Ketoquinolones as photoinitiators.

Abstract

The present invention relates to a novel class of photoinitiators and their use in photopolymerizable compositions. The present invention also relates to a method of photopolymerizing compositions containing the photoinitiators.

Description

[Technical Field]

[0001] The present invention relates to a novel class of photoinitiators and their use in photopolymerizable compositions. The present invention also relates to a method of photopolymerizing compositions containing the photoinitiators. [Background technology]

[0002] The dynamic growth of UV curing relies on continuous innovation to support this technology in overcoming ever-new challenges, which is reflected in the rapid development of new materials required for formulations. In particular, one of the key components is the photoinitiator (PI), whose role is to convert light into chemical energy in the form of reactive intermediates, which are radicals capable of initiating the radical polymerization of double bonds present in the formulation to be cured.

[0003] Developments in the field of photoinitiators are driven by a variety of factors. First, there is the continuous improvement of photoinitiators for existing applications such as coatings, inks, adhesives, and electronics, as no single photoinitiator can meet all application requirements, such as line speed, surface cure, color change after cure, and solubility. Second, the introduction of new lamps such as LED lamps has stimulated the development of photoinitiators tuned to their wavelengths. Third, an increasing number of photoinitiators are being banned due to toxicity or reproductive toxicity.

[0004] Therefore, there is a constant need to research new photoinitiators to mimic standard photoinitiators and overcome problems such as yellowing, increased linear speed, curing under LED lamps, and improved cure.

[0005] In recent years, several new types have been explored, and some examples thereof include acylgermanium photoinitiators (European Patent Application Publication No. 3150641 (Patent Document 1), European Patent Application Publication No. 2649981 (Patent Document 2)), benzoylphenyl telluride photoinitiators (Macromolecules, 2014, 47(16), pp. 5526-5531 (Non-Patent Document 1)), silicon-based photoinitiators (Japanese Patent Laid-Open No. 2010-229169 (Patent Document 3), Macromolecules, 2009, 5 42(16), pp. 6031-6037 (Non-Patent Document 2), Macromolecules, 2007, 40(24), pp. 8527-8530 (Non-Patent Document 3), Macromol. Rapid Commun., 2017, 38, 1600470 (Non-Patent Document 4), Macromolecules, 2017, 50(17), pp. 6911-6923 (Non-Patent Document 5), etc.

[0006] Ketoquinolones are a group of compounds known in the literature for their pharmacological properties. Although much effort has been made in recent years to improve their synthesis, no one has tested these compounds for their ability as photoinitiators. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] European Patent Application Publication No. 3150641 [Patent Document 2] European Patent Application Publication No. 2649981 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-229169 [Non-patent literature]

[0008] [Non-Patent Document 1] Macromolecules,2014,47(16),pp.5526-5531 [Non-patent document 2] Macromolecules,2009,5 42(16),pp.6031-6037 [Non-patent document 3] Macromolecules,2007,40(24),pp.8527-8530 [Non-patent document 4] Macromol.Rapid Commun.,2017,38,1600470 [Non-patent document 5] Macromolecules,2017,50(17),pp.6911-6923 Summary of the Invention [Problem to be solved by the invention]

[0009] Accordingly, a first object of the present invention is to provide a novel photocurable composition containing a ketoquinolone.

[0010] Another object of the present invention is to provide novel ketoquinolones, their use as photoinitiators, and photocurable compositions containing them.

[0011] It is yet another object of the present invention to provide a method for photocuring ethylenically unsaturated compounds with ketoquinolones and products produced thereby. [Means for solving the problem]

[0012] Surprisingly, the inventors discovered that a type of ketoquinolone generates radicals upon photoirradiation. Furthermore, by using appropriate substituents, the inventors also achieved photopolymerization under LEDs. This means that the absorption properties of this class of compounds can be tuned without affecting their reactivity. The new compounds were tested in various formulations and compared with known commercially available photoinitiators, demonstrating their superior performance.

[0013] Unexpectedly, the present inventors have found that certain ketoquinolones respond well to light sources in the range of 200 to 800 nm, preferably in the range of 200 to 500 nm, and more preferably to LED light sources emitting in the range of 350 to 420 nm, demonstrating novelty compared to the prior art.

[0014] Accordingly, the present invention relates to certain ketoquinolones useful as photopolymerization initiators, compositions containing the photopolymerization initiators, and methods for photopolymerizing compositions containing the ketoquinolones.

[0015] According to one aspect of the present invention, the present invention relates to a photocurable composition comprising: a) a polymerizable compound having a hydroxyl group and a hydroxyl group; a) 50 to 99.9% by mass, preferably 70 to 98.9% by mass, of at least one ethylenically unsaturated compound, based on the total mass of the composition; b) 0.1 to 35% by mass, preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass of at least one compound represented by the following formula (I): [ka] (I) wherein R1 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl; Qui is a quinolone group represented by the following formula (A): [ka] (A) [wherein R2, R3, R4, and R5 each independently represent hydrogen, substituted or unsubstituted C1-C20 alkyl, —N(C1-C6 alkyl)2, piperidino, morpholino, piperazino, —O—R8, —S—R8, —O—[CH2] n -COOR8, and -S-[CH2] n-COOR8 (wherein n is 1 to 8, and R8 is selected from hydrogen, substituted or unsubstituted C1 to C20 alkyl, C1 to C50 alkyl interrupted by one or more oxygen atoms and optionally having a terminal hydroxyl group, substituted or unsubstituted C2 to C12 alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and C5 to C6 cycloalkyl); R6 is hydrogen, hydroxyl, or a C1 to C4 alkyl group; and R7 is hydrogen or a C1 to C10 alkyl group); Or a substituted or unsubstituted benzoquinolone group represented by any of the following formulas (B) to (D): [ka] (B) [ka] (C) [ka] (D) (wherein R7 is hydrogen or a C1-C10 alkyl group, and the asterisk indicates the carbon atom bonded to the keto group represented by formula (I) above).

[0016] According to the present invention, the terms "photocuring," "photopolymerization," and related terms are synonymous.

[0017] As used herein, the expression "based on the total weight of the composition" means that the weight percentages of the compounds and additional components in the composition are calculated based on the sum of the weights of said compounds and said additional components, regardless of the fact that water and / or solvents may be present in the composition.

[0018] According to another aspect, the present invention relates to a compound of formula (Ia): [ka] (Ia) wherein R'1 is a substituted or unsubstituted aryl or a substituted or unsubstituted heteroaryl; Qui' is a quinolone group represented by the following formula (A'): [ka] (A') [wherein R'2, R'3, R'4 and R'5 each independently represent a substituted or unsubstituted C2-C20 alkyl, -N(C1-C6 alkyl)2, piperidino, morpholino, piperazino, -O-R8, -S-R8, -O-[CH2] n -COOR8, and -S-[CH2] n -COOR8 (wherein n is 1 to 8, and R8 is selected from hydrogen, substituted or unsubstituted C1 to C20 alkyl, C1 to C50 alkyl interrupted by one or more oxygen atoms and optionally having a terminal hydroxyl group, substituted or unsubstituted C2 to C12 alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and C5 to C6 cycloalkyl); R'6 is hydrogen or a C1 to C4 alkyl group; and R'7 is a C1 to C10 alkyl group); Or a substituted or unsubstituted benzoquinolone group represented by the following formula (B'), (C') or (D'): [ka] (B') [ka] (C') [ka] (D') (wherein R'7 is a C1-C10 alkyl group and the asterisk indicates the carbon atom bonded to the keto group of formula (Ia)).

[0019] According to yet another aspect of the present invention, the present invention relates to a photopolymerization method comprising the following steps (i) and (ii): (i) preparing or providing a photopolymerizable composition comprising (a) and (b) as defined above; (ii) photopolymerizing the composition of step (i) using a light source emitting light in the wavelength range of 200 to 800 nm. DETAILED DESCRIPTION OF THE INVENTION

[0020] In this description, the notation "alkyl" or "alkyl group", unless otherwise specified, means a saturated alkyl chain, linear or branched, containing the specified number of carbon atoms, and includes all possibilities for each number of carbon atoms in the alkyl group, i.e., alkyl groups with 3 carbon atoms include n-propyl and isopropyl, alkyl groups with 4 carbon atoms include n-butyl, isobutyl and tertiary butyl, alkyl groups with 5 carbon atoms include n-pentyl, 1,1-dimethyl-propyl, 2,2-dimethylpropyl and 2-methyl-butyl.

[0021] The notation "alkenyl" or "alkenyl group" means an unsaturated group containing 2 to 12 carbon atoms, preferably C3 to C12 carbon atoms, such as, for example, allyl, methallyl, or undecenyl.

[0022] The designation "cycloalkyl" or "cycloalkyl group", unless otherwise specified, means an aliphatic ring containing 5 or 6 carbon atoms, including cyclopentyl or cyclohexyl.

[0023] The designation "aryl" or "aryl group" includes, but is not limited to, for example, substituted or unsubstituted phenyl groups, substituted or unsubstituted naphthyl groups, anthracenyl groups, indenyl groups, fluorenyl groups, and the like.

[0024] The designation "heteroaryl" or "heteroaryl group" includes, but is not limited to, for example, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, pyran, pyridine, pyrrolidine, piperidine, indole, quinoline, isoquinoline, xanthene, carbazole, acridine, indeline, julolidine, and the like.

[0025] The expression "C1-C50 alkyl interrupted by one or more oxygen atoms" means that there is more than one oxygen atom present and that the oxygen atoms are separated from one another by at least one methylene group, i.e., the oxygen atoms are non-consecutive. Preferably, the oxygen atoms are separated by an ethylene or n-propylene chain. Preferably, there are 1 to 20, more preferably 2 to 18 oxygen atoms present. Examples include: -O-CH2-OCH3, -O-CH2CH2-OCH2CH3, -O-[CH2CHO] v CH3, -O-[CH2CH2O] v OH, -O-[CH2CH2O] v CH2CH3, -CH2-O-[CH2CH2O] v CH3 (where v is 1 to 24), -O-[CH2CH2CH2O] p OH, -O-[CH2CH2CH2O] p CH3, -O-[CH2CH2CH2O] p CH2CH3, -CH2-O-[CH2CH2CH2O] p CH3 (where p is 1 to 16).

[0026] When a group is substituted, the term "substituted" means that the group contains one or more substituents, preferably selected from halogen atoms, alkyl, cycloalkyl, alkoxy, alkylamino, dialkylamino, alkylthio or arylthio groups, and heterocyclic groups. Preferably, it is selected from methyl, ethyl, isopropyl, tert-butyl, phenyl, trifluoromethyl, cyano, acetyl, ethoxycarbonyl, carboxyl, carboxylate, amino, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, diisopropylamino, cyclohexylamino, dicyclohexylamino, acetylamino, piperidino, pyrrolidyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, phenoxy, hydroxyl, acetoxy, -POH, methylthio, ethylthio, i-propylthio, n-propylthio, phenylthio, mercapto, acetylthio, thiocyano, methylsulfinyl, methylsulfonyl, dimethylsulfonyl, sulfonic acid group, fluorine atom, chlorine atom, bromine atom, iodine atom, trimethylsilyl, triethylsilyl, trimethylstannyl, furyl, thienyl, pyridyl and morpholino. Among these substituents, electron-donating groups are preferred, and examples thereof include alkoxy groups such as methoxy, ethoxy, isopropoxy, tert-butoxy, and phenoxy; methyl, ethyl, isopropyl, hydroxyl, acetoxy, and benzoyloxy; thioalkyl groups such as methylthio, ethylthio, n-propylthio, i-propylthio, butylthio, and pentylthio; and arylthio groups such as phenylthio.

[0027] Unless otherwise specified, all percentages in this specification are by weight.

[0028] According to one embodiment, in formula (I) of the present description, R2, R3, R4 and R5 are selected from substituted or unsubstituted C2-C20 alkyl. According to a preferred embodiment, in formula (I) of the present description, it is preferred that at least one of the following conditions is met: - R1 is a substituted or unsubstituted aryl group, preferably a phenyl group, more preferably an aryl group substituted with a C1-C20 alkyl group, preferably a phenyl group substituted with a C1-C20 alkyl group; Qui is a quinolone group of formula (A) wherein at least one of R2, R3, R4 and R5 is not hydrogen, more preferably a quinolone group of formula (A) wherein at least one of R2, R3, R4 and R5 is -O-R8 or -S-R8, where R8 is C1-C20 alkyl, most preferably a quinolone group of formula (A) wherein R3 is -O-R8 or -S-R8, where R8 is C1-C20 alkyl; - R6 is hydrogen; R7 is C1-C8 alkyl.

[0029] According to a preferred embodiment, two, three or all of the above conditions are met simultaneously.

[0030] According to another preferred embodiment, in the compound of formula (I), Qui is a quinolone group of formula (A), R6 is hydrogen, and at least two of R2, R3, R4 and R5 are -O-R8 groups, and R8 is a C1-C20 alkyl group.

[0031] According to a preferred embodiment, in formula (Ia) of the present description, it is preferred that at least one of the following conditions is met: - R'1 is a substituted or unsubstituted aryl group, preferably a phenyl group, more preferably an aryl group substituted with a C1 to C20 alkyl group, preferably a phenyl group substituted with a C1 to C20 alkyl group; - Qui' is a quinolone group represented by formula (A'), in which at least one of R'2, R'3, R'4 and R'5 is -O-R8 or -S-R8, and R8 is C1-C20 alkyl; - R'6 is hydrogen; - R'7 is C1-C8 alkyl.

[0032] According to a preferred embodiment, two, three or all of the above conditions are met simultaneously.

[0033] According to another preferred embodiment, in the compound represented by formula (Ia), Qui' is a quinolone group represented by formula (A'), R'6 is hydrogen, and at least two of R'2, R'3, R'4 and R'5 are -O-R8 groups, and R8 is a C1 to C20 alkyl group, preferably a C1 to C10 alkyl group.

[0034] The compounds of formula (I) or (Ia) can be prepared according to conventional methods known to those skilled in the art, for example as reported in Eur. J. Org. Chem, (2018), pp. 896-900.

[0035] According to the present invention, the photoinitiator represented by formula (I) or (Ia) can be used to prepare a photocurable composition containing an ethylenically unsaturated compound (a).

[0036] The unsaturated compounds (a) may have one or more olefinic double bonds and may be either low molecular weight compounds (monomeric compounds) or high molecular weight compounds (oligomeric compounds).

[0037] Examples of suitable low molecular weight monomers (monomer compounds) having one double bond include alkyl- or hydroxyalkyl-containing acrylates or methacrylates, such as methyl-, ethyl-, butyl-, 2-ethylhexyl-, 2-hydroxyethyl- or isobornyl-containing acrylates, and methyl or ethyl methacrylate.

[0038] Further examples include silicone or fluorine modified resins such as silicone acrylates. Further examples of monomers include acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamides, styrene, alkylstyrenes and halogenostyrenes, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride.

[0039] Examples of monomers having more than one double bond include ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate, bisphenol A diacrylate, 4,4'-bis-(2-acryloyloxyethoxy)-diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris-(2-acryloylethyl)isocyanurate.

[0040] Examples of high molecular weight (oligomeric) unsaturated polymers include acrylated epoxy resins, acrylated polyesters, vinyl ether or epoxy group-containing polyesters, acrylated polyurethanes, and acrylated polyethers. Further examples of unsaturated oligomers include unsaturated polyester resins, usually prepared from maleic acid, phthalic acid, and one or more diols, and having a molecular weight of about 500 Da to 3,000 Da. Such unsaturated oligomers can also be called prepolymers.

[0041] Examples of compounds (a) particularly suitable for carrying out the present invention include esters of ethylenically unsaturated carboxylic acids with polyols or polyepoxides, and polymers containing ethylenically unsaturated groups in the chain or in side groups, such as unsaturated polyesters, polyamides, polyurethanes and their copolymers, alkyl resins; polybutadiene and butadiene copolymers; polyisoprene and isoprene copolymers; polymers and copolymers having (meth)acrylic groups in the side chain; and mixtures thereof.

[0042] Examples of unsaturated carboxylic acids or anhydrides useful in preparing the above esters include acrylic acid, methacrylic acid, maleic anhydride, crotonic acid, itaconic acid, cinnamic acid, and unsaturated fatty acids such as linoleic acid and oleic acid. Acrylic acid and methacrylic acid are preferred.

[0043] Examples of polyols that may also be esterified include aromatic, aliphatic and cycloaliphatic polyols, preferably aliphatic and cycloaliphatic polyols.

[0044] Aromatic polyols include, for example, hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl)propane, as well as novolaks and resols. Polyepoxides that can be esterified include those based on the above polyols, particularly the reaction products of aromatic polyols with epichlorohydrin. Suitable polyols also include polymers and copolymers containing hydroxyl groups in the polymer chain or in side groups, such as polyvinyl alcohol and its copolymers, or poly(hydroxyalkyl methacrylate esters) and its copolymers. Further suitable polyols are oligoesters with hydroxyl end groups.

[0045] Examples of aliphatic and cycloaliphatic polyols include alkylene diols preferably containing 2 to 12 carbon atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3-, or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycol preferably having a molecular weight of 200 Da to 1,500 Da, 1,3-cyclopentanediol, 1,2-, 1,3-, or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris(β-hydroxyethyl)amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol.

[0046] Further suitable ethylenically unsaturated compounds (a) are unsaturated polyamides obtained from unsaturated carboxylic acids and aromatic, aliphatic, and cycloaliphatic polyamines, preferably having 2 to 6, preferably 2 to 4, amino groups. Examples of such polyamines include ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3-, or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di-(β-aminoethyl)ether, diethylenetriamine, triethylenetetramine, di(β-aminoethoxy)- and di(β-aminopropoxy)ethane, etc. Other suitable polyamines are polymers and copolymers that can contain additional amino groups in the side chain, and oligoamides containing amino end groups.

[0047] Specific examples of such unsaturated polyamides include methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)ethane, and N-[(β-hydroxyethoxy)ethyl]-acrylamide.

[0048] Unsaturated polyurethanes are also suitable for the practice of the present invention, for example as component (a) derived from saturated or unsaturated diisocyanates and unsaturated or saturated diols. Polybutadiene, polyisoprene and copolymers thereof may also be used.

[0049] Suitable monomers include, for example, olefins such as ethylene, propene, butene, and hexene, (meth)acrylates, acrylonitrile, styrene, and vinyl chloride.

[0050] Polymers having unsaturated (meth)acrylate groups in the side chains can also be used as component (a). These may typically be reaction products of novolac-based epoxy resins with (meth)acrylic acid, homo- or copolymers of vinyl alcohol or its hydroxyalkyl derivatives esterified with (meth)acrylic acid, and homo- and copolymers of (meth)acrylates esterified with hydroxyalkyl (meth)acrylates.

[0051] The photocurable compositions of the present invention may also contain, in addition to compounds (a) and (b), one or more of the following components: (c) a photosensitizer, and / or (d) an accelerator / co-initiator, and / or yet another (e) photoinitiator, and / or (f) an additive.

[0052] The photocurable composition of the present invention can also be incorporated into a composition further containing a solvent such as water and / or an organic solvent.

[0053] The photosensitizer (c) can be contained in an amount in the range of 0.01 to 15% by mass, preferably in the range of 0.01 to 10% by mass, based on the total mass of the composition.

[0054] Examples of photosensitizers include 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, as well as eosin dyes, rhodamine dyes, and erythrosin dyes.

[0055] Examples of thioxanthone include thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthioxanthone, and 1-cyano-3-chlorothioxanthone. Xanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl-3-phenylsulfurylthioxanthone, 3,4-di[2-(2-methoxyethoxy)ethoxycarbonyl]thioxanthone, 1-ethoxycarbonyl-3-(1-methyl-1-morpholinoethyl)thioxanthone, 2-methyl-6-dimethoxymethylthioxanthone, 2-methyl -6-(1,1-dimethoxybenzyl)thioxanthone, 2-morpholinomethylthioxanthone, 2-methyl-6-morpholinomethylthioxanthone, N-allylthioxanthone-3,4-dicarboximide, N-octylthioxanthone-3,4-dicarboximide, N-(1,1,3,3-tetramethylbutyl)-thioxanthone-3,4-dicarboximide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-1-2-methoxythioxanthone, 6-ethoxycarbonyl Examples of such compounds include n-dodecyl-7-methyl-thioxanthone-3-carboxylate and N,N-diisobutyl-7-methyl-thioxanthone-3-carbamide, as well as thioxanthone-2-polyethylene glycol ester, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, and the like, as described in patent application PCT / EP2011 / 069514.Also suitable are polymeric thioxanthone derivatives (eg Omnipol® TX from IGM Resins BV, Genopol® TX-1 from Rahn AG, Speedcure® 7010 from Lambson Limited, etc.).

[0056] Examples of benzophenones include benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-(4-methylthiophenyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, methyl 2-benzoylbenzoate, 4-(2 -hydroxyethylthio)benzophenone, 4-(4-tolylthio)benzophenone, 4-benzoyl-N,N,N-trimethylbenzenemethanaminium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propanaminium chloride monohydrate, 4-(13-acryloyl-1,4,7,10,13-pentaoxatridecyl)benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyl)oxyethyl-benzenemethanaminium chloride, and the like. Polymeric benzophenone derivatives are also suitable (e.g. Omnipol® BP, Omnipol® 2702 and Omnipol® 682 from IGM Resins BV, Genopol® BP-2 from Rahn AG, Speedcure® 7005 from Lambson Limited, etc.).

[0057] Examples of 3-acylcoumarin derivatives include 3-benzoylcoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-di(propoxy)coumarin, 3-benzoyl-6,8-dichlorocoumarin, 3-benzoyl-6-chlorocoumarin, 3,3'-carbonyl-bis[5,7-di(propoxy)coumarin], 3,3'-carbonyl-bis(7-methoxycoumarin), 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-isobutylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-diethoxycoumarin, 3-benzoyl-5,7-dibutoxycoumarin, and 3-benzoyl-5,7-diisobutylcoumarin. di(methoxyethoxy)coumarin, 3-benzoyl-5,7-di(allyloxy)coumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-isobutyroyl-1,7-dimethylaminocoumarin, 5,7-dimethoxy-3-(1-naphthoyl)coumarin, 5,7-dimethoxy-3(1-naphthoyl)-coumarin, 3-benzoylbenzo[f]coumarin, 7-diethylamino-3-thienoylcoumarin, 3-(4-cyanobenzoyl)-5,7-dimethoxycoumarin, and the like, as well as those described in EP 2909243 and WO 2017 / 216699.

[0058] Examples of 3-(aroylmethylene)thiazolines include 3-methyl-1,2-benzoylmethylene-β-naphthothiazoline, 3-methyl-2-benzoylmethylene-benzothiazoline, and 3-ethyl-2-propionylmethylene-β-naphthothiazoline.

[0059] Examples of other aromatic carbonyl compounds include acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzil, etc., as described in WO 2013 / 164394; 2-acetylnaphthalene, 2-naphthalaldehyde, 9,10-anthraquinone, 9-fluorenone, dibenzosuberone, xanthone, 2,5-bis(4-diethylaminobenzylidene)cyclopentanone, α-(para-dimethylaminobenzylidene)ketones such as 2-(4-dimethylamino-benzylidene)-indan-1-one or 3-(4-dimethylaminophenyl)-1-indan-5-yl-propenone, 3-phenylthiophthalimide, N-methyl-3,5-di(ethylthio)phthalimide, etc. Particularly preferred are thioxanthones and 3-acylcumarines.

[0060] It has been observed that the above component (c) increases the activity of the photoinitiator (b) without shortening the shelf life of the composition. Furthermore, such compositions have the special advantage that the spectral sensitivity of the photoinitiator (b) can be shifted to any desired wavelength region by appropriately selecting the photosensitizer (c). Those skilled in the art can select an appropriate photosensitizer (c) to make the photoinitiator (b) operate in any desired wavelength region.

[0061] The accelerator / co-initiator (d) can be contained in an amount in the range of 0.2 to 15% by mass, preferably in the range of 0.2 to 8% by mass, based on the total mass of the composition.

[0062] Examples of suitable accelerators / co-initiators include alcohols, thiols, thioethers, amines or ethers having an available hydrogen attached to the carbon adjacent to the heteroatom, disulfide and phosphine, for example, as described in EP 438123 and GB 2180358.

[0063] Suitable amine accelerators / co-initiators include, but are not limited to, aliphatic, cycloaliphatic, aromatic, arylaliphatic, heterocyclic, oligomeric, or polymeric amines, such as primary, secondary, or tertiary amines, such as butylamine, dibutylamine, tributylamine, cyclohexylamine, benzyldimethylamine, dicyclohexylamine, N-phenylglycine, triethylamine, phenyl-diethanolamine, triethanolamine, piperidine, piperazine, morpholine, pyridine, quinoline, esters of dimethylaminobenzoic acid, Michler's ketone (4,4'-bis-dimethylaminobenzophenone) and its derivatives.

[0064] Amine-modified acrylate compounds can be used as amine accelerators / co-initiators.Examples of amine-modified acrylate compounds include the acrylates modified by reaction with primary or secondary amines, as described in US Patent No. 3,844,916, EP Patent Application Publication No. 280,222, US Patent No. 5,482,649 or US Patent No. 5,734,002.

[0065] Multifunctional amines and polymeric amine derivatives are also suitable coinitiators, some examples of which include Omnipol® ASA from IGM Resins BV, Genopol® AB-2 from Rahn AG, Speedcure® 7040 from Lambson Limited, or those described in U.S. Patent Application Publication No. 2013 / 0012611.

[0066] The other photopolymerization initiator (e) may be contained in an amount in the range of 0.5 to 15% by mass, preferably in the range of 1 to 10% by mass, based on the total mass of the composition.

[0067] Other suitable examples of photoinitiators (e) include camphorquinone, benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, dialkoxyacetophenones, α-hydroxyketones, α-aminoketones, 4-aroyl-1,3-dioxolanes, benzoin alkyl ethers and benzil ketals, e.g., benzil dimethyl ketal, ketosulfones, e.g., 1-[4-[(4-benzoyl-phenyl)-thio]-phenyl]-2-methyl-2-[(4-methyl-phenyl)-sulfonyl]-propan-1-one (IGM Resins Esacure® 1001 from BV), 3-ketocoumarin, for example as described in EP 2909243 and WO 2017 / 216699, phenylglyoxylate and its derivatives, dimeric phenylglyoxylate, peresters, for example benzophenonetetracarboxylic acid peresters (for example as described in EP 126541), acylphosphine photoinitiators (monoacylphosphine oxides, bisacylphosphine oxides), and acyl oxime ester photoinitiators, such as aryl acyl phosphine oxides, trisacyl phosphine oxides, trisacyl phosphine oxides, and polyfunctional mono- or bisacyl phosphine oxides; halomethyl triazines; hexaaryl bisimidazole / co-initiator systems, such as orthochlorohexaphenyl bisimidazole in combination with 2-mercaptobenzothiazole; ferrocenium compounds or titanocenes, such as dicyclopentadienyl-bis(2,6-difluoro-3-pyrrolophenyl)titanium; and O-acyl oxime ester photoinitiators.

[0068] Examples of α-hydroxyketones and α-aminoketones include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, and 2-hydroxy-1-{4 -[4-(2-hydroxy-2-methyl-propionyl)-phenoxy]-phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone).

[0069] Examples of O-acyloxime ester photoinitiators include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), or those described in GB 2339571.

[0070] Examples of acylphosphine photoinitiators include, but are not limited to, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-(2,4-dipentyloxyphenyl), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and ethyl (2,4,6-trimethylbenzoyl)(phenyl)phosphinate, phenyl(2,4,6-trimethylbenzoyl)phosphinic acid, glycerol ethoxylated triester (Omnipol® TP, manufactured by IGM Resins BV).

[0071] Examples of halomethyltriazine photopolymerization initiators include 2-[2-(4-methoxy-phenyl)-vinyl]-4,6-bis-trichloromethyl[1,3,5]triazine, 2-(4-methoxy-phenyl)-4,6-bis-trichloromethyl[1,3,5]triazine, 2-(3,4-dimethoxyphenyl)-4,6-bis-trichloromethyl[1,3,5]triazine, and 2-methyl-4,6-bis-trichloromethyl[1,3,5]triazine.

[0072] When the photocurable composition according to the present invention is used in a hybrid system (in this context, hybrid system means a mixture of a free radical curable system and a cationic curable system), a cationic photoinitiator may also be used as the photoinitiator (e). Examples of suitable cationic photoinitiators include aromatic sulfonium salts, phosphonium salts, or iodonium salts, as described in U.S. Pat. No. 4,950,581, or cyclopentadienyl arene-iron(II) complex salts, such as (η 6 -isopropylbenzene)(η 5 -cyclopentadienyl)iron(II) hexafluorophosphate or oxime-based photolatent acids.

[0073] Additives (f) include, for example, thermal initiators, binders, stabilizers, and mixtures thereof.

[0074] The photocuring process according to the invention is accelerated, in particular in the case of pigmented compositions, by adding as additional additive (f) a thermal initiator (a compound which generates free radicals when heated), such as an azo compound, for example 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), triazenes, diazosulfides, pentaazadienes, or a peroxy compound, for example a hydroperoxide or peroxycarbonate, for example tertiary-butyl hydroperoxide (as described, for example, in EP-A-245639).

[0075] A binder is also added to the photocurable composition of the present invention. The addition of a binder is particularly advantageous when the photocurable compound is a liquid or viscous substance. The amount of binder is, for example, 5 to 60% by mass, preferably 10 to 50% by mass, of the total mass of the composition. The binder is selected depending on the field of use and the required properties, such as developability in aqueous and organic solvent systems, adhesion to substrates, and sensitivity to oxygen.

[0076] Suitable binders are, for example, polymers having a weight average molecular weight (Mw) of about 5,000 to 2,000,000 Da, preferably 10,000 to 1,000,000 Da. Examples include homopolymers and copolymers of acrylates and methacrylates, such as copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, poly(methacrylic acid alkyl esters), poly(acrylic acid alkyl esters); cellulose esters and ethers, such as cellulose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose; polyvinyl butyral, polyvinyl formal, cyclized rubbers, polyethers, such as polyethylene oxide, polypropylene oxide, polytetrahydrofuran, polystyrene, polycarbonate, polyurethanes, chlorinated polyolefins, such as polyvinyl chloride, vinyl chloride / vinylidene chloride copolymers, copolymers of vinylidene chloride with acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, (ethylene / vinyl acetate) copolymers, such as polymers of polycaprolactam and poly(hexamethylene adipamide), polyesters such as poly(ethylene glycol terephthalate) and poly(hexamethylene glycol succinate).

[0077] Suitable stabilizers include, for example, thermal inhibitors such as hydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol, or sterically hindered phenols such as 2,6-di(tert-butyl)-p-cresol, which prevent premature polymerization. To enhance dark storage stability, for example, copper compounds such as copper naphthenate, copper stearate, or copper octenoate, phosphorus compounds such as triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite, or tribenzyl phosphite, quaternary ammonium compounds such as tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives such as N,N-diethylhydroxylamine can be used. To remove atmospheric oxygen during polymerization, paraffin or similar wax-like substances (insoluble in the polymer) can be used; these substances migrate to the surface at the onset of polymerization and form a transparent surface layer that blocks air penetration.

[0078] Light stabilizers, such as UV absorbers, for example, of the hydroxyphenylbenzotriazole, hydroxyphenylbenzophenone, oxalic acid amide, or hydroxyphenyl-s-triazine type, can be used, either alone or in mixtures, with or without sterically hindered amines (HALS).

[0079] The photocurable compositions according to the invention may also contain, as further additives (f), photoreducible dyes, such as xanthene, benzoxanthene, benzothioxanthene, thiazine, pyronine, porphyrin, or acridine dyes, and / or radiation-cleavable trihalomethyl compounds, as described, for example, in EP-A-445624.

[0080] Further customary additives (f) include optical brighteners, fillers, pigments (both white and colored), colorants, antistatic agents, wetting agents, or flow improvers, depending on the intended use. Additives customary in the art, such as antistatic agents, flow improvers, and adhesion promoters, can also be used.

[0081] Chain transfer agents customary in the art are also added to the compositions according to the invention, examples being mercaptans, amines and benzothiazoles.

[0082] The compositions of the present invention may contain colorants and / or colored pigments. Both inorganic and organic pigments can be used depending on the intended application. Such additives are known to those skilled in the art. Some examples include carbon black, iron oxides such as yellow iron oxide, red iron oxide, chrome yellow, chrome green, nickel titanium yellow, ultramarine blue, cobalt blue, bismuth vanadate, cadmium yellow, and cadmium red. Examples of organic pigments include mono- or bis-azo pigments and their metal complexes, phthalocyanine pigments, polycyclic pigments such as perylene, anthraquinone, thioindigo, quinacridone, or triphenylmethane pigments, and diketo-pyrrolo-pyrrole, isoindolinone, such as tetrachloroisoindolinone, isoindolinone, dioxazine, benzimidazolone, and quinophthalone pigments. In the formulation, pigments can be used alone or in mixtures.

[0083] Depending on the intended use, pigments are added to the formulation in amounts customary in the art, for example, in amounts of 0.1 to 30% by weight, or 10 to 25% by weight, based on the total weight of the composition.

[0084] The composition may contain, for example, a wide variety of organic colorants, such as azo dyes, methine dyes, anthraquinone dyes, and metal complex dyes, typically in concentrations of, for example, 0.1 to 20% by weight, particularly 1 to 5% by weight, based on the total weight of the composition.

[0085] The choice of additive is determined by the field of use and the properties desired for that field. The additives (f) above are known in the art and are therefore used in amounts customary in the art.

[0086] The photocurable composition of the present invention may contain water.

[0087] The photocurable compositions of the present invention can be used for a variety of purposes, for example as printing inks, e.g. screen printing inks, flexographic printing inks, offset printing inks and ink jet printing inks, as clear coats, e.g. as pigmented coats for wood or metal, as powder coatings, in particular as coating materials for paper, wood, metal or plastics, for structural and road markings, for reprographic processes, for holographic recording materials, in image recording processes or reproduction of printing plates using organic solvents or using aqueous alkaline media, as sunlight-curable paints for the production of screen printing masks, as dental filling materials, as adhesives, as pressure-sensitive adhesives, as laminating resins, as photoresists, e.g. galvano-resists, etch or permanent resists (both liquid and dry film). They can be used as photostructurable insulators and as solder masks for electronic circuits, in the manufacture of color filters for various types of display screens, or in the formation of structures during the manufacture of plasma and electroluminescent displays, or in the manufacture of optical switches, optical gratings (interference gratings), in the manufacture of three-dimensional articles by bulk curing (UV curing in transparent molds) or by stereolithography methods (as described, for example, in U.S. Pat. No. 4,575,330), in the manufacture of composite materials (for example styrene polyesters which may contain glass fibers and / or other fibers and other auxiliaries) or in three-dimensional printing methods well known to those skilled in the art, as resists in the coating or encapsulation of electronic components, or as coatings for optical fibers.

[0088] The photocurable compositions of the present invention are also suitable for the production of optical lenses, such as contact lenses or Fresnel lenses, for medical devices, aids or implants, and for the production of dry film coatings.

[0089] The photocurable compositions of the invention are also suitable for the preparation of gels with thermotropic properties, such as those described, for example, in DE-A-19700064 and EP-A-678534.

[0090] Various articles of manufacture comprising the compounds of formula (I) or (Ia) or photocurable compositions of the present invention are other subjects of the present invention.

[0091] The compounds and compositions according to the present invention are also used as free radical photoinitiators or photoinitiating systems for radiation curable powder coatings.

[0092] The photocurable compositions according to the invention are suitable, for example, as coating materials for all kinds of substrates (e.g., wood, textiles, paper, ceramics, glass, plastics (e.g., polyester, polyethylene terephthalate, polyolefins, and cellulose acetate), in particular for film-like substrates, and for substrates of metals (e.g., Al, Cu, Ni, Fe, Zn, Mg, or Co), and GaAs, Si, or SiO (to which a protective layer is applied or to which an image is applied, for example, by imagewise exposure).

[0093] According to another of its aspects, a further subject of the present invention is a method for photocuring photopolymerizable compositions and inks, the method comprising: (i) preparing or providing a photopolymerizable composition comprising: - compounds (a) and (b) as defined above; or - one or more selected from the compounds (a) and (b) as defined above and the components (c), (d), (e) and (f) as defined above; (ii) photopolymerizing the composition of step I using a light source.

[0094] According to a preferred embodiment, the photopolymerizable composition used in step (i) above comprises at least (a), (b) and (d).

[0095] The light source can be any of the most diverse types, emitting light in the wavelength range from about 200 nm to about 800 nm. Both point sources and planar radiators (lamp carpets) are suitable. Examples include carbon arc lamps, xenon arc lamps, medium-, high- or low-pressure mercury arc radiators (optionally doped with metal halides (metal halide lamps)), microwave-excited metal vapor lamps, excimer lamps, actinic fluorescent tubes, fluorescent lamps, argon incandescent lamps, flash lamps, photographic floodlights, light-emitting diodes (LEDs), electron beams, X-rays and lasers.

[0096] According to one embodiment, the light source includes UV light in at least one of the ranges UVA, UVB and UVC.

[0097] According to a preferred embodiment, the light source is an LED light source, and particularly preferred are LED light sources that emit light at wavelengths between 365 nm and 420 nm, more preferably at wavelengths of 365 nm, 385 nm and 395 nm.

[0098] According to the invention, the distance between the lamp and the substrate to be exposed may vary depending on the intended use and the type and strength of the lamp, and is, for example, from 0.1 cm to 150 cm, preferably from 1 cm to 50 cm.

[0099] The photopolymerizable composition can also be applied onto a substrate that already contains a coating or printed layer, and after photopolymerization with the light source, the photopolymerizable composition can be overprinted or overcoated with one or more compositions suitable for printing or coating.

[0100] The product obtained by applying the photopolymerizable composition to the substrate as described above by coating or printing as described above and photopolymerizing it with the light source as described above, with or without further finishing the product by further coating or printing, is a further subject of the present invention.

[0101] Thus, the present inventors have surprisingly discovered that the compounds represented by formulas (I) and (Ia) are effective as photopolymerization initiators and have measured their activity for the first time. Furthermore, the present inventors have found that the compounds represented by formulas (I) and (Ia) are highly reactive to LED lamps in both transparent and pigmented systems.

[0102] The present invention will now be described in more detail by the following illustrative, non-limiting examples.

[0103] In the event of a conflict between the chemical name and the chemical structure, the chemical structure shall prevail.

[0104] The wavy bond below means that both cis and trans isomerism is possible. [ka]

[0105] Example 1 1 H NMR spectra were recorded on a Bruker Avance 400 MHz or a Bruker DMX 500 MHz or a Bruker DMX 600 MHz. Infrared spectra were recorded on an FT-IR 430 - Jasco. [Example]

[0106] [ka] Synthesis of 19.22 g (156.06 mmol) of m-anisidine and 25.00 g (130.07 mmol) of ethyl benzoylacetate were dissolved in 75 mL of N,N-dimethylformamide. The reaction mixture was stirred at 150 °C for 4 hours, and the ethanol was removed by distillation. The reaction progress was monitored by TLC. After completion of the reaction, the mixture was cooled, poured into 625 mL of 6 M hydrochloric acid, and extracted with 375 mL of diethyl ether. The organic layer was washed twice with 375 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure to give 27.92 g of a yellow oil (80% yield). 1 H-NMR(CDCl3,δ ppm):3.80(s,3H),4.10(s,2H),6.68(d,1H),7.08(d,1H),7.22(t,1H),7.31(s,1H),7.51(t,2H),7.64(t,1H),8.02(d,2H),9.30(br s,1H) [Example]

[0107] [ka] Synthesis of To a warm solution containing 22.06 g (81.92 mmol) of the product from Example 1 and 10.83 g (81.95 mmol) of trans-cinnamaldehyde in 220 mL of toluene, 0.698 g (8.197 mmol) of piperidine, 0.492 g (8.193 mmol) of acetic acid, and 11.03 g of anhydrous sodium sulfate were added, in order. The reaction mixture was refluxed under a nitrogen atmosphere for 1 hour. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was cooled, poured into 300 mL of brine, and extracted with 220 mL of ethyl acetate. The organic layer was washed three times with 300 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation to give 31.40 g of crude product as a mixture of two regioisomers.

[0108] The resulting crude product was dissolved in 310 mL of anhydrous tetrahydrofuran and cooled to 0 °C. Then, 9.66 g (86.09 mmol) of potassium tert-butoxide was added portionwise slowly with stirring. After stirring for 10 minutes, 12.81 g (90.25 mmol) of iodomethane was carefully added to the reaction mixture. The resulting mixture was then stirred at room temperature under a nitrogen atmosphere for 1.5 hours. The progress of the reaction was monitored by TLC. After the reaction was complete, the mixture was poured into 150 mL of saturated ammonium chloride solution, diluted with 150 mL of water, and extracted with 300 mL of ethyl acetate. The organic layer was washed twice with 300 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation to give 32.12 g of crude product. This crude product was used in the next step without further purification. [Example]

[0109] [ka] Synthesis of To a solution containing 4.55 g (11.45 mmol of crude product) of the crude product of Example 2 in 135 mL of chlorobenzene, 9.16 g (68.70 mmol) of aluminum chloride was added portionwise slowly with stirring. The resulting mixture was gradually heated to 120 °C and then stirred at this temperature for 1.5 hours. The progress of the reaction was monitored by TLC. After the reaction was complete, the mixture was cooled, poured into 450 mL of ice water, and extracted four times with 100 mL of dichloromethane / methanol (80:20). The organic layer was collected, and the solvent was removed by distillation under vacuum. The crude product was solidified by treatment with 55 mL of toluene / cyclohexane (30:70), and the solid was washed with stirring at 100 °C for 15 minutes. The mixture was then cooled and filtered to give 2.56 g of an off-white solid, which was recovered (80% yield). 1 H-NMR(DMSO-d6,δ ppm):3.55(s,3H),6.82(dd,1H),6.88(d,1H),7.50(t,2H),7.62(t,1H),7.70(d,1H),7.79(d,2H),8.10(s,1H) [Example]

[0110] [ka] Synthesis of To a solution containing 3.20 g (11.46 mmol) of the product prepared in Example 3 in 35 mL of N,N-dimethylformamide, 4.75 g (34.37 mmol) of potassium carbonate, 0.34 g (2.27 mmol) of sodium iodide, and 4.43 g (22.94 mmol) of 2-ethylhexyl bromide were added, in that order. The reaction mixture was stirred at 80 °C for 8 hours. The reaction progress was monitored by TLC. After completion of the reaction, the mixture was cooled, poured into 200 mL of water, and extracted with 100 mL of toluene. The organic layer was washed three times with 100 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was purified by flash column chromatography on silica gel (petroleum ether / ethyl acetate (80:20)) and then crystallized from cyclohexane to give 2.50 g of a white solid (56% yield). 1 H-NMR(CDCl3,δ ppm):0.90-0.98(m,6H),1.35(m,4H),1.40-1.58(m,4H),1.80(m,1H),3.70(s,3H),3.9 8(m,2H),6.80(d,1H),6.88(dd,1H),7.43(t,2H),7.55(m,2H),7.85(d,2H),7.95(s,1H) [Example]

[0111] [ka] Synthesis of To an ice-cooled solution containing 44.00 g (327.82 mmol) of isobutylbenzene and 27.02 g (344.20 mmol) of acetyl chloride in 200 mL of dichloromethane, 45.90 g (344.23 mmol) of aluminum chloride was added portionwise slowly with stirring. The resulting mixture was stirred at room temperature under a nitrogen atmosphere for 1 hour. After the reaction was complete, the mixture was poured into 800 mL of ice-water. The organic layer was separated, washed twice with water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure to give 57.45 g of a pale yellow oil (99% yield). 1 H-NMR(CDCl3,δ ppm):0.90(d,6H),1.90(m,1H),2.52(d,2H),2.57(s,3H),7.21(d,2H),7.86(d,2H) [Example]

[0112] [ka] Synthesis of To a mixture containing 50.00 g (283.67 mmol) of the product from Example 5 and 255.50 g (2836.37 mmol) of dimethyl carbonate in 240 mL of toluene, 16.90 g (312.85 mmol) of sodium methoxide was added portionwise over 20 minutes while stirring at 90°C. The mixture was stirred at 90°C for 1 hour, and methanol was removed by distillation. After stirring for 1 hour, a solution containing 53.50 g (593.92 mmol) of dimethyl carbonate in 50 mL of toluene was added to the mixture. The temperature was then increased again to 90°C, and an additional 16.90 g (312.85 mmol) of sodium methoxide was added portionwise over 20 minutes. The mixture was stirred at 90°C for an additional 1 hour, and methanol was removed by distillation. After the reaction was complete, the mixture was cooled, poured into 600 mL of 12% hydrochloric acid, and extracted with 200 mL of ethyl acetate. The organic layer was washed twice with 300 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure to give 66.52 g of a yellow oil (100% yield). 1H-NMR(CDCl3,δ ppm):0.89(d,6H),1.90(m,1H),2.52(d,2H),3.73(s,3H),3.98(s,2H),7.23(d,2H),7.85(d,2H) [Example]

[0113] [ka] Synthesis of 8.20 g (53.53 mmol) of 3,4-dimethoxyaniline and 11.40 g (48.66 mmol) of the product from Example 6 were dissolved in 120 mL of N,N-dimethylformamide. The reaction mixture was stirred at 150 °C for 3 hours, and the methanol was removed by distillation. The reaction progress was monitored by TLC. After completion of the reaction, the mixture was cooled, diluted with 300 mL of toluene / ethyl acetate (60:40), and poured into 500 mL of 6 M hydrochloric acid. The organic layer was separated, washed three times with 500 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure to give 17.00 g of a gray solid (98% yield). 1 H-NMR(CDCl3,δ ppm):0.90(d,6H),1.90(m,1H),2.52(d,2H),3.84(s,3H),3.87(s,3H),4.07(s, 2H),6.80(d,1H),7.01(dd,1H),7.27(d,2H),7.30(d,1H),7.93(d,2H),9.25(br s,1H) [Example]

[0114] [ka] Synthesis of To a warm solution containing 17.00 g (47.83 mmol) of the product from Example 7 and 6.32 g (47.82 mmol) of trans-cinnamaldehyde in 200 mL of toluene, 0.407 g (4.78 mmol) of piperidine, 0.287 g (4.78 mmol) of acetic acid, and 8.50 g of anhydrous sodium sulfate were added, in that order. The reaction mixture was refluxed under a nitrogen atmosphere for 1 hour. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was cooled, poured into 400 mL of brine, and extracted twice with 200 mL of dichloromethane. The organic layer was washed three times with 200 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation to give 22.40 g of crude product as a mixture of two regioisomers. This crude product was used in the next step without further purification. [Example]

[0115] [ka] Synthesis of To an ice-cooled solution containing 22.40 g (47.70 mmol of crude product) of the crude product from Example 8 in 300 mL of anhydrous tetrahydrofuran, 5.77 g (51.42 mmol) of potassium tert-butoxide was added portionwise slowly with stirring. After stirring for 10 minutes, 7.65 g (53.90 mmol) of iodomethane was carefully added to the reaction mixture. The resulting mixture was then stirred at room temperature under a nitrogen atmosphere for 1.5 hours. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was poured into 200 mL of saturated ammonium chloride solution, diluted with 200 mL of water, and extracted with 300 mL of ethyl acetate. The organic layer was washed twice with 400 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent removed by vacuum distillation to give 23.00 g of crude product, which was used directly in the next step. [Example]

[0116] [ka] Synthesis of To a solution of 23.00 g (47.56 mmol of crude product) of the crude product from Example 9 in 460 mL of dichloromethane, 34.06 g (354.39 mmol) of methanesulfonic acid was slowly added with stirring. After stirring for 10-15 minutes at room temperature, the reaction mixture was poured into 800 mL of water. The organic layer was separated, washed twice with 800 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was purified by flash column chromatography on silica gel (toluene / ethyl acetate (90:10)) and then crystallized from cyclohexane to give 10.11 g of an off-white solid (44% yield). 1 H-NMR(CDCl3,δ ppm):0.90(d,6H),1.90(m,1H),2.52(d,2H),3.46(s,3H),3.83(s,3H),3.95(s,3H),4.15(t,1H), 4.68(d,1H),6.22(dd,1H),6.48(d,1H),6.67(s,1H),6.71(s,1H),7.22-7.35(m,7H),7.91(d,2H). [Example]

[0117] [ka] Synthesis of 8.00 g (16.54 mmol) of the product from Example 10 was dissolved in 59.20 g (615.96 mmol) of methanesulfonic acid with vigorous stirring. The reaction mixture was stirred at room temperature for 4 hours. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was poured into 800 mL of water and extracted with 300 mL of dichloromethane. The organic layer was washed successively with 300 mL of saturated sodium bicarbonate solution and 300 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was purified by flash column chromatography on silica gel (toluene / ethyl acetate (65:35)) and then crystallized from cyclohexane / ethyl acetate (75:25) to give 1.85 g of a whitish-yellow solid (29% yield). 1H-NMR(CDCl3,δ ppm):0.90(d,6H),1.90(m,1H),2.52(d,2H),3.74(s,3H),3.93(s,3H),4. 04(s,3H),6.80(s,1H),7.00(s,1H),7.20(d,2H),7.79(d,2H),7.88(s,1H) [Example]

[0118] [ka] Synthesis of 4.95 g (35.55 mmol) of 3-(methylthio)aniline and 7.57 g (32.31 mmol) of the product from Example 6 were dissolved in 80 mL of N,N-dimethylformamide. The reaction mixture was stirred at 150 °C for 4 hours, and the methanol was removed by distillation. The progress of the reaction was monitored by TLC. After the reaction was complete, the mixture was cooled and poured into 400 mL of 6 M hydrochloric acid and extracted with 300 mL of diethyl ether. The organic layer was washed twice with 300 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure to give 10.37 g of a yellow oil (94% yield). 1 H-NMR(CDCl3,δ ppm):0.90(d,6H),1.90(m,1H),2.47(s,3H),2.54(d,2H),4.07(s,2H),7.00(d ,1H),7.21(t,1H),7.27(d,2H),7.32(d,1H),7.55(s,1H),7.93(d,2H),9.40(br s,1H) [Example]

[0119] [ka] Synthesis of To a warm solution containing 10.00 g (29.29 mmol) of the product from Example 12 and 3.87 g (29.28 mmol) of trans-cinnamaldehyde in 120 mL of toluene, 0.249 g (2.92 mmol) of piperidine, 0.175 g (2.91 mmol) of acetic acid, and 5.00 g of anhydrous sodium sulfate were added, in that order. The reaction mixture was refluxed under a nitrogen atmosphere for 1 hour. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was cooled, poured into 250 mL of brine, and extracted twice with 150 mL of dichloromethane. The organic layer was washed three times with 150 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent removed by vacuum distillation to give 13.00 g of crude product as a mixture of two regioisomers. This crude product was used in the next step without further purification. [Example]

[0120] [ka] Synthesis of To an ice-cooled solution containing 13.00 g (28.53 mmol of crude product) of the crude product from Example 13 in 180 mL of anhydrous tetrahydrofuran, 3.36 g (29.94 mmol) of potassium tert-butoxide was added portionwise slowly with stirring. After stirring for 10 minutes, 4.45 g (31.35 mmol) of iodomethane was carefully added to the reaction mixture. The resulting mixture was then stirred at room temperature under a nitrogen atmosphere for 1.5 hours. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was poured into 100 mL of saturated ammonium chloride solution, diluted with 100 mL of water, and extracted with 200 mL of ethyl acetate. The organic layer was washed twice with 200 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent removed by vacuum distillation to yield 13.40 g of crude product. This crude product was used in the next step without further purification. [Example]

[0121] [ka] Synthesis of To a solution containing 10.60 g (22.57 mmol of crude product) of the crude product from Example 14 in 300 mL of chlorobenzene, 18.06 g (135.44 mmol) of aluminum chloride was added portionwise slowly with stirring. The resulting mixture was gradually heated to 120 °C and then stirred at this temperature for 1 hour. The reaction progress was monitored by TLC. Upon completion of the reaction, the mixture was cooled, poured into 1000 mL of ice water, and extracted with 300 mL of dichloromethane. The organic layer was washed with 800 mL of water / brine (75:25), dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was purified by flash column chromatography on silica gel (toluene / ethyl acetate (90:10)) and then crystallized from cyclohexane / ethyl acetate (75:25) to give 1.07 g of a white solid (13% yield). 1 H-NMR(CDCl3,δ ppm):0.94(d,6H),1.91(m,1H),2.55(d,2H),2.63(s,3H),3.75(s,3H),7.1 5(dd,1H),7.19(d,1H),7.24(d,2H),7.54(d,1H),7.82(d,2H),7.91(s,1H) [Example]

[0122] [ka] Synthesis of 2.38 g (25.56 mmol) of aniline and 5.00 g (21.34 mmol) of the product from Example 6 were dissolved in 60 mL of N,N-dimethylformamide. The reaction mixture was stirred at 150 °C for 3.5 hours, and the methanol was removed by distillation. The progress of the reaction was monitored by TLC. After the reaction was complete, the mixture was cooled, poured into 300 mL of 6 M hydrochloric acid, and extracted with 250 mL of diethyl ether. The organic layer was washed twice with 250 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure to give 5.97 g of an off-white solid (95% yield). 1H-NMR(CDCl3,δ ppm):0.90(d,6H),1.90(m,1H),2.54(d,2H),4.07(s,2H),7.10(t,1H),7.25(d,2H),7.35(t,2H),7.60(d,2H),7.95(d,2H),9.35(br s,1H) [Example]

[0123] [ka] Synthesis of To a warm solution containing 5.90 g (19.97 mmol) of the product from Example 16 and 2.64 g (19.98 mmol) of trans-cinnamaldehyde in 70 mL of toluene, 0.170 g (2.00 mmol) of piperidine, 0.120 g (2.00 mmol) of acetic acid, and 2.95 g of anhydrous sodium sulfate were added, in that order. The reaction mixture was refluxed under a nitrogen atmosphere for 1 hour. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was cooled, poured into 175 mL of brine, and extracted twice with 70 mL of dichloromethane. The organic layer was washed three times with 175 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation to give 8.17 g of crude product as a mixture of two regioisomers. This crude product was used in the next step without further purification. [Example]

[0124] [ka] Synthesis of To an ice-cooled solution containing 8.17 g (19.95 mmol of crude product) of the crude product from Example 17 in 125 mL of anhydrous tetrahydrofuran, 2.35 g (20.94 mmol) of potassium tert-butoxide was added portionwise slowly with stirring. After stirring for 10 minutes, 3.11 g (21.91 mmol) of iodomethane was carefully added to the reaction mixture. The resulting mixture was then stirred at room temperature under a nitrogen atmosphere for 1.5 hours. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was poured into 50 mL of saturated ammonium chloride solution, diluted with 100 mL of water, and extracted with 150 mL of ethyl acetate. The organic layer was washed twice with 150 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent removed by vacuum distillation to yield 8.45 g of crude product. This crude product was used in the next step without further purification. [Example]

[0125] [ka] Synthesis of 8.40 g (19.83 mmol) of the crude product from Example 18 was dissolved in 51.80 g (538.97 mmol) of methanesulfonic acid with vigorous stirring. The reaction mixture was stirred at 55°C for 1.5 hours. The reaction progress was monitored by TLC. After completion of the reaction, the mixture was poured into 600 mL of water and extracted with 300 mL of dichloromethane. The organic layer was washed twice with 300 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was purified by flash column chromatography on silica gel (toluene / ethyl acetate (85:15)) and then crystallized from cyclohexane / ethyl acetate (90:10) to give 2.58 g of a white solid (41% yield). 1 H-NMR(DMSO-d6,δ ppm):0.88(d,6H),1.90(m,1H),2.54(d,2H),3.67(s,3H),7.29-7.38(m,3H),7.63(d,1H),7.71-7.78(m,3H),7.85(dd,1H),8.17(s,1H) [Example]

[0126] [ka] Synthesis of To a mixture containing 3.50 g (12.53 mmol) of the product from Example 3 in 70 mL of N,N-dimethylformamide was added 1.82 g (13.16 mmol) of potassium carbonate. After stirring at room temperature for 10 minutes, 1.50 g (13.82 mmol) of methyl chloroacetate was added to the mixture. The reaction mixture was stirred at room temperature for 1.5 hours and then at 65°C for 1.5 hours. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was cooled and poured into 250 mL of 1 M hydrochloric acid. The resulting precipitate was removed by filtration, suspended in 35 mL of toluene, and washed with stirring at 100°C for 15 minutes. The mixture was then cooled, and the solid was collected by filtration to give 3.94 g of a white solid (89% yield). 1 H-NMR(DMSO-d6,δ ppm):3.62(s,3H),3.75(s,3H),5.05(s,2H),7.01(dd,1H),7.06(d,1H),7.51(t,2H),7.63(t,1H),7.82(m,3H),8.15(s,1H) [Example]

[0127] [ka] Synthesis of To a warm mixture containing 0.690 g (1.964 mmol) of the product from Example 20 and 2.946 g (4.910 mmol) of polyethylene glycol 600 in 6.9 mL of toluene, 0.096 g (0.197 mmol) of zirconium(IV) acetylacetonate was added with stirring. The reaction mixture was stirred at 105 °C for 2.5 hours, and the methanol was removed by distillation. Next, an additional 0.048 g (0.098 mmol) of zirconium(IV) acetylacetonate was added, and the reaction mixture was stirred at 105 °C for 1 hour, and the methanol was further removed by distillation. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was cooled, dissolved in 30 mL of dichloromethane / EtOAc (50:50), and washed with 30 mL of 1 M hydrochloric acid. The brown-dark precipitate obtained during the procedure was removed by filtration through a pad of Celite, and the phases were separated. The organic layer was washed four times with 30 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure to give 1.33 g of a light brown-yellow oil (74% yield). 1 H-NMR(DMSO-d6,δ ppm):3.30-3.58(m,48H),3.62-3.67(m,5H),4.29(m,2H),5.06(s,2H),7.0 1(dd,1H),7.06(d,1H),7.51(t,2H),7.65(t,1H),7.80(m,3H),8.15(s,1H) [Example]

[0128] [ka] Synthesis of 8.05 g (52.55 mmol) of 3,5-dimethoxyaniline and 11.20 g (47.80 mmol) of the product from Example 6 were dissolved in 100 mL of N,N-dimethylformamide. The reaction mixture was stirred at 150 °C for 4 hours, and the methanol was removed by distillation. The reaction progress was monitored by TLC. After completion of the reaction, the mixture was cooled, poured into 500 mL of 6 M hydrochloric acid, and extracted with 250 mL of ethyl acetate / toluene (1:1). The organic layer was separated, washed three times with 300 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure to give 16.88 g of an off-white solid (99% yield). 1 H-NMR(DMSO-d6,δ ppm):0.87(d,6H),1.89(m,1H),2.53(d,2H),3.71(s,6H),4.10(s,2H),6.23(t,1H),6.84(d,2H),7.33(d,2H),7.93(d,2H) [Example]

[0129] [ka] Synthesis of To a warm solution containing 16.88 g (47.49 mmol) of the product from Example 22 and 6.28 g (47.52 mmol) of trans-cinnamaldehyde in 170 mL of toluene, 0.405 g (4.76 mmol) of piperidine, 0.285 g (4.75 mmol) of acetic acid, and 8.44 g of anhydrous sodium sulfate were added, in that order. The reaction mixture was refluxed under a nitrogen atmosphere for 1 hour. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was cooled, poured into 200 mL of brine, and extracted with 200 mL of ethyl acetate. The organic layer was washed three times with 200 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation to give 22.30 g of crude product as a mixture of two regioisomers. This crude product was used in the next step without further purification. [Example]

[0130] [ka] Synthesis of To an ice-cooled solution containing 22.30 g (47.49 mmol of crude product) of the crude product from Example 23 in 223 mL of anhydrous tetrahydrofuran, 5.60 g (49.91 mmol) of potassium tert-butoxide was added portionwise slowly with stirring. After stirring for 10 minutes, 7.41 g (52.21 mmol) of iodomethane was carefully added to the reaction mixture. The resulting mixture was then stirred at room temperature under a nitrogen atmosphere for 1.5 hours. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was poured into 100 mL of saturated ammonium chloride solution, diluted with 100 mL of water, and extracted with 150 mL of ethyl acetate. The organic layer was washed twice with 100 mL of water, dried over anhydrous sodium sulfate, filtered, and the solvent removed by vacuum distillation to yield 22.26 g of crude product. This crude product was used in the next step without further purification. [Example]

[0131] [ka] Synthesis of 22.26 g (46.03 mmol) of the crude product from Example 24 was dissolved in 164.39 g (1710.44 mmol) of methanesulfonic acid with vigorous stirring. The reaction mixture was stirred at room temperature for 24 hours. The reaction progress was monitored by TLC. After completion of the reaction, the mixture was poured into 500 mL of cold water and extracted with 250 mL of dichloromethane. The organic layer was washed with 300 mL of water and brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was purified by flash column chromatography on silica gel (toluene / ethyl acetate (75:25)) and then crystallized from cyclohexane / ethyl acetate (71:29) to give 1.71 g of a white solid (10% yield). 1H-NMR(DMSO-d6,δ ppm):0.88(d,6H),1.88(m,1H),2.53(d,2H),3.62(s,3H),3.93(s,3H),3. 97(s,3H),6.54(d,1H),6.62(d,1H),7.28(d,2H),7.70(d,2H),8.14(s,1H)

[0132] Comparative Test The ketoquinolones of the present invention were compared with 4,4-bis(diethylamino)benzophenone (Comparative Example-1).

[0133] Test Example 12.1 Comparative Test Test Example 12.1.1. Clear formulation A photopolymerizable composition for testing was prepared by dissolving the photoinitiator, co-initiator, and Esacure® EDB (manufactured by IGM Resins BV) in a mixture of Ebecryl® 605 and Ebecryl® 350 (manufactured by Allnex) in a 99.5:0.5 (mass ratio) mixture at a concentration of 3 wt% each.

[0134] The photopolymerizable composition was placed at the sample base of an FT-IR (FT-IR 430-Jasco) and exposed to an LED lamp (400 nm) positioned 25 mm away from the sample at an angle of 30°. IR spectra were acquired at regular time intervals during photopolymerization, and the 1408 cm spectrum, which was assigned to the acrylic double bond, was recorded using IR software. -1 and 810 cm -1 The decrease in the peak area at 0.05 with time was measured, which allows for the quantification of the degree of polymerization, and thus the efficacy of the photoinitiator.

[0135] The results (expressed as % degree of polymerization over time) are shown in Table 1.

[0136] [Table 1] *Comparative example

[0137] These tests confirmed that the compounds represented by formulas (I) and (Ia) have very high reactivity as photopolymerization initiators.

[0138] Test Example 12.1.2. Cyan inkjet ink - LED lamp (400nm) A photopolymerizable composition for testing was prepared by dissolving the photoinitiator, coinitiator, and Esacure® EDB (manufactured by IGM Resins BV) in a cyan inkjet ink at a concentration of 5% by weight each.

[0139] The photopolymerizable composition was placed at the sample base of an FT-IR (FT-IR 430-Jasco) and exposed to an LED lamp (400 nm) positioned 25 mm away from the sample at an angle of 30°. IR spectra were acquired at regular time intervals during photopolymerization, and the 1408 cm spectrum, which was assigned to the acrylic double bond, was recorded using IR software. -1 and 810 cm -1 The decrease in the peak area at 0.05 with time was measured, which allows for the quantification of the degree of polymerization, and thus the efficacy of the photoinitiator.

[0140] The results (expressed as % degree of polymerization over time) are shown in Table 2.

[0141] [Table 2] *Comparative example

[0142] These tests confirmed that the compounds represented by formulas (I) and (Ia) also exhibit high reactivity in pigment systems.

Claims

1. A photocurable composition comprising the following a) and b): a) 50 to 99.9 weight percent of at least one ethylenically unsaturated compound, based on the total weight of the composition; b) 0.1 to 35% by weight, based on the total weight of the composition, of at least one compound represented by formula (I): 【Chemistry 1】 (I) where R 1 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl; Qui is a quinolone group represented by the following formula (A): 【Chemistry 2】 (A) [where R 2 , R 3 , R 4 and R 5 are each independently hydrogen, substituted or unsubstituted C1-C20 alkyl, -N(C1-C6 alkyl) 2 , piperidino, morpholino, piperazino, -OR 8 , -SR 8 , -O-[CH 2 ] n -COOR 8 , or -S-[CH 2 ] n -COOR 8 (where n is 1 to 8, and R 8 is hydrogen, substituted or unsubstituted C1-C20 alkyl, C1-C50 alkyl interrupted by one or more oxygen atoms and optionally having a terminal hydroxyl group, C1-C20 alkyl, C2-C12 alkenyl, substituted or unsubstituted aryl, heteroaryl, or C5-C6 cycloalkyl; R 6 is hydrogen, hydroxyl, or C1-C4 alkyl; R 7 is hydrogen or a C1-C10 alkyl group; Or a substituted or unsubstituted benzoquinolone group represented by any one of the following formulas (B) to (D): 【Transformation 3】 (B) 【Chemistry 4】 (C) 【Transformation 5】 (D) (where R 7 is hydrogen or a C1-C10 alkyl group, and the asterisk indicates the carbon atom bonded to the keto group represented by formula (I) above.

2. 2. The photocurable composition according to claim 1, wherein R 1 is a substituted or unsubstituted aryl group, or a substituted or unsubstituted phenyl group.

3. 3. The photocurable composition according to claim 1, wherein Qui in formula (I) is a quinolone group represented by formula (A), and R 2 , R 3 , R 4 and R 5 wherein at least one of is not hydrogen.

4. The photocurable composition according to any one of claims 1 to 3, wherein R in formula (I) 6 is hydrogen.

5. The photocurable composition according to any one of claims 1 to 4, wherein R in formula (I) 7 is a C1 to C8 alkyl.

6. The photocurable composition according to any one of claims 1 to 5, further comprising one or more of the following components c) to f): c) 0.01 to 15% by weight, based on the total weight of the composition, of one or more photosensitizers; and / or d) 0.2 to 15 wt. % of an accelerator / co-initiator, based on the total weight of the composition; and / or e) 0.5 to 15% by weight, based on the total weight of the composition, of one or more additional photoinitiators; and / or f) Additives.

7. A photopolymerization initiator represented by the following formula (Ia): 【Transformation 6】 (Ia) where R' 1 is a substituted or unsubstituted aryl; Qui' is a quinolone group represented by the following formula (A'): 【Transformation 7】 (A') [where R' 2 , R' 3 , R' 4 and R' 5 are each independently hydrogen, substituted or unsubstituted C2-C20 alkyl, -N(C1-C6 alkyl) 2 , piperidino, morpholino, piperazino, -OR 8 , -SR 8 , -O-[CH 2 ] n -COOR 8 , and -S-[CH 2 ] n -COOR 8 (where n is 1 to 8 and R 8 is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, C1-C50 alkyl interrupted by one or more oxygen atoms and optionally having a terminal hydroxyl group, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and C5-C6 cycloalkyl; R' 6 is hydrogen or a C1-C4 alkyl group; R' 7 is a C1-C10 alkyl group; 2 , R' 3 , R' 4 and R' 5 At least one of the is -OR 8 or -SR 8 and R 8 is limited to being a C1-C20 alkyl; Or a substituted or unsubstituted benzoquinolone group represented by any one of the following formulas (B') to (D'): 【Transformation 8】 (B') 【Chemistry 9】 (C') 【Chemistry 10】 (D') (where R' 7 is a C1-C10 alkyl group, and the asterisk indicates the carbon atom bonded to the keto group represented by formula (Ia).

8. 8. The photopolymerization initiator according to claim 7, wherein R' in formula (Ia) 1 is a substituted or unsubstituted aryl group.

9. 9. The photopolymerization initiator according to claim 7, wherein R' in formula (Ia) 6 is hydrogen.

10. The photopolymerization initiator according to any one of claims 7 to 9, wherein R' in formula (Ia) 7 is a C1 to C8 alkyl.

11. 8. The photopolymerization initiator according to claim 7, wherein Qui′ in formula (Ia) is a quinolone group represented by formula (A′), and R′ 6 is hydrogen and R' 2 , R' 3 , R' 4 and R' 5 At least two of the 8 is a group, and R 8 is a C1 to C20 alkyl group.

12. 1. A method for photocuring a photocurable composition or ink, comprising the steps of: (i) preparing or providing the photocurable composition according to claim 1 or 6 or an ink comprising the same; (ii) photopolymerizing said composition or ink of step (i) using a light source.

13. 13. The method of claim 12, wherein the light source includes ultraviolet radiation including at least one of the UVA, UVB, and UVC regions.

14. 13. The method of claim 12, wherein the light source is an LED light source emitting in the range of 350 to 420 nm.

15. The method of any one of claims 12 to 14, further comprising the step of applying the photocurable composition to a substrate prior to photopolymerization.

16. Use of a compound represented by the following formula (Ia) as a photopolymerization initiator: The compound represented by formula (Ia): 【Chemistry 11】 (Ia) where R' 1 is a substituted or unsubstituted aryl or a substituted or unsubstituted heteroaryl; Qui' is a quinolone group represented by the following formula (A'): 【Chemistry 12】 (A') [where R' 2 , R' 3 , R' 4 and R' 5 are each independently hydrogen, substituted or unsubstituted C2-C20 alkyl, -N(C1-C6 alkyl) 2 , piperidino, morpholino, piperazino, -OR 8 , -SR 8 , -O-[CH 2 ] n -COOR 8 , and -S-[CH 2 ] n -COOR 8 (where n is 1 to 8 and R 8 is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, C1-C50 alkyl interrupted by one or more oxygen atoms and optionally having a terminal hydroxyl group, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and C5-C6 cycloalkyl; R' 6 is hydrogen or a C1-C4 alkyl group; R' 7 is a C1-C10 alkyl group; Or a substituted or unsubstituted benzoquinolone group represented by any one of the following formulas (B') to (D'): 【Chemistry 13】 (B') 【Chemistry 14】 (C') 【Chemistry 15】 (D') (where R' 7 is a C1-C10 alkyl group, and the asterisk indicates the carbon atom bonded to the keto group represented by formula (Ia).

17. The compound represented by formula (Ia) according to claim 16 is used as a photopolymerization initiator, wherein R' in formula (Ia) 1 is a substituted or unsubstituted aryl group.

18. In the use of the compound represented by formula (Ia) according to claim 16 or 17 as a photopolymerization initiator, Qui' in formula (Ia) is a quinolone group represented by formula (A'), and R' 2 , R' 3 , R' 4 and R' 5 At least one of the is -OR 8 or -SR 8 and R 8 is a C1 to C20 alkyl.

19. In the use of the compound represented by formula (Ia) according to any one of claims 16 to 18 as a photopolymerization initiator, R' in formula (Ia) 6 is used hydrogen.

20. In the use of the compound represented by formula (Ia) according to any one of claims 16 to 19 as a photopolymerization initiator, R' in formula (Ia) 7 is C1 to C8 alkyl.

21. In the use of the compound represented by formula (Ia) as a photopolymerization initiator according to claim 16, Qui' in formula (Ia) is a quinolone group represented by formula (A'), and R' 6 is hydrogen and R' 2 , R' 3 , R' 4 and R' 5 At least two of the 8 is a group, and R 8 is an alkyl group of C1 to C20.

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