is a clear mixture free of solid particles and / or droplets that separate at ambient temperature and pressure. DETAILED DESCRIPTION OF THE INVENTION

[0013] According to a preferred embodiment, the present invention provides a method for manufacturing a semiconductor device comprising: a. At least one liquid or solid photoinitiator belonging to the Norrish Type I photoinitiator group (at least one acylphosphine oxide); b. At least one liquid or solid photoinitiator belonging to the Norrish Type II photoinitiator group (at least one ketocoumarin); and c. optionally, one or more co-initiators and a photoinitiator combination comprising:

[0014] According to a preferred embodiment, any one or more of said co-initiators (c) are present.

[0015] According to a preferred embodiment, the present invention provides a method for manufacturing a semiconductor device comprising: a'. 60 to 90% by weight, preferably 70 to 85% by weight, of at least one Norrish Type I photoinitiator selected from acylphosphine oxides; b'. 1 to 20% by weight, preferably 5 to 20% by weight, of at least one, preferably one, Norrish type II photoinitiator selected from ketocoumarins; and c'. 0 to 20% by weight, preferably 5 to 20% by weight, of at least 1, preferably 1 co-initiator and a photoinitiator combination comprising:

[0016] According to a preferred embodiment, said at least one liquid or solid photoinitiator (a.) or (a'.) belonging to the Norrish Type I photoinitiator group is an acylphosphine oxide.

[0017] According to a preferred embodiment, said at least one photoinitiator (b.) or (b'.) belonging to the Norrish type II photoinitiator group is a ketocoumarin.

[0018] According to a preferred embodiment, the present invention provides a method for manufacturing a semiconductor device comprising: a''. 0-30% by weight, preferably 10-30% by weight, of a solid photoinitiator belonging to the Norrish Type I photoinitiator group, and 50-80% by weight of a liquid photoinitiator belonging to the Norrish Type I photoinitiator group (the Norrish Type I photoinitiator is preferably selected from acylphosphine oxides); b''. 5 to 20% by weight, preferably 10 to 15% by weight, of at least one photoinitiator belonging to Norrish type II photoinitiators, preferably selected from ketocoumarins; and c''. 10 to 20% by weight of at least one co-initiator and a photoinitiator combination comprising:

[0019] According to a preferred embodiment, the present invention provides a method for manufacturing a semiconductor device comprising: 0-30% by weight, preferably 10-30% by weight, of a solid photoinitiator belonging to the Norrish Type I photoinitiator group and 50-80% by weight of a liquid photoinitiator belonging to the Norrish Type I photoinitiator group; 5 to 20% by weight, preferably 10 to 15% by weight, of at least one photoinitiator belonging to Norrish type II photoinitiators; and 0 to 20% by weight, preferably 10 to 20% by weight, of at least one co-initiator and a photoinitiator combination comprising:

[0020] Unless otherwise specified, all percentages are expressed by weight of the component relative to the total weight of the combination. If water and / or solvent are present, their amounts are not included in the total weight of the combination for purposes of calculating the above percentages.

[0021] The terms "liquid," "fluid," and "solid" refer to the state of matter at ambient temperature and pressure.

[0022] Surprisingly, it has been newly discovered that mixtures of different radical Norrish type photoinitiators, as in the present invention, produce homogeneous, stable liquid combinations that are liquid / fluid even in the absence of a diluent. The combinations of the present invention are easy to handle and have shown rapid dissolution in formulations for curing.

[0023] definition Liquid combinations (or blends) A homogeneous, transparent, and liquid / fluid material at ambient temperature, consisting of a mixture of two or more photoinitiators of different Norrish types and optionally (and preferably) one co-initiator. Furthermore, the homogeneous liquid combinations of the present invention are liquid / fluid and exhibit excellent stability, even in the absence of organic diluents or acrylic monomers.

[0024] Photoinitiator A liquid or solid substance that undergoes a photoreaction upon absorption of light. The photoinitiators used in the present invention are radical Norrish types I and II.

[0025] Co-initiator A liquid or solid substance that promotes radical polymerization as a result of its interaction with a Norrish Type II photoinitiator. Examples of co-initiators are aromatic or aliphatic amines, such as tertiary amines or N,N-dialkylaniline derivatives, alcohols, ethers, or thiols.

[0026] Synergy Synergy generally refers to a mixture of two or more products that produces a photosensitivity benefit compared to each individual substance used alone (definition by W.A. Green - Industrial Photoinitators). Synergy is often found to be defined as a combined effect that is greater than the expected additive effect, as described in Frontiers in Pharmacology April 2017, Vol 8, Article 158.

[0027] Norrish Type I and Norrish Type II Photoinitiators Norrish Type I and Norrish Type II photoinitiators are well known in the art, see, for example, W. A Green, Industrial Photoinitiators, CRC Press; K. Dietliker, "Photoinitiators for Free Radical and Cationic Polymerization", SITA Technology Ltd; NJ Turro, Modern Molecular Photochemistry.

[0028] percentage Unless otherwise specified, % is by weight and is based on the total weight of the composition / mixture.

[0029] According to a preferred embodiment, the at least one liquid or solid Norrish type I photoinitiator (a) acylphosphine oxide is selected from the following formulae (I) to (IV):

[0030] Formula (I) [ka] (I) [where: R1, R2, R3, R 1a , R 2a and R 3a are, independently of each other, C1-C4 alkyl, C1-C4 alkoxy, or halogen; X is a direct single bond, and R4 is C1-C28 alkyl, substituted C1-C28 alkyl, or C1-C28 alkoxy; or X is O, NR5, S or a direct single bond; Y is O or S; n is 1; R4 is hydrogen, (CO)R6, (CO)OR6, (CO)NR5R6, (SO2)-R6, [Si(R7)(R8)] o -Si(R7)(R8)(R9), [Si(R7)(R8)-O] o -Si(R7)(R8)(R9), C1-C28 alkyl, C2-C28 alkyl interrupted by one or more O, NR5, S, (CO), (CO)O, or SO2, wherein said C1-C28 alkyl or interrupted C2-C28 alkyl is unsubstituted or is selected from the group consisting of OH, C6-C14 aryl, [Si(R7)(R8)] o -Si(R7)(R8)(R9), [Si(R7)(R8)-O] o -Si(R7)(R8)(R9), N(R5)2, [ka] TIFF0007823811000003.tif11471 propenoyloxy, 2-methylpropenoyloxy, C3-C12 cycloalkyl (unsubstituted or substituted with C1-C4 alkyl, C1-C4 alkoxy, or OH), C3-C12 cycloalkyl interrupted by one or more O, NR5, or S (said interrupted C3-C12 cycloalkyl is unsubstituted or substituted with C1-C4 alkyl, C1-C4 alkoxy, or OH), and C6-C14 aryl (unsubstituted or substituted with C1-C4 alkyl, C1-C4 alkoxy, or OH). or R4 is C6-C10 aryl (unsubstituted or substituted by one or more C1-C12 alkyl, C2-C20 alkyl interrupted by one or more O, C1-C12 alkoxy, or OH); or when X is NR5, R4 together with R5 and the N atom form a 5- or 6-membered saturated ring (uninterrupted or interrupted by O or NR5), said uninterrupted or interrupted ring being unsubstituted or substituted by one or more C1-C4 alkyl, C1-C4 alkoxy, or OH; A is PF6, SbF6, AsF6, or B(C6F5)4; R5 is hydrogen, (CO)R6, phenyl, C1-C12 alkyl, C2-C12 alkyl interrupted by one or more O (wherein said C1-C12 alkyl or interrupted C2-C12 alkyl is unsubstituted or substituted by one or more C3-C7 cycloalkyl, OH, or NCO), C3-C12 cycloalkyl (unsubstituted or substituted by one or more C1-C4 alkyl, C1-C4 alkoxy, OH, or NCO); R6 is C1-C12 alkyl, C2-C12 alkyl interrupted by one or more O, wherein said C1-C12 alkyl or interrupted C2-C12 alkyl is unsubstituted or substituted by one or more C3-C7 cycloalkyl, OH, NCO, or phenyl (NCO); or R6 is C3-C12 cycloalkyl, C2-C10 alkenyl (unsubstituted or substituted by one or more C1-C4 alkyl, OH, or C1-C4 alkoxy); or R6 is C6-C14 aryl (unsubstituted or substituted with C1-C12 alkyl, C1-C12 alkoxy, NCO, or NCO-substituted C1-C12 alkyl); or R5 and R6 together with the N atom form a 5- or 6-membered saturated ring (uninterrupted or interrupted by one or more O or NR5), wherein the uninterrupted or interrupted ring is unsubstituted or substituted by one or more C1-C4 alkyl, C1-C4 alkoxy, or OH; R7, R8, and R9 are, independently of one another, C1-C4 alkyl, C6-C14 aryl, or C1-C4 alkoxy; o is 0 to 10; Y1 is a direct single bond, O, S, NR5, O(CO)-*, or O(CO)-CH2-O-* (where the asterix indicates the attachment of group (A), (B), (D), or (E) to the phenyl group); Y2 is a direct single bond, O, S, or NR5; R 11 and R 12 are, independently of one another, C1-C10 alkyl, C2-C10 alkenyl, or phenyl-C1-C4 alkyl (unsubstituted or substituted by C1-C alkyl), or R 11 and R 12 together with the C atom to which they are attached are cyclohexyl or cyclopentyl; Z is OH or NR 13 R 14 and; Z1 is C1-C12 alkoxy or C2-C12 alkoxy interrupted by one or more O, wherein said C1-C12 alkoxy or interrupted C2-C12 alkoxy is unsubstituted or substituted by OH; R 13 and R14 are, independently of each other, C1-C12 alkyl, C1-C12 alkyl substituted by one or more OH or halogen; or R 13 and R 14 together with the N to which they are attached form a 5- or 6-membered unsaturated or saturated ring, said ring being uninterrupted or 15 being interrupted by); R 15 is C1-C4 alkyl; R 16 is hydrogen or C1-C4 alkyl; however, (i) when R1, R2, and R3 as C1-C4 alkyl are CH3 and X is O, then R4 as C1-C28 alkyl is not methyl, ethyl, n-propyl, 2-propyl, n-butyl, 1-methyl-propyl-1-yl, t-butyl, n-hexyl; (ii) when R1 and R3 as halogen are Cl, R2 is hydrogen, and X is O, then R4 as substituted C3-C10 aryl is not 4-butyl-phenyl; (iii) when R and R as C-C alkoxy are methoxy, R is hydrogen, X is NR, and R together with R and the N atom form a 5- or 6-membered saturated ring, the ring is not piperidyl-1; For example, as described in U.S. Patent Application Publication No. 2016 / 0039851.];

[0031] Formula (II) [ka] (II) [where: Ar1 and Ar2 are independently [ka] or naphthyl (unsubstituted or substituted one or more times by R1, R2, R3, or R'); R1 and R3 are, independently of each other, C1-C4 alkyl, C1-C4 alkoxy, or halogen; R2 is hydrogen, C1-C4 alkyl, halogen, C1-C4 alkoxy, or C2-C20 alkoxy interrupted by one or more O; Q is C1-C4 alkylene; R4 is methyl or ethyl; R' and R'' are, independently of each other, hydrogen or PG-Y-R'''-X-; PG is a polymerizable group or methyl or ethyl; Y is a direct single bond, O or S; X is a direct single bond, O or S; R''' is a direct single bond, C1-C20 alkylene, or C2-C20 alkylene interrupted by one or more O; R5 is C3-C30 alkyl (unsubstituted or substituted with OH and [ka] and wherein the substituted group is one or more groups selected from the group consisting of R5 is a C2-C28 alkyl interrupted by one or more O or C3-C8 cycloalkylene, wherein the interrupted C3-C28 alkyl is unsubstituted or is selected from the group consisting of OH and [ka] and Optionally, for example, a compound of formula R5-O (wherein R5 is as defined above) as disclosed in WO 2015 / 004566;

[0032] Formula (III) [ka] (III) [where: R1 is C1-C4 alkyl, C1-C4 alkoxy, or halogen; R2 is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, or halogen; and R3 is C1-C20 alkyl, cyclopentyl, cyclohexyl, phenyl-C1-C4 alkyl, or a group of the formula [ka] or R3 is naphthyl, biphenylyl, or an O-, S-, or N-containing 5- or 6-membered heterocyclic group, wherein said naphthyl, biphenylyl, or O-, S-, or N-containing 5- or 6-membered heterocyclic group is unsubstituted or substituted by C1-C4 alkyl, C1-C4 alkoxy, halogen, C1-C4 alkylthio; R4, R5, R6, R7, and R8 are, independently of one another, hydrogen, halogen, C1-C20 alkyl, cyclopentyl, cyclohexyl, C2-C12 alkenyl, C2-C20 alkyl interrupted by one or more discontinuous O atoms, phenyl-C1-C4 alkyl, C1-C20 alkoxy, or phenyl (unsubstituted or substituted by 1 or 2 C1-C4 alkyl or / and C1-C4 alkoxy substituents); For example, as disclosed in U.S. Pat. No. 6,251,963.]; and

[0033] Formula (IV) [ka] (IV) [where: each A independently represents O, S, or NR3; G is a multifunctional compound (core) G-(AH) m+n where each AH represents an alcohol, amino, or thiol group; m and n are both integers, and m+n is 3 to 10; m is 3 to 8; R1, R2 are each independently a group selected from C1-C18 alkyl, C6-C12 aryl, and C5-C12 cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, or an oxygen and / or nitrogen and / or sulfur atom-containing 5- or 6-membered heterocyclic group, each of which may be substituted by an aryl, alkyl, aryloxy, alkoxy, heteroatom, and / or heterocyclic group; R2 can be R1-(C=O)-; Y is O or S; R3 is hydrogen or C1-C4 alkyl; provided that the photoinitiator of formula (IV) does not contain a photocurable ethylenically unsaturated group; For example, as disclosed in U.S. Patent Application Publication No. 2017 / 0240659.]

[0034] The expression "polyfunctional compound" (or core) refers to a branched polyethoxylated chain having a molecular weight of 1500 Da or less, most preferably 500 Da or less. The core is preferably selected from among glycerol, ethoxylated / propoxylated glycerol, diglycerol, ethoxylated / propoxylated diglycerol, trimethylolpropane, ethoxylated / propoxylated trimethylolpropane, pentaerythritol, and ethoxylated / propoxylated pentaerythritol.

[0035] Acylphosphine oxide Norrish Type I photoinitiators include bis-(2,4,6-trimethylbenzoyl)phenylphosphine oxide (currently commercially available as Omnirad® 819); bis-(2,6-dimethoxybenzoyl)2,4,4-trimethylphosphine oxide (currently commercially available as Omnirad® 403); diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (currently commercially available as Omnirad® TPO); ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (currently commercially available as Omnirad® TPO-L); polymeric TPO-L (currently commercially available as Omnipol® TP); 2,5,8,11-tetraoxatridecan-13-yl-bis(2,4,6-trimethylbenzoyl)phosphinate (and its analogs and mixtures containing 3 or 5 ethoxy groups in the side chain); butyl bis(2,4,6-trimethylbenzoyl)phosphinate; and those disclosed in WO 2015 / 004566 and U.S. Patent Application Publication No. 2016 / 039851, and mixtures thereof.

[0036] According to a preferred embodiment, the at least one Norrish Type II ketocoumarin photoinitiator (b) is selected from the following formulae (V) to (VII):

[0037] Formula (V) [ka] [where: R1 and R2 are each independently a C1-C4 alkyl group; R3 is Branched C6-C20 alkyl groups or a mixture of linear and branched C6-C20 alkyl groups; C6-C20 alkyl-aryl, arylC6-C20 alkyl, C6-C20 alkyl-heteroaryl, heteroaryl-C6-C20 alkylene oxide, -COO-C6-C20 alkyl, and COOaryl Selected from:

[0038] Formula (VI) [ka] (VI) [where: G is the residue of an optionally alkoxylated polyhydroxy compound; m, n, and p are numbers, and m+n+p has a value from 2 to 10; p has a value between 0 and 8; x is an integer of 0 to 10, and when x is 0, the phenyl group is directly bonded to the carboxyl group; Each Y independently represents a direct single bond or a substituted or unsubstituted divalent linking group containing 1 to 14 carbon atoms; Z represents a radically polymerizable functional group; R3 each independently represents hydrogen, C1-C12 alkyl, substituted or unsubstituted phenyl, aryl or heteroaryl, C5-C6 cycloalkyl, C1-C12 cycloalkyl (substituted with -SH, -N(C1-C6 alkyl)2, piperidino, morpholino, piperazino, -OH, -O(C1-C12 alkyl), -COOH), or C1-C12 alkoxy; R1 and R2 are each independently hydrogen, C1-C12 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, C5-C6 cycloalkyl, C1-C12 alkyl (substituted with -SH, -N(C1-C6 alkyl)2, piperidino, morpholino, piperazino, -OH, -O(C1-C12 alkyl), COOH), or C1-C12 alkoxy; and

[0039] Formula (VII) [ka] (VII) [where: R1 is hydrogen or a substituted or unsubstituted C1-C12 alkyl group; Cou is expressed by the formula (a) [ka] (where, R2, R3, R4, and R5 are, independently of one another, hydrogen or -S-R7 (wherein R7 is substituted with hydrogen, C1-C12 alkyl, C2-C12 alkenyl, substituted or unsubstituted phenyl, aryl or heteroaryl, C5-C6 cycloalkyl, C1-C12 alkyl (SH, -N(C1-C6 alkyl)2, piperidino, morpholino, piperazino, -OH, -O(C1-C12 alkyl), -COOH); or C1-C12 alkoxy; and at least one of R2, R3, R4, and R5 is other than H; R6 is hydrogen, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms; or Cou is a substituted or unsubstituted group of the formula: [ka] , [ka] , or [ka] is a naphtha-coumarin group; With the proviso that when at least one of R2, R3, R4, and R5 is other than H, and Cou is (a), and at least one of R2, R3, R4, and R5 is C1-C12 alkyl, or Cou is (b), (c), or (d), then R1 is a substituted or unsubstituted C1-C12 alkyl group; For example, as disclosed in WO 2014 / 063997.]

[0040] Particularly preferred ketocoumarins are selected from 3-(4-dodecylbenzoyl)-5,7-dimethoxy-coumarin (now commercially available as Esacure® 3644, WO 2017 / 216699, IGM Resins BV) and other compounds described in said application, or from the acrylated ketocoumarins described in WO 2019 / 116176 (IGM Resins Italia), or from the ketocoumarins described in WO 2014 / 018826 (Sun Chemical Corporation).

[0041] Other preferred coumarins are coumarin, 3-phenylcoumarin, 3-benzoylcoumarin, 3-thenoylcoumarin, coumarin 3-carboxylic acid, 3-methylcoumarin, 7-hydroxycoumarin, 6-methylcoumarin, 4-hydroxycoumarin, 3-(4-cyanobenzoyl)coumarin, 3-(4-methoxybenzoyl)coumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-(2-benzofuroyl)-7-diethylaminocoumarin, 7-(diethylamino)-3-thenoylcoumarin, 3-(4-cyanobenzoyl)-5,7-dimethoxycoumarin, 3-(4-cyanobenzoyl)-7-methoxycoumarin, 5,7-dimethoxy-3-(4-methoxybenzoyl)coumarin, 5,7-dimethoxy-3-thenoylcoumarin, coumarin, 3-benzoyl-7-methoxycoumarin, 7-methoxy-3-(4-methoxybenzoyl)coumarin, 3-thenoyl-7-methoxycoumarin, 5,7-dimethoxycoumarin, 7-hydroxy-4-methylcoumarin, 4-methyl-7-dimethylaminocoumarin, 4-methyl-7-ethylaminocoumarin, 4-methylpiperidino[3.2-g]coumarin, 4-methyl-7-cyclohexylaminocoumarin, 4-trifluoromethyl-7-diethylaminocoumarin, 3-phenyl-4-methyl-7-diethylaminocoumarin, 3-(2'-n-methylbenzimidazole)-7-diethylaminocoumarin, 4-trifluoromethyl-6-methyl-7-ethylaminocoumarin, 3-phenyl-7-aminocoumarin, and those disclosed in WO 2014 / 018826 (Sun Chemical Patent).

[0042] The present invention also contemplates any combination of at least one compound of formulas (I) to (IV) and at least one compound of formulas (V) to (VII). The present invention also contemplates combinations of the preferred Norrish Type I and Norrish Type II photoinitiators described above. In particular, the combinations disclosed in the examples below are also preferred.

[0043] According to a preferred embodiment, the combination of the present invention comprises one or more co-initiators.

[0044] Typically, a co-initiator is a molecule that acts as a hydrogen donor. Known co-initiators include amines, alcohols, and thiols, and include, but are not limited to, aliphatic, cycloaliphatic, aromatic, aryl-aliphatic, heterocyclic, oligomeric, polymeric, acrylic, or methacrylic derivatives.

[0045] Examples of suitable co-initiators are bis-N,N-[4-dimethylaminobenzoyl)oxyethylene-1-yl]-methylamine (currently commercially available as Esacure® A198), ethyl-4-dimethylaminobenzoate (currently commercially available as Omnirad® EDB), 2-ethylhexyl-4-dimethylaminobenzoate (currently commercially available as Omnirad® EHA), N-phenylglycine, poly(ethylene glycol) bis(p-dimethylaminobenzoate) (currently commercially available as Omnipol® ASA), or acrylic amines (compounds currently commercially available as Photomer® 4250, Photomer® 4771, Photomer® 4775, Photomer® 4780), or the compounds disclosed in Example 4 of U.S. Patent Application Publication No. 2013 / 0012611.

[0046] The compounds listed above are merely examples of preferred photoinitiators or co-initiators and are not intended to limit the invention.

[0047] A preferred combination of the present invention is (a) at least one acylphosphine oxide selected from: phenylbis-(2,4,6-trimethylbenzoyl)phosphine oxide (Omnirad® 819); polymeric TPO-L (Omnipol® TP); 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Omnirad® TPO); (ocrituphosphoryl)bis-(mesitylmethanone) (referred to herein as "Compound 1"); and Bis-(2,4,6-trimethylbenzoyl)-phosphinic acid polyethylene glycol-monomethyl ether ester (referred to herein as "Compound 2"); (b) at least one ketocoumarin selected from the following: Esacure® 3644 (3-((4-dodecyl)benzoyl)-5,7-dimethoxycoumarin); Coumarin 3-(benzoyl)-7-ethyl sulfide (referred to herein as "Compound 3"); 3-((4-t-butyl)benzoyl)-7-methoxycoumarin (referred to herein as "Compound 4"); and 3-((4-t-butyl)benzoyl)β-naphthocoumarin (referred to herein as "Compound 5"); (c) at least one co-initiator selected from the following: 1H-Azepine-1-propanoic acid hexahydro-2,2-bis[[(1-oxo-2-propen-1-yl)oxylmethyl]butyl ester (Photomer® 4250); and 1,1,1-trimethylolpropane tri-(3-[N-methyl-N-phenylamino]propionate) The compound comprises:

[0048] A particularly preferred combination is Compound 1 and / or Compound 2 and Esacure® 3644, preferably with Photomer® 4250.

[0049] Preferably, the combination of the present invention does not include organic diluents or acrylic monomers.

[0050] When some of the components of the combination of the present invention are solids, the combination may be carried out by the following steps: 1) blending and stirring the combined liquid ingredients at ambient temperature; 2) heating the mixture at 40 to 80°C, preferably at 60°C; 3) adding the solid components of the formulation while stirring at 40 to 80°C, preferably 60°C, followed by stirring at 100 to 140°C, preferably 120°C, for about 1 hour, thus obtaining a clear solution; 4) Cooling the solution to ambient temperature, thus obtaining a clear liquid blend. It is prepared by a method comprising:

[0051] Alternatively, if all of the components of the combination are liquid, the blend can be obtained by simply mixing them at ambient temperature.

[0052] The liquid combinations of the present invention are suitable for fast photopolymerization of photocurable compositions with near UV or visible LED lamps.

[0053] The photoinitiator combinations of the present invention have been shown to exhibit synergistic effects between selected Norrish Type I and II photoinitiators. Indeed, acylphosphine oxides are fast photoinitiators, but are very sensitive to oxygen inhibition. Acylphosphine oxides are known to provide good through-cure due to photobleaching, but additives must be incorporated to improve surface cure.

[0054] Typically, those skilled in the art add amines as co-initiators because they have a beneficial effect on the polymerization rate. Acylphosphine oxides usually have a positive effect, but the improvement is not always significant. Surprisingly, the addition of small amounts of Norrish Type II photoinitiators, especially ketocoumarins such as the compound currently available as Esacure® 3644 (which absorbs in the wavelength range of the acylphosphine oxides), reliably and significantly improves the curing rate.

[0055] In accordance with the present invention, the combination is used to prepare a photocurable composition comprising an ethylenically unsaturated compound containing one or more olefinic double bonds.

[0056] Said compositions, comprising the combination of the invention and at least one ethylenically unsaturated compound, represent another subject of the present invention.

[0057] According to a preferred embodiment, the present invention relates to a photocurable composition comprising: i) 80 to 99% by weight of at least one ethylenically unsaturated compound; ii) 1 to 20% by weight of the combination according to the present invention The compound comprises:

[0058] Unless otherwise specified, all percentages are expressed by weight of the component relative to the total weight of the composition. If water or solvent is present, their amount is not included in the total weight of the composition for the purposes of calculating the above percentages.

[0059] Examples of suitable ethylenically unsaturated compounds (e.g., monomeric or oligomeric polyunsaturated compounds) having one double bond include alkyl or hydroxyalkyl (meth)acrylates, such as methyl, ethyl, butyl, 2-ethylhexyl, or 2-hydroxyethyl (meth)acrylate, and isobornyl acrylate. Silicon- or fluorine-modified resins, such as silicone acrylates, are also suitable. Further examples of suitable monomers include acrylonitrile, (meth)acrylonitrile, (meth)acrylamide, N-substituted (meth)acrylamide, styrene, alkylstyrenes, and halogenostyrenes, vinyl esters (e.g., vinyl acetate), vinyl ethers (e.g., isobutyl vinyl ether), N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylcarbazole, and vinyl chloride.

[0060] Further examples of suitable monomers having more than one double bond are ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate, bisphenol A diacrylate, 4,4'-bis-(2-acrylooxyethoxy)-diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, or tris-(2-acryloylethyl)isocyanurate.

[0061] Suitable examples of oligomeric polyunsaturated compounds are acrylated epoxy resins, acrylated or vinyl-ether or epoxy group-containing polyesters, acrylated polyurethanes, or acrylated polyesters.

[0062] Examples of compounds (i) that are particularly suitable for carrying out the present invention are esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers containing ethylenically unsaturated groups in the chain or in the side chain, such as unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers having (meth)acrylic groups in the side chain, and mixtures of one or more of such polymers.

[0063] Illustrative of unsaturated carboxylic acids or anhydrides useful in preparing the esters are (meth)acrylic acid, maleic anhydride, crotonic acid, itaconic acid, cinnamic acid, and unsaturated fatty acids such as linoleic acid and oleic acid. (Meth)acrylic acid is preferred.

[0064] Further suitable ethylenically unsaturated compounds are unsaturated polyamides obtained from unsaturated carboxylic acids and, preferably, aromatic, aliphatic, and alicyclic polyamides having 2 to 6 amino groups. Examples of such polyamides are ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,2-butylenediamine, 1,3-butylenediamine, 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di-(β-aminoethyl)ether, diethylenetriamine, triethylenetetraamine, and di-(β-aminoethoxy)- and di-(β-aminopropoxy)-ethane. Specific examples of such unsaturated polyamides are methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)ethane, and N-[(β-hydroxyethoxy)ethyl]-acrylamide.

[0065] Also suitable as ethylenically unsaturated compounds for the implementation of the present invention are unsaturated polyurethanes, such as aliphatic urethane diacrylates, for example, Photomer® 6009, aliphatic urethane triacrylates, for example, Photomer® 6008 or Photomer® 6010, and aliphatic urethane hexaacrylates, for example, Photomer® 6621. Further examples are aromatic urethane diacrylates, for example, Photomer® 6581, or aromatic urethane hexaacrylates, for example, Photomer® 6720.

[0066] In addition to the combination of the present invention and the ethylenically unsaturated compound, the composition of the present invention can further comprise, but is not limited to, a binder, which is advantageous when the photopolymerizable compound is a liquid or viscous substance. The binder is selected according to the field of use and the required properties. Suitable binders are acrylate and methacrylate homo- and copolymers, polyethers such as polyethylene oxide, and polyvinyl acetate. Further additives include wetting agents that improve the wettability of solids and dispersants that prevent particle aggregation, such as those in the BYK product line.

[0067] One of the key ingredients in ink formulations is artificial or natural fillers, which modify the rheological properties of the ink and increase color consistency. The role of fillers is to replace a certain percentage of expensive pigments and to positively influence the printability of the ink. Common fillers used in the production of printing inks are barium sulfate, aluminum hydroxide, magnesium carbonate, calcium carbonate, talc, clay, and silica.

[0068] Adhesion promoters are used to improve adhesion of UV inks on difficult substrates such as plastics, metals, PVC, polystyrene, aluminum, and glass. Examples of this type of additive are chelated titanates, BASF's Loxanol series, or DOXA's Addox series.

[0069] The ink, coating, or adhesive may comprise a lubricant to provide improved breakthrough properties. Examples of such lubricants are fluorocarbon oils or resins or functionalized silicone compounds.

[0070] Those skilled in the art will be fully capable of selecting other suitable ingredients for the compositions of the present invention.

[0071] The compositions of the present invention may also comprise one or more photosensitizers.

[0072] When one or more photosensitizers are added to the compositions of the present invention, they may be present in an amount of 0.05 to 12% by weight, preferably 0.1 to 10% by weight.

[0073] The homogeneous liquid combinations and compositions of the present invention comprise: Printing industry for producing screen printing ink, offset printing ink, flexographic printing ink, gravure printing ink, digital printing ink, white ink, etc.; The electronics industry for solder resists, etch resists, insulating layers, and inks for printed circuits, protective coatings, encapsulants, displays, and other manufacturing electronic components; Optical industry for optical fiber coatings, waveguides, and lenses; the production of three-dimensional objects, so-called 3D printing or additive manufacturing; glue Used in.

[0074] Examples of sensitizers are those commonly used in the art: aromatic carbonyl compounds, such as benzophenone, thioxanthone, anthraquinone, and 3-acylcoumarin derivatives, terphenyls, styryl ketones, and 3-(aroylmethylene)-thiazolines, camphorquinone, and eosin, rhodamine, and erythrosine dyes.

[0075] The combinations and compositions of the present invention are also suitable for inclusion in holographic applications, wood, vinyl, ceramic, metal, and plastic coatings.

[0076] The above-mentioned uses of the combinations and compositions of the invention are further subjects of the present invention.

[0077] Other subjects of the invention are printing and coating methods comprising the combinations and compositions of the invention, and the articles produced by said methods.

[0078] More specifically, the method of the present invention comprises: coating or printing a photopolymerizable composition according to the present invention onto a substrate; and photopolymerizing the coated or printed composition on the substrate with a light source; It comprises:

[0079] Preferably, the light source is a near-UV or visible LED.

[0080] As shown in the Examples section, the addition of even small amounts of a Norrish Type II photoinitiator of the present invention to a Norrish Type I photoinitiator (an acylphosphine) of the present invention provides unexpected results in terms of improved overall performance. Indeed, the addition of a Norrish Type II photoinitiator (especially a ketocoumarin) improves the degree of polymerization and reactivity of the surface portion of the coating (the portion in contact with air), which are weaknesses of a Norrish Type I photoinitiator (especially an acylphosphine) when used alone.

[0081] The invention is further described, without limitation, in the Examples section that follows.

[0082] [Examples] Identifying raw materials TIFF0007823811000018.tif157169

[0083] General Procedure A three-necked 250 ml flask is charged with the liquid ingredients at ambient temperature, then heated to 60° C. before adding the solid ingredients. The clear solution is stirred at 120° C. for 1 hour, then the blend is slowly cooled to ambient temperature and discharged.

[0084] Composition and Stability The compositions of the blends prepared according to the general procedure are reported in Table 1. Table 1: Blend composition (mass%) TIFF0007823811000019.tif77169 The stability of the blends was evaluated protected from light at 20° C. and 40° C. Stable blends were evaluated for reactivity, surface cure, and through cure in pigmented formulations.

[0085] Application results [Example]

[0086] Surface hardening and through hardening Test formulations were prepared by dissolving 6% by weight of the blend in a multifunctional acrylate-based industrial cyan offset ink containing 15-20% pentaerythritol [5EO] tetraacrylate, 5-10% di-trimethylolpropane tetraacrylate, 5-10% trimethylolpropane [3EO] triacrylate, 1-2% glyceryl [4PO] triacrylate, and 15-18% cyan pigment (15:3 phthalo blue) (all percentages are by weight). The test formulations were homogenized for 1 hour at ambient temperature using a mechanical stirrer and then applied to Leneta paper at a thickness of 1.5 μm using an IGT Retro-Tester device. The formulations were cured using a Phoseon Fire Power 395 nm UV-LED lamp (4 W / cm) at a distance of 5 mm. The surface cure was evaluated taking into account the number of passes at a speed of 100 m / min to obtain a dry surface (cotton test): the fewer the number of passes, the better the surface cure. Furthermore, the surface hardening was performed at approximately 1407 cm -1 The conversion of acrylate double bonds (DBC) in the acrylic acid esters was checked by FT-IR spectroscopy. The through cure test is a measurement of the complete ink cure obtained at a given speed, checked by the "thumb twist pressure test." Faster speed corresponds to more reactivity. The results are shown in Table 2.

[0087] Table 2: Surface and through cure of cyan industrial offset ink cured with an LED lamp at 395 nm (4 W / cm) in the presence of air. TIFF0007823811000020.tif53165

[0088] These results demonstrate that the inventive fluid of Example 11 provides either good through-cure performance or improved surface cure compared to Omnirad® 819, or especially compared to Compound 1 alone and the mixture of Compound 1 and Photomer® 4250. Furthermore, Esacure® 3644 and Photomer® 4250 showed very low reactivity at the same concentration (see Table 2).

[0089] The previous results were confirmed by FT-IR: Example 11 provides improved surface performance as the DBC% is greater than the other coatings after one pass at 100 m / min, as shown in Table 3. Table 3: Conversion (DBC%) by AT-IR measurement TIFF0007823811000021.tif44165 [Example]

[0090] Synergism of LFC3644 and other ketocoumarins with acylphosphine oxides. An LED-curable ink was prepared by adding 4.32 parts of acylphosphine oxide and 0.72 parts of Esacure® 3644 to an industrial cyan offset ink, and the mixture was stirred at ambient temperature for 1 hour until homogeneous. The ink was printed onto Leneta paper at a thickness of 1.5 μm using an IGT Retrotester device and cured with a Phoseon Flare Power 395 nm UV-LED lamp (4 W / cm) at a distance of 5 mm. The surface cure and through cure were checked as described in Example 1. The results are shown in Table 4.

[0091] Table 4: Reactivity of acylphosphine oxides and ketocoumarin Esacure® 3644 TIFF0007823811000022.tif47154

[0092] These results demonstrate that even in the absence of a co-initiator, liquid blends such as Compound 1 plus Esacure® 3644 can be obtained that perform well in either surface cure or through cure. Combinations of Compound 1 with other ketocoumarins were tested under similar conditions, and the results are shown in Table 5.

[0093] Table 5: Effect of ketocoumarins on compound 1 TIFF0007823811000023.tif46155

[0094] These results show that the cure rate is significantly increased in the presence of ketocoumarin compared to Compound 1 alone. The combination with Esacure® 3644 did not perform the best, but it does offer interesting advantages, such as good solubility and very low post-cure yellowing. [Example]

[0095] Synergistic effect of ketocoumarins on compound 1 in the presence of co-initiator Photomer® 4250 Blends of Compound 1, different ketocoumarins, and amine co-initiators were prepared by adding 4.32 parts of Compound 1, 0.72 parts of ketocoumarin, and 0.96 parts of co-initiator Photomer™ 4250 to an industrial cyan offset ink. A similar formulation without Photomer 4250 was prepared as a reference. Testing was performed as reported in the previous examples. The results are shown in Table 6.

[0096] Table 6: Synergistic activity of Compound 1 blends containing ketocoumarin and Photomer™ 4250 TIFF0007823811000024.tif67167(*)Maximum belt speed The results demonstrated that the presence of an amine co-initiator further improved the performance of the blend relative to the binary combination.

Claims

1. a. at least one liquid or solid photoinitiator belonging to the Norrish Type I photoinitiator group, which is at least one acylphosphine oxide; b. Formula (V) to (VII): Formula (V) 【Chemistry 1】 (V) [where: R 1 and R 2 are each independently a C1-C4 alkyl group; R 3 teeth, Branched C6-C20 alkyl groups or a mixture of linear and branched C6-C20 alkyl groups; C6-C20 alkyl-aryl, arylC6-C20 alkyl, C6-C20 alkyl-heteroaryl, heteroaryl-C6-C20 alkylene oxide, -COO-C6-C20 alkyl, and COOaryl Selected from: Formula (VI) 【Chemistry 2】 (VI) [where: G is the residue of an optionally alkoxylated polyhydroxy compound; m, n, and p are numbers, and m+n+p has a value from 2 to 10; p has a value from 0 to 8; x is an integer from 0 to 10, and when x is 0, the phenyl group is directly bonded to the carboxyl group; Each Y independently represents a direct single bond or a substituted or unsubstituted divalent linking group comprising 1 to 14 carbon atoms; Z represents a radical polymerizable functional group; R 3 are each independently hydrogen, C1-C12 alkyl, substituted or unsubstituted phenyl, aryl or heteroaryl, C5-C6 cycloalkyl, C1-C12 cycloalkyl (-SH, -N(C1-C6 alkyl) 2 , piperidino, morpholino, piperazino, -OH, -O(C1-C12 alkyl), -COOH-substituted), or C1-C12 alkoxy; R 1 and R 2 are each independently hydrogen, C1-C12 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, C5-C6 cycloalkyl, C1-C12 alkyl (-SH, -N(C1-C6 alkyl) 2 , piperidino, morpholino, piperazino, -OH, -O(C1-C12 alkyl), substituted with COOH, or C1-C12 alkoxy; and Formula (VII) 【Transformation 3】 (VII) [where: R 1 is hydrogen or a substituted or unsubstituted C1-C12 alkyl group; Cou is expressed by the formula (a) 【Chemistry 4】 (where, R 2 , R 3 , R 4 , and R 5 are, independently of one another, hydrogen or -SR 7 (where R 7 is hydrogen, C1-C12 alkyl, C2-C12 alkenyl, substituted or unsubstituted phenyl, aryl or heteroaryl, C5-C6 cycloalkyl, C1-C12 alkyl (SH, -N(C1-C6 alkyl) 2 , piperidino, morpholino, piperazino, —OH, —O(C1-C12 alkyl), —COOH), or C1-C12 alkoxy; and R 2 , R 3 , R 4 , and R 5 at least one of which is other than H; R 6 is hydrogen, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms; or Cou has the formula: 【Transformation 5】 、 【Transformation 6】 , or 【Transformation 7】 is a substituted or unsubstituted naphtha-coumarin group of the formula: However, R 2 , R 3 , R 4 , and R 5 is other than H, and Cou is (a) and R 2 , R 3 , R 4 , and R 5 is C1-C12 alkyl, or Cou is (b), (c), or (d), then R 1 is a substituted or unsubstituted C1-C12 alkyl group.] At least one photoinitiator belonging to the Norrish Type II photoinitiator group, which is at least one ketocoumarin selected from formulas (V) to (VII) above; and c. optionally, one or more co-initiators selected from aromatic or aliphatic amines, alcohols, ethers, or thiols; A photoinitiator combination comprising:

2. a'. 60 to 90% by weight, preferably 70 to 85% by weight, of at least one Norrish Type I photoinitiator selected from acylphosphine oxides; b'. 1 to 20% by weight, preferably 5 to 20% by weight, of at least one Norrish Type II photoinitiator selected from at least one ketocoumarin; and c'. 0 to 20% by weight, preferably 5 to 20% by weight, of at least one co-initiator 2. The combination of claim 1, comprising:

3. a''. 0 to 30% by weight, preferably 10 to 30% by weight, of a solid photoinitiator belonging to Norrish Type I photoinitiator selected from acylphosphine oxides, and 50 to 80% by weight of a liquid photoinitiator belonging to Norrish Type I photoinitiator; b''. 5 to 20% by weight, preferably 10 to 15% by weight, of at least one photoinitiator belonging to Norrish type II photoinitiators selected from ketocoumarins; and c''. 10 to 20% by weight of at least one co-initiator 3. The combination according to claim 1 or 2, comprising:

4. 4. The combination according to claim 1, wherein at least one liquid or solid acylphosphine oxide is selected from the group consisting of the following formulae (I) to (IV): Formula (I) 【Transformation 8】 (I) [where: R 1 , R 2 , R 3 , R 1a , R 2a and R 3a are, independently of each other, C1-C4 alkyl, C1-C4 alkoxy, or halogen; X is O, NR 5 , S, or a direct single bond; Y is O or S; n is 1; R 4 is hydrogen, (CO)R 6 , (CO)OR 6 , (CO)NR 5 R 6 , (SO 2 )-R 6 , [Si(R 7 )(R 8 )] o -Si(R 7 )(R 8 )(R 9 ), [Si(R 7 )(R 8 )-O] o -Si(R 7 )(R 8 )(R 9 ), C1-C28 alkyl, one or more O, NR 5 , S, (CO), (CO)O, or SO 2 wherein the C1-C28 alkyl or interrupted C2-C28 alkyl is unsubstituted or is selected from the group consisting of OH, C6-C14 aryl, [Si(R 7 )(R 8 )] o -Si(R 7 )(R 8 )(R 9 ), [Si(R 7 )(R 8 )-O] o -Si(R 7 )(R 8 )(R 9 ), N(R 5 ) 2 , 【Chemistry 9】 (A) 【change】 (B) 【change】 (C) 【change】 (D) 【change】 (E) 【change】 (F) 【change】 (G) 【change】 (H), propenoyloxy, 2-methylpropenoyloxy, C3-C12 cycloalkyl (unsubstituted or substituted with C1-C4 alkyl, C1-C4 alkoxy, or OH), one or more O, NR 5 or C3-C12 cycloalkyl interrupted by S, said interrupted C3-C12 cycloalkyl being unsubstituted or substituted by C1-C4 alkyl, C1-C4 alkoxy, or OH, and C6-C14 aryl being unsubstituted or substituted by C1-C4 alkyl, C1-C4 alkoxy, or OH; or R 4 is C6-C10 aryl (unsubstituted or substituted by one or more C1-C12 alkyl, C2-C20 alkyl interrupted by one or more O, C1-C12 alkoxy, or OH); or X is NR 5 If R 4 is R 5 and together with the N atom, a 5- or 6-membered saturated ring (uninterrupted or O or NR 5 wherein the uninterrupted or interrupted ring is unsubstituted or substituted by one or more C1-C4 alkyl, C1-C4 alkoxy, or OH; A is PF 6 , SbF 6 , AsF 6 , or B(C 6 F 5 ) 4 and R 5 is hydrogen, (CO)R 6 phenyl, C1-C12 alkyl, C2-C12 alkyl interrupted by one or more O (wherein said C1-C12 alkyl or interrupted C2-C12 alkyl is unsubstituted or substituted by one or more C3-C7 cycloalkyl, OH, or NCO), C3-C12 cycloalkyl (unsubstituted or substituted by one or more C1-C4 alkyl, C1-C4 alkoxy, OH, or NCO); R 6 is C1-C12 alkyl, C2-C12 alkyl interrupted by one or more O, wherein said C1-C12 alkyl or interrupted C2-C12 alkyl is unsubstituted or is substituted by one or more C3-C7 cycloalkyl, OH, NCO, or phenyl (substituted by NCO); or R 6 is C3-C12 cycloalkyl, C2-C10 alkenyl (unsubstituted or substituted by one or more C1-C4 alkyl, OH, or C1-C4 alkoxy); or R 6 is a C6-C14 aryl (unsubstituted or substituted with C1-C12 alkyl, C1-C12 alkoxy, NCO, or NCO-substituted C1-C12 alkyl); or R 5 and R 6 together with the N atom form a 5- or 6-membered saturated ring (uninterrupted or containing one or more O or NR 5 wherein the uninterrupted or interrupted ring is unsubstituted or substituted by one or more C1-C4 alkyl, C1-C4 alkoxy, or OH; R 7 , R 8 , and R 9 are, independently of each other, C1-C4 alkyl, C6-C14 aryl, or C1-C4 alkoxy; o is 0 to 10; Y 1 is a bond, O, S, NR 5 , O(CO)-*, or O(CO)-CH 2 -O-*, where the asterix indicates the attachment of group (A), (B), (D), or (E) to the phenyl group; Y 2 is a bond, O, S, or NR 5 and R 11 and R 12 are, independently of each other, C1-C10 alkyl, C2-C10 alkenyl, or phenyl-C1-C4 alkyl (unsubstituted or substituted with C1-C4 alkyl), or R 11 and R 12 together with the C atom to which they are attached are cyclohexyl or cyclopentyl; Z is OH or NR 13 R 14 and Z 1 is C1-C12 alkoxy or C2-C12 alkoxy interrupted by one or more O, wherein said C1-C12 alkoxy or interrupted C2-C12 alkoxy is unsubstituted or substituted by OH; R 13 and R 14 are, independently of one another, C1-C12 alkyl, C1-C12 alkyl substituted by one or more OH or halogen; or R 13 and R 14 together with the N to which they are attached form a 5- or 6-membered unsaturated or saturated ring, said ring being uninterrupted or 15 (interrupted by R 15 is C1-C4 alkyl; R 16 is hydrogen or C1-C4 alkyl; however, (i) R as C1-C4 alkyl 1 , R 2 , and R 3 is CH 3 and when X is O, R as C1-C28 alkyl 4 is not methyl, ethyl, n-propyl, 2-propyl, n-butyl, 1-methyl-propyl-1-yl, t-butyl, n-hexyl; (ii) R as halogen 1 and R 3 is Cl and R 2 is hydrogen and X is O, then R as substituted C-C aryl 4 is not 4-butyl-phenyl; (iii) R as C1-C4 alkoxy 1 and R 3 is methoxy and R 2 is hydrogen, and X is NR 5 and R 4 But R 5 and together with the N atom form a 5- or 6-membered saturated ring, said ring is not piperidyl-1; Formula (II) 【Chemistry 10】 (II) [where: Ar 1 and Ar 2 are independent of each other, 【Chemistry 11】 or naphthyl (unsubstituted or R 1 , R 2 , R 3 or R'; R 1 and R 3 are, independently of each other, C1-C4 alkyl, C1-C4 alkoxy, or halogen; R 2 is hydrogen, C1-C4 alkyl, halogen, C1-C4 alkoxy, or C2-C20 alkoxy interrupted by one or more O; Q is C1-C4 alkylene; R' and R'' are, independently of each other, hydrogen or PG-Y-R'''-X-; PG is a polymerizable group or methyl or ethyl; Y is a direct single bond, O or S; X is a direct single bond, O or S; R''' is a direct single bond, C1-C20 alkylene, or C2-C20 alkylene interrupted by one or more O; R 5 is a C3-C30 alkyl (unsubstituted or substituted with OH and 【Chemistry 12】 or R 5 is a C2-C28 alkyl interrupted by one or more O or C3-C8 cycloalkylene, wherein the interrupted C3-C28 alkyl is unsubstituted or is selected from the group consisting of OH and 【Chemistry 13】 and substituted with one or more groups selected from: Formula (III) 【Chemistry 14】 (III) [where: R 1 is C1-C4 alkyl, C1-C4 alkoxy, or halogen; R 2 is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, or halogen, and R 3 is C1-C20 alkyl, cyclopentyl, cyclohexyl, phenyl-C1-C4 alkyl, or a group of the formula 【Chemistry 15】 is a group, or R 3 is naphthyl, biphenylyl, or an O-, S-, or N-containing 5- or 6-membered heterocycle, wherein said naphthyl, biphenylyl, or O-, S-, or N-containing 5- or 6-membered heterocycle group is unsubstituted or substituted by C1-C4 alkyl, C1-C4 alkoxy, halogen, C1-C4 alkylthio; R 4 , R 5 , R 6 , R 7 , and R 8 are, independently of one another, hydrogen, halogen, C1-C20 alkyl, cyclopentyl, cyclohexyl, C2-C12 alkenyl, C2-C20 alkyl interrupted by one or more discontinuous O atoms, phenyl-C1-C4 alkyl, C1-C20 alkoxy, or phenyl (unsubstituted or substituted by one or two C1-C4 alkyl and / or C1-C4 alkoxy substituents); and Formula (IV) 【Chemistry 16】 (IV) [where: Each A is independently O, S, or NR 3 represents; G is the multifunctional compound (core) G-(AH) m+n where each AH represents an alcohol, amino, or thiol group; m and n are both integers, and m+n is 3 to 10; m is 3 to 8; R 1 , R 2 are, independently of one another, groups selected from C1-C18 alkyl, C6-C12 aryl, and C5-C12 cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, or an oxygen and / or nitrogen and / or sulfur atom-containing 5- or 6-membered heterocyclic group, each of which may be substituted by an aryl, alkyl, aryloxy, alkoxy, heteroatom, and / or heterocyclic group; R 2 is R 1 may be -(C=O)-; Y is O or S; R 3 is hydrogen or C1-C4 alkyl; However, the photoinitiator of formula (IV) does not contain a photocurable ethylenically unsaturated group.

5. A photocurable composition comprising at least one combination according to any one of claims 1 to 4, at least one ethylenically unsaturated compound, and optionally one or more additives.

6. 6. The photocurable composition of claim 5, wherein the at least one ethylenically unsaturated compound is selected from alkyl or hydroxyalkyl (meth)acrylates, oligomeric polyunsaturated compounds, acrylated epoxy resins, acrylated vinyl ethers, acrylated polyurethanes, and acrylated polyethers.

7. i) 80 to 99% by weight of at least one ethylenically unsaturated compound; ii) 1 to 20% by mass of the combination according to any one of claims 1 to 4 The photocurable composition according to claim 5 or 6, comprising:

8. 5. Use of a combination according to any one of claims 1 to 4 in the manufacture of printing inks, screen printing inks, gravure printing inks, solder resists, etch resists, offset printing inks, flexographic printing inks, gravure printing inks, inkjet inks, resist materials, insulators, encapsulants, image recording materials, solder resists, passivation layers, protective coatings, 3D printing objects and moulds, holographic applications, optical fibre coatings, wave guides and lenses, overprint varnishes, wood, vinyl, metal and plastic coatings.

9. 1. A method of photocuring photopolymerizable compositions, coatings, adhesives, and inks, comprising: Coating or printing the photopolymerizable composition of any one of claims 5 to 7 onto a substrate; and photopolymerizing the coated or printed composition on the substrate with a light source; A photocuring method comprising:

10. A method for producing a three-dimensional object, comprising photopolymerizing at least one photocurable composition according to any one of claims 5 to 7.

11. An industrial product, preferably a printed film, ink, coating, adhesive layer or three-dimensional object, obtained according to the method of claim 9 or 10.

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