Coumarin glyoxylate for LED photocuring

Abstract

The present invention relates to novel coumarin trioxylates, their preparation, and their use as photoinitiators in photopolymerizable compositions. The present invention also relates to a method for photopolymerizing compositions comprising said coumarin trioxylates.

Description

Technical Field

[0001] The present invention relates to novel coumarin glyoxylates, methods for producing the same, and their use as photoinitiators in photopolymerizable compositions. The present invention also relates to a method for photopolymerizing a composition comprising the coumarin glyoxylate.

Background Art

[0002] Photopolymerizable systems contain photoinitiators having a functional group that generates radicals upon exposure to light irradiation of an appropriate wavelength or generates radicals capable of initiating photopolymerization by another chemical species.

[0003] Among the light irradiation sources used in this field, light-emitting diodes (LEDs) have been the subject of important development over the past few years due to advantages such as a low operating temperature and an extremely long lifespan compared to conventional medium-pressure mercury arc curing lamps. Thus, LED lamps are advantageous because the LED units are inherently small in size, have structural stability, and can be easily applied to, for example, commercially available printing systems.

[0004] When using an LED lamp to photocure inks and coatings, it is necessary to use a special photoinitiator system that is compatible with the wavelength of this light source. Mercury arc lamps have a multi-color emission spectrum, while LED lamps have only a single emission band in the range of 350 - 420 nm.

[0005] Thus, for using an LED lamp, a photoinitiator that absorbs in the region of 350 - 420 nm is required. Furthermore, since the application of LEDs usually requires a high concentration of photoactive substances, the photoinitiator must have a high degree of compatibility with the photopolymerizable system. Thioxanthones, for example, isopropylthioxanthone (ITX) and its derivatives, and acylphosphine oxides are examples of photoinitiators commonly used in this field.

[0006] Unfortunately, thioxanthone derivatives tend to turn yellow when exposed, while acylphosphine oxides are oxygen-sensitive, and these drawbacks limit many LED applications.

[0007] In the past few years, various attempts have been made to develop new photoinitiators that can overcome these problems, and some examples of them are 3-ketocoumarin (US 9951034, WO 2017 / 216699), acylgermane photoinitiators (EP 3150641, EP 2649981), phenyltellurated benzoyl photoinitiators (Macromolecules, 2014, 47(16), 5526-5531), acylphosphine oxides (EP 2877500), polycyclic glyoxylates (WO 2018 / 041935).

[0008] In particular, glyoxylates have recently attracted attention due to their easy synthetic route and low yellowing characteristics. Unfortunately, new glyoxylate compounds have been shown to be less reactive under LED wavelengths.

[0009] The preparation of coumarin glyoxylate derivatives was first hypothesized in 2012 (Tetrahedron 68 (2012) 8817-8822). However, this document does not show that all of the desired compounds are prepared, nor does it provide experimental tests regarding the use / activity of the compounds disclosed herein.

Summary of the Invention

Problems to be Solved by the Invention

[0010] There is always a need for new photoinitiators that overcome the drawbacks of the prior art, such as yellowing and oxygen sensitivity, and exhibit further interesting properties, such as being reactive even at LED wavelengths.

Means for Solving the Problems

[0011] Surprisingly, the inventors have found that certain coumarin glyoxylates react well in the UVA, UVB, and UVC wavelength ranges and also react more preferably with an LED source that emits light in the wavelength range of 350 to 420 nm (reacting with an LED source is a technological advancement compared to the prior art).

[0012] Accordingly, the present invention relates to a special coumarin glyoxylate useful as a photoinitiator, a composition comprising the photoinitiator, a method for producing the same, and a photopolymerization method of a composition comprising the coumarin glyoxylate.

Mode for Carrying Out the Invention

[0013] According to one aspect thereof, the present invention is 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 content of the composition excluding any water and solvent); and 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 of formula (I) (based on the total content of the composition excluding any water and solvent) relates to a photocurable composition comprising. Formula (I)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0014] The expression "excluding accessible water and solvents" means that the amounts in mass % of the compounds and additional components of the composition are based on the total content of said compounds and said additional components, regardless of the fact that water and / or solvents may be present in the composition.

[0015] According to another aspect, the invention relates to a compound of formula (Ia). Formula (Ia)

Chemical formula

[0016] According to a specific example, in formula (Ia), when R1 is methyl, R3 is not methoxy.

[0017] According to a specific example, C2-C12 alkenyl is C3-C12 alkenyl.

[0018] According to another aspect, the present invention relates to a method for producing a compound of formula (I) or (Ia) as defined above according to the following scheme. Scheme

Chemical formula

[0019] Alternatively, the reaction is carried out without a solvent.

[0020] According to a specific example, in the above method, the catalyst is not FeCl3.

[0021] According to the present invention, the terms "photocuring" and "photopolymerization" and related terms are synonyms.

[0022] According to another aspect, the present invention (i) Providing a composition comprising compounds (a) and (b) defined as above; and (ii) Photopolymerizing the composition of step (i) with a light source relates to a photopolymerization method comprising:

[0023] In this specification, the term "alkyl" or "alkyl group", unless otherwise indicated, means a straight-chain or branched saturated alkyl chain having a predetermined number of carbon atoms, and all possibilities for each number of carbon atoms in the alkyl group, for example, for 3 carbon atoms (n-propyl and isopropyl); for 4 carbon atoms (n-butyl, isobutyl, and tertiary-butyl); for 5 carbon atoms (n-pentyl, 1,1-dimethyl-propyl, 2,2-dimethyl-propyl, and 2-methyl-butyl), etc. are included.

[0024] "Alkenyl" or "alkenyl group" means an unsaturated group containing 3 to 12 carbon atoms, for example, allyl, methallyl, or undecenyl.

[0025] The term "cycloalkyl" or "cycloalkyl group", unless otherwise indicated, means an aliphatic ring containing 5 or 6 carbon atoms, for example, cyclopentyl or cyclohexyl.

[0026] The term "aryl" or "aryl group" includes, but is not limited to, for example, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, an anthracenyl group, an indenyl group, a fluorenyl group.

[0027] The term "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, indoline, julolidine, etc.

[0028] The expression "C1-C50 alkyl interrupted by oxygen atoms of 1 or more" means that when there are oxygen atoms greater than 1, the oxygen atoms are separated from each other by at least 1 methylene group, that is, the oxygen atoms are non-consecutive. Examples include -O-CH2-OCH3, -O-CH2CH2-OCH2CH3, -O-[CH2CH2O] v CH3, -O-[CH2CH2O] v OH, -O-[CH2CH2O] v CH2CH3, CH2-O-[CH2CH2O] v CH3 (v = 1-24), -O-[CH2CH2CH2O] p OH, -O-[CH2CH2CH2O] p CH3, -O-[CH2CH2CH2O] p CH2CH3, -CH2O-[CH2CH2CH2O] p CH3 (p = 1-16) are included.

[0029] The term "substituted" group means that the group has one or more substituents, and the substituents are preferably selected from a halogen atom, alkyl, cycloalkyl, alkoxy, alkylamino, dialkylamino, alkylthio or arylthio group, a heterocyclic group, preferably methyl, ethyl, isopropyl, tertiary-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, -PO3H, methylthio, ethylthio, i-propylthio, n-propylthio, phenylthio, mercapto, acetylthio, thiocyano, methylsulfinyl, methylsulfonyl, dimethylsulfonyl, sulfonate group, fluorine atom, chlorine atom, bromine atom, iodine atom, trimethylsilyl, triethylsilyl, trimethylstannyl, furyl, thienyl, pyridyl, and morpholino. Among the said substituents, an electron-donating group such as an alkoxy group (e.g., methoxy, ethoxy, isopropoxy, tertiary-butoxy, or phenoxy group), methyl, ethyl, ethyl, isopropyl, hydroxyl, acetoxy, benzoyloxy group, etc., or a thioalkyl group (e.g., methylthio, ethylthio, n-propylthio, i-propylthio, butylthio, pentylthio) or arylthio (e.g., phenylthio) is preferred.

[0030] According to a preferred specific example, in formula (I) or (Ia) defined as above, at least one of the following conditions is preferred: R1 is a substituted or unsubstituted C1-C20 alkyl group, more preferably a C1-C12 alkyl group; Cou is a coumarin group of formula (A) (wherein at least one of R2, R3, R4, and R5 is different from hydrogen), more preferably a coumarin group of formula (A) (wherein at least one of R2, R3, R4, and R5 is -O-R7 or -S-R7, and R7 is C1-C20 alkyl), and most preferably a coumarin group of formula (A) (wherein R3 is -O-R7 or -S-R7, and R7 is C1-C20 alkyl); R6 is preferably hydrogen.

[0031] According to preferred specific examples, two, three, or all of the above conditions are simultaneously satisfied.

[0032] According to preferred specific examples, Cou is (C).

[0033] In other preferred specific examples, in the compound of formula (I) or (Ia), Cou is a coumarin group of formula (A) (wherein R6 is hydrogen, at least two of R2, R3, R4, and R5 are -O-R7 groups, and R7 and R1 are C1-C20 alkyl groups).

[0034] According to preferred specific examples, in the compound of formula (I) or (Ia), when R3 is a methoxy group and R1 is a methyl group, at least one of R2, R4, R5, and R6 is not hydrogen.

[0035] In all preferred specific examples regarding the compound of formula (Ia), the above conditions (i)-(v) must be satisfied

[0036] The compound represented by formula (I) or (Ia) is prepared according to general methods known to those skilled in the art, for example, as reported in Tetrahedron 68 (2012) 8817-8822.

[0037] Alternatively, the compound is prepared according to the method disclosed herein, and surprisingly, this method can also provide compounds that cannot be prepared according to the methods of the prior art (refer to the position of the ethylhexyl substituent of coumarin in Example 1).

[0038] According to the present invention, the photoinitiator of formula (I) or (Ia) is used for preparing a photocurable composition comprising an ethylenically unsaturated compound (a).

[0039] The unsaturated compound (a) can contain one or more olefinic double bonds. These can be of low molecular weight (monomer-based) or high molecular weight (oligomer-based).

[0040] Examples of suitable low molecular weight monomers having one double bond are alkyl or hydroxyalkyl acrylates or methacrylates, such as methyl-, ethyl-, butyl-, 2-ethylhexyl-, 2-hydroxyethyl-, isobornyl-acrylate, and methyl or ethyl methacrylate. Further examples are resins modified with silicon or fluorine, such as silicone acrylate. Further examples of these monomers are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamide, styrene, alkylstyrene, and halogenostyrene, vinyl esters (e.g., vinyl acetate), vinyl ethers (isobutyl vinyl ether), N-vinylpyrrolidone, vinyl chloride, or vinylidene chloride.

[0041] Examples of monomers having more than one double bond are ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl diacrylate, hexamethylene glycol diacrylate, bisphenylene A diacrylate, 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.

[0042] Examples of high molecular weight (oligomeric) polyunsaturated compounds are acrylated epoxy resins, acrylated or vinyl-ether- or epoxy group-containing polyesters, acrylated polyurethanes, or acrylated polyethers. Further examples of unsaturated oligomers are unsaturated polyester resins usually prepared from maleic acid, phthalic acid, and one or more diols and having a molecular weight of about 500 to 3,000 Da. Such unsaturated oligomers are also referred to as prepolymers.

[0043] Examples of compound (a) particularly suitable for the practice of the present invention are esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers containing ethylenically unsaturated groups in the chain or side chain, such as unsaturated polyesters, polyamides, and polyurethanes, and copolymers thereof, alkyl resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers having (meth)acrylic groups in the side chain, and mixtures thereof.

[0044] Exemplary examples of unsaturated carboxylic acids or anhydrides useful in the preparation of the above esters are acrylic acid, methacrylic acid, maleic anhydride, crotonic acid, itaconic acid, cinnamic acid, and unsaturated fatty acids such as linolenic acid and oleic acid. Acrylic acid and methacrylic acid are preferred.

[0045] Examples of polyols to be esterified are aromatic, aliphatic, and alicyclic polyols, preferably aliphatic and alicyclic polyols.

[0046] Aromatic polyols are, for example, hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane, together with novolac and resorcinol. Polyepoxides to be esterified include those based on said polyols, especially aromatic polyols, and epichlorohydrin. Polymers and copolymers containing hydroxyl groups in the polymer chain or side chains, such as polyvinyl alcohol and its copolymers, or hydroxyalkyl esters of polymethacrylic acid or its copolymers, are also suitable as polyols. Further suitable polyols are oligoesters having hydroxyl end groups.

[0047] Examples of aliphatic and alicyclic polyols preferably include alkylene diols 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, preferably polyethylene glycol having a molecular weight of 200 to 1,500 Da, 1,3-cyclopentanediol, 1,2-, 1,3-, or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris(β-hydroxy-ethyl)amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol.

[0048] A more preferred ethylenically unsaturated compound (a) is an unsaturated polyamide obtained from an unsaturated carboxylic acid and, preferably, an aromatic, aliphatic, and alicyclic unsaturated polyamine having 2 to 6, preferably 2 to 4 amino groups. Examples of such polyamines are 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, and di(β-aminoethoxy)- and di(β-aminopropoxy)-ethane. Other preferred polyamines are polymers and copolymers that can contain additional amino groups in the side chain and oligoamines containing amino end groups.

[0049] Specific examples of such unsaturated polyamides are methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriamine trismethacrylamide, bis(methacrylamidepropane)ethane, and N-[(β-hydroxyethoxy)ethyl]-acrylamide.

[0050] For the practice of the present invention, unsaturated polyurethanes, for example, those derived from saturated or unsaturated diisocyanurates and saturated or unsaturated diols are also suitable. Polybutadiene and polyisoprene and their copolymers are also used. Suitable comonomers include, for example, olefins such as ethylene, propene, butene, and hexene, (meth)acrylates, acrylonitrile, styrene, and vinyl chloride.

[0051] Polymers having an unsaturated (meth)acrylate group in the side chain are used as component (a). These are generally reaction products of novolak-based epoxy resins and (meth)acrylic acid; homopolymers or copolymers of hydroxyalkyl derivatives esterified with vinyl alcohol or (meth)acrylic acid; and homopolymers and copolymers of (meth)acrylates esterified with hydroxyalkyl (meth)acrylates.

[0052] In addition to the above components (a) and (b), the photocurable composition of the present invention can also contain one or more of the following components: (c) a photosensitizer and / or (d) an accelerator / co-initiator and / or (e) a further photoinitiator and / or (f) an additive.

[0053] The photocurable composition of the present invention is also formulated as a composition further containing water and / or a solvent, for example, an organic solvent.

[0054] The photosensitizer (c) is present in an amount of 0.01 to 15% by mass, preferably 0.01 to 10% by mass, based on the total content (excluding accessible water and solvent).

[0055] Examples of photosensitizers are those commonly used in the art, aromatic carbonyl compounds such as benzophenone, thioxanthone, anthraquinone, and 3-acylcoumarin derivatives, terphenyl, styryl ketone, and 3-(aroylmethylene)-thiazoline, camphorquinone, and eosin, rhodamine, and erythrosine dyes.

[0056] Examples of thioxanthones are 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, 1 - cyano - 3 - chlorothioxanthone, 1 - ethoxycarbonyl - 3 - chlorothioxanthone, 1 - ethoxycarbonyl - 3 - ethoxythioxanthone, 1 - ethoxycarbonyl - 3 - aminothioxanthone, 1 - ethoxycarbonyl - 3 - phenylsulfurylthioxanthone, 3,4 - bis[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 - 2 - methylthioxanthone, thioxanthone - 2 - polyethylene glycol ester, 2 - hydroxy - 3-(3,4 - dimethyl - 9 - oxo - 9H - thioxanthon - 2 - yloxy)-N,N,N - trimethyl - 1 - propanaminium chloride, or those described in PCT / EP2011 / 069514, for example, n - dodecyl - 7 - methyl - thioxanthone - 3 - carboxylate, and N,N - diisobutyl - 7 - methyl - thioxanthone - 3 - carbamide. Polymeric thioxanthone derivatives (for example, Omnipol®TX (IGM Resins B.V.), Genopol®TX - 1 (Rahn A.G.), Speedcure®7010 (Lambson Limited)) are also suitable.

[0057] Examples of benzophenones are 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. Polymerizable benzophenone derivatives (Omnipol® BP, Omnipol 2702 and Omnipol 682 (all from IGM Resins B.V.), Genopol® BP-2 (Rahn A.G.), and Speedcure® 7005 (Lambson Limited)) are also suitable.

[0058] Examples of 3-acylcoumarin derivatives are 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-isobutyroylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-diethoxycoumarin, 3-benzoyl-5,7-dibutoxycoumarin, 3-benzoyl-5,7-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, or those described in EP 2909243 and WO 2017 / 216699.

[0059] Examples of 3-(aroylmethylene)thiazolidine are 3-methyl-1,2-benzoylmethylene-β-naphthothiazoline, 3-methyl-2-benzoylmethylene-benzothiazoline, 3-ethyl-2-propionylmethylene-β-naphthothiazoline.

[0060] Examples of other aromatic carbonyl compounds are acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzyl (e.g., those described in WO 2013 / 164394), 2-acetylnaphthalene, 2-naphthaldehyde, 9,10-anthraquinone, 9-fluorenone, dibenzosuberone, xanthone, 2,5-bis(4-diethylaminobenzylidene)cyclopentanone, α-(p-dimethylaminobenzylidene); ketones such as 2-(4-dimethylamino-benzylidene)-indan-1-one, or 3-(4-dimethylaminophenyl)-1-indan-5-yl-propenone, 3-phenylthophthalimide, N-methyl-3,5-di(ethylthio)phthalimide.

[0061] Thioxanthone and 3-acylcoumarin are particularly preferred.

[0062] The above component (c) increases the activity of the photoinitiator (b) without shortening the shelf life of the composition. Furthermore, the composition has the special advantage that the spectral sensitivity of the photoinitiator (b) can be shifted to a desired wavelength region by appropriately selecting the photosensitizer (c). A person skilled in the art can select a suitable photosensitizer (c) so that the photoinitiator (b) operates in a desired wavelength region.

[0063] The accelerator / cocatalyst (d) can be present in an amount of 0.2 to 15% by mass, preferably 0.2 to 8% by mass, based on the total content of the composition (excluding accessible water and solvents).

[0064] Examples of suitable accelerators / cocatalysts are alcohols, thiols, thioethers, amines, or ethers, disulfides, and phosphines having active hydrogen bonded to a carbon adjacent to a heteroatom (e.g., as described in EP 438123 and GB 2180358).

[0065] Suitable examples of amine accelerators / co-initiators include, but are not limited to, aliphatic, cycloaliphatic, aromatic, aryl-aliphatic, heterocyclic, oligomeric or polymeric amines. These are primary, secondary, or tertiary amines, for example, butylamine, dibutylamine, tributylamine, cyclohexylamine, benzyldimethylamine, dicyclohexylamine, N-phenylglycine, triethylamine, phenyldiethanolamine, triethanolamine, piperidine, piperazine, morpholine, pyridine, quinoline, esters of dimethylaminobenzoic acid, Michler's ketone (4,4'-bis-dimethylaminobenzophenone) and corresponding derivatives.

[0066] Amine-modified acrylates are used as amine accelerators / co-initiators. Examples of such amine-modified acrylates include acrylates modified by reaction with primary or secondary amines (described in US 3,844,916, EP 280222, US 5,482,649, or US 734,002).

[0067] Polyfunctional amines and polymeric amine derivatives are also used as co-initiators. Some examples are those described in Omnipol® ASA (IGM Resins B.V.), Genopol® AB-2 (Rahn A.G.), Speedcure® 7040 (Lambson Limited), or US 2013 / 0012611.

[0068] Furthermore, the photoinitiator (e) can be present in an amount of 0.5 to 15% by weight, preferably 1 to 10% by weight, based on the total content of the composition (excluding accessible water and solvents).

[0069] Examples of other suitable photoinitiators (e) are camphorquinone, benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, dialkoxyacetophenone, α-hydroxyketones, α-aminoketones, 4-aroyl-1,3-dioxolanes, benzoin alkyl ethers, and benzyl ketals, for example, benzyldimethyl ketal, ketosulfones, for example, 1-[4-[(4-benzoyl-phenyl)-thio]-phenyl]-2-methyl-2-[(4-methyl-phenyl)-sulfonyl]-propan-1-one (Esacure® 1001 (IGM Resins B.V.)), 3-ketocoumarins, for example, those described in EP 2909243 and WO 2017 / 216699, phenylglyoxylates and their derivatives, dimeric phenylglyoxylates, peresters, for example, benzophenone tetracarboxylic acid peresters, for example, those described in EP 126541, acylphosphine photoinitiators (selected from mono-acylphosphine oxides, bis-acylphosphine oxides, tris-acylphosphine oxides, and polyfunctional mono- or bis-acylphosphine oxides), halomethyltriazines, hexaarylbiimidazole / cocatalyst systems, for example, the combination of o-chlorohexaphenylbiimidazole and 2-mercaptobenzothiazole; ferrocenium compounds or titanocenes, for example, dicyclopentadienyl-bis(2,6-difluoro-3-pyrrolyl-phenyl)titanium; O-acryloxime ester photoinitiators.

[0070] Examples of α-hydroxy ketones and α-amino ketones are 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), 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).

[0071] Examples of O-acyl oxime ester photoinitiators are 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] 1-(O-acetoxime), or those described in GB 2339571.

[0072] 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)phenylphosphinate, phenyl(2,4,6-trimethylbenzoyl)phosphinic acid, glycerol ethoxylated trimester (Omnipol® TP (IGM Resins B.V.)).

[0073] Examples of haloalkyltriazine-based photoinitiators are 2-[2-(4-methoxyphenyl)-vinyl]-4,6-bis-trichloromethyl[1,3,5]triazine, 2-(4-methoxyphenyl)-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.

[0074] When the photocurable composition according to the present invention is used in a hybrid system (wherein, in this context, the hybrid system means a mixture of a free radical curable system and a cationic curable system), a cationic photoinitiator is also used as the additional photoinitiator (e). Examples of suitable cationic photoinitiators are, for example, aromatic sulfonium salts, phosphonium salts, or iodonium salts as described in US 4950,581, or, for example, cyclopentadienyl arene-iron(II) complex salts as described in GB 2348644, US 4,450,598, US 4,136,055, WO 00 / 10972, and WO 00 / 26219, for example, (η 6 -isopropylbenzene)(η 5 -cyclopentadienyl)iron(II) hexafluorophosphate or an oxime-based photoacid latent.

[0075] The additive (f) is, for example, a thermal initiator, a binder, a stabilizer, and mixtures thereof.

[0076] The curing method according to the present invention is particularly promoted, in the case of pigmented compositions, by adding, as an additional additive (f), a thermal initiator (a compound that generates free radicals when heated), for example, an azo compound, for example, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), a triazene, a diazosulfide, a pentaazadiene, or a peroxy compound, for example, a hydroperoxide or a peroxicarbonate, for example, tertiary-butyl hydroperoxide (as described in, for example, EP 245639).

[0077] A binder is also added to the photocurable composition of the present invention. The addition of the binder is particularly advantageous when the photocurable compound is a liquid or viscous substance. The amount of the binder is, for example, 5 to 60% by mass, preferably 10 to 50% by mass, based on the total content (excluding any possible water and solvents) of the composition. The binder is selected according to the field of use and the required properties, such as developability in aqueous and organic solvent systems, adhesion to substrates, and sensitivity to oxygen.

[0078] 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. Exemplary examples are homopolymers and copolymers of acrylates and methacrylates, such as copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, poly(alkyl methacrylate esters), poly(alkyl acrylate esters); cellulose esters and ethers, such as cellulose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose; polyvinyl butyral, polyvinyl formal, cyclized rubber, polyethers, such as polyethylene oxide, polypropylene oxide, polytetrahydrofuran, polystyrene, polycarbonate, polyurethane, polyolefin chlorides, such as polyvinyl chloride, vinyl chloride / vinylidene chloride copolymer, copolymers of vinylidene chloride with acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, co-poly(ethylene / vinyl acetate), polymers, such as polycaprolactam and poly(hexamethylene adipamide), polyesters, such as poly(ethylene glycol terephthalate) and poly(hexamethylene glycol succinate).

[0079] Suitable stabilizers are, for example, heat 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 increase storage stability in the dark, 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. During polymerization, paraffin or a similar wax-like substance (insoluble in the polymer) can be used for the purpose of removing oxygen in the atmosphere, and the substance migrates to the surface at the start of polymerization to form a transparent surface layer that prevents air intrusion.

[0080] Light stabilizers such as UV absorbers such as hydroxyphenylbenzotriazole, hydroxyphenylbenzophenone, oxalic acid amide, or hydroxyphenyl-s-triazine type can be used. Such compounds are used alone or in the form of a mixture, with or without using sterically hindered amines (HALS).

[0081] The photocurable composition according to the present invention can further contain, as additional additive (f), a photoreductive dye such as xanthene, benzoxanthene, benzothioxanthene, thiazine, pyronin, porphyrin, or acridine dye, and / or a radiation-cleavable trihalomethyl compound. These compounds are described, for example, in EP 445624.

[0082] Furthermore, typical additives (f) are, depending on the intended use, optical brighteners, fillers, pigments (both white and colored pigments), colorants, antistatic agents, wetting agents, or fluidity improvers. Additives typical in the art such as antistatic agents, fluidity improvers, and adhesion enhancers can also be used.

[0083] Chain transfer agents customary in the art are also added to the composition according to the present invention. Examples are mercaptans, amines, and benzothiazoles.

[0084] The composition of the present invention may contain a colorant and / or a colored pigment. Depending on the intended use, both inorganic pigments and organic pigments can be used. Such additives are known to those skilled in the art. Some examples are carbon black, iron oxide, for example, yellow iron oxide, red iron oxide, chrome yellow, chrome green, nickel titanium yellow, ultramarine, cobalt blue, bismuth vanadate, cadmium yellow, and cadmium red. Examples of organic pigments are mono- or bis-azo pigments and their metal complexes, phthalocyanine pigments, polycyclic pigments, for example, perylene, anthraquinone, thioindigo, quinacridone, or triphenylmethane pigments, and diketo-pyrrolo-pyrrole, isoindolinone, for example, tetrachloroisoindolinone, isoindolinone, dioxazine, benzimidazolone, and quinophthalone pigments. In the formulation, the pigments are used alone or as a mixture.

[0085] Depending on the intended use, the pigments are added to the formulation in an amount customary in the art, for example, in an amount of 0.1 to 30% by mass, or 10 to 25% by mass, based on the total mass (excluding any water and solvents present).

[0086] The composition may contain, for example, a wide variety of organic colorants. Examples are azo dyes, methine dyes, anthraquinone dyes, and metal complex dyes. The normal concentration is, for example, 0.1 to 20% by mass, in particular 1 to 5% by mass, based on the total mass of the composition.

[0087] The choice of additives is determined by the field of use and the properties desired for that field. The above additive (f) is known in the art and is therefore used in an amount customary in the art.

[0088] The photocurable composition of the present invention can contain water.

[0089] The photocurable composition of the present invention can be used for various purposes, for example, as printing inks such as screen printing inks, flexographic printing inks, offset printing inks, and inkjet printing inks, as clear coats, for example, as colored coats for wood or metal, as powder coatings, particularly as coating materials for paper, wood, metal, or plastics, for structures and road markings, for photoduplication, for hologram recording materials, for image recording methods or for reproducing plates using organic solvents or aqueous alkaline media, as daylight-curable paints for manufacturing screen printing masks, as dental filling materials, as adhesives, as pressure-sensitive adhesives, as laminate resins, as photoresists, for example, as galvanoresists, as etch resists or permanent resists (both liquid and dry films), as photo-structurable 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 displays 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 a transparent mold) or by stereolithography methods (for example, as described in US 4,575,330), in the manufacture of composite materials (for example, styrene polyesters which can 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 coating agents for optical fibers.

[0090] The photocurable composition of the present invention is also suitable for the manufacture of optical lenses, for example, contact lenses or Fresnel lenses, and for the manufacture of medical devices, aids or implants, and dry film paints.

[0091] The photocurable composition of the present invention is also suitable for the preparation of gels having thermotropic properties. Such gels are described, for example, in DE 19700064 and EP 678534.

[0092] Various products comprising the photo-curable composition of formula (I) or (Ia) of the present invention are another subject of the present invention.

[0093] The compounds and compositions according to the present invention are also used as free radical photoinitiators or photoinitiating systems for radiation-curable powder coatings.

[0094] The photo-curable composition according to the present invention is suitable, for example, as a coating material for all kinds of substrates (for example, wood, fabric, paper, ceramics, glass, plastics (for example, polyester, polyethylene terephthalate, polyolefin, and cellulose acetate), especially for film-like substrates, and metals (for example, Al, Cu, Ni, Fe, Zn, Mg, or Co), and substrates of GaAs, Si, or SiO2 (where a protective film is applied, or for example, an image is applied by imagewise exposure).

[0095] According to another aspect of the present invention, a further subject of the present invention is a method for photocuring a photopolymerizable composition and an ink, the method comprising: (i) providing a photopolymerizable composition comprising the above-mentioned compound components (a) and (b); or the above-mentioned (a) and (b) and one or more components selected from the above-mentioned (c), (d), (e), and (f); (ii) photopolymerizing the composition of step (i) with a light source. The method comprises the steps of.

[0096] According to a preferred embodiment, the photopolymerizable composition in step (i) above comprises at least the above-mentioned components (a), (b), and (d).

[0097] The term "providing" in the first step of the above method includes preparing the composition or obtaining the composition by other possible means, such as purchasing.

[0098] According to one embodiment, the light source comprises UV light in at least one of the UVA, UVB, and UVC regions.

[0099] According to a preferred specific example, the light source is an LED source, and in particular, an LED light source emitting at wavelengths of 365 to 400 nm, more preferably 365 nm, 385 nm, and 395 nm is particularly preferred.

[0100] According to the present invention, the distance between the lamp and the substrate to be exposed can vary depending on the intended use, the type of lamp, and the intensity, and is 0.1 to 150 cm, preferably 1 to 50 cm.

[0101] The photopolymerizable composition is also applied onto a substrate comprising a layer already coated or printed. After being photopolymerized by the light source, the photopolymerizable composition is overprinted or overcoated with one or more compositions suitable for printing or coating.

[0102] Applying the photopolymerizable composition onto the substrate by means of the coating or printing means, photopolymerizing with the light source, and further coating or printing to obtain a precise finish of the article or an article without finishing is a further subject of the present invention.

[0103] Surprisingly, the inventors have found that the compounds of formula (I) and (Ia) are active as photoinitiators and that their activity is higher than that of the glyoxylate compounds described in the literature (WO 2018 / 041935). Furthermore, the compounds of formula (I) and (Ia) are highly reactive with LED lamps in both transparent and colored systems.

[0104] The present invention will be described in detail below by the following examples (for illustrative purposes only and not limited thereto).

[0105] If the chemical structure does not match the displayed chemical name, the chemical structure takes precedence.

[0106] [Examples] 11H NMR spectra were recorded on a Bruker Avance 400 MHz, Bruker DMX 500 MHz or Bruker DMX 600 MHz. Infrared spectra were recorded on a FT-IR 430-Jasco.

Example

[0107] Synthesis of methyl 2-[7-(2-ethylhexyloxy)-2-oxo-2H-chromen-3-yl]-2-oxoacetate

Chemical formula

Example

[0108] Synthesis of Methyl 2-[7-(2-Ethylhexyl-sulfanyl)-2-oxo-2H-chromen-3-yl]-2-oxoacetate

Chemical Structure

Example

[0109] Synthesis of 2-Ethylhexyl 2-Oxo-2-(2-oxo-2H-chromen-3-yl)acetate

Chemical Structure

Example

[0110] Synthesis of methyl 2-[7-(dimethylamino)-2-oxo-2H-chromen-3-yl]-2-oxoacetate

Chem.

Example

[0111] Synthesis of 2-ethylhexyl 2-[7-(diethylamino)-2-oxo-2H-chromen-3-yl]-2-oxoacetate

Chemical formula

Example

[0112] Synthesis of methyl 2-(5,7-dimethoxy-2-oxo-2H-chromen-3-yl)-2-oxoacetate

Chem.

Example

[0113] Synthesis of 2 - ethylhexyl 2 - (5,7 - dimethoxy - 2 - oxo - 2H - chromen - 3 - yl) - 2 - oxoacetate

Chem.

Example

[0114] Synthesis of methyl 2-(7-ethoxy-2-oxo-2H-chromen-3-yl)-2-oxoacetate

Chem.

Example

[0115]

Chem.

Example

[0116] Synthesis of methyl 2-oxo-2-(3-oxo-3H-benzo[f]chromen-2-yl)acetate

Chemical formula

Example

[0117] Synthesis of 2-ethylhexyl 2-oxo-2-(3-3H-benzo[f]chromen-2-yl)acetate [Chemical formula] 0.19 g (0.39 mmol) of zirconium(IV) acetylacetonate was added to a warm solution containing 1.10 g (3.90 mmol) of methyl 2-oxo-2-(3-oxo-3H-benzo[f]chromen-2-yl)acetate and 1.27 g (9.75 mmol) of 2-ethyl-1-hexanol in 25 ml of toluene with stirring. The reaction mixture was stirred at 105 °C for 2 hours, and methanol was removed by distillation. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was cooled, diluted with dichloromethane, and washed successively with 1M hydrochloric acid and brine. The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under vacuum. The crude product was purified by flash column chromatography on silica gel (toluene / EtOAc (97.5 / 2.5)) to give 1.33 g of a yellow solid (yield 90%). 1 H-NMR (DMSO-d6, δ ppm): 0.76 - 0.91 (m, 6H), 1.18 - 1.42 (m, 8H), 1.68 (m, 1H), 4.25 (d, 2H), 7.65 - 7.73 (m, 2H), 7.83 (m, 1H), 8.12 (d, 1H), 8.42 (d, 1H), 8.70 (d, 1H), 9.54 (s, 1H)

[0118] [Comparative Example] The coumarin glyoxylate of the present invention was compared with the prior art ethyl 2-(9H-fluorenone-2-yl)-2-oxo (COMP-1) and ethyl 2-oxo-2-thianthren-2-yl-acetate (COMP-2) prepared as described in WO 2018 / 041935.

[0119] [Example 12.1] comparison test [Example 12.1.1] transparent formulation A photopolymerizable composition for testing was prepared by dissolving a photoinitiator and a co-initiator, Esacure® EDB (IGM Resins B.V.), in a mixture of Ebecryl® 605 and Ebecryl® 350 (Allnex) (99.5:0.5 (by mass)) at a concentration of 3% by mass. The photopolymerizable composition placed at the sample point of FT-IR (FT-IR 430-Jasco) was exposed to an LED lamp (400 nm) arranged at a distance of 25 mm from the sample and at an angle of 30°. During photopolymerization, IR spectra were acquired at regular time intervals, and using IR software, 1408 cm -1 and 810 cm -1 The decrease over time in the peak areas at was measured. This enables the quantification of the degree of polymerization and thus the efficacy of the photoinitiator. The results (shown as the degree of polymerization over time %) are reported in Table 1.

[0120]

Table 1

[0121] [Comparative Example 12.1.2] cyan inkjet ink LED lamp (400 nm) A photopolymerizable composition for testing was prepared by dissolving a photoinitiator and a co-initiator, Esacure® EDB (IGM Resins B.V.), in a cyan inkjet ink at a concentration of 5% by mass. The photopolymerizable composition placed at the sample station of FT-IR (FT-IR 430-Jasco) was exposed to an LED lamp (400 nm) placed at a distance of 25 mm from the sample at an angle of 30°. During photopolymerization, IR spectra were acquired at regular time intervals, and using IR software, the peak areas assigned to the acrylic double bonds at 1408 cm -1 and 810 cm -1 were measured for their decrease over time. This enables the quantification of the degree of polymerization and thus the efficacy of the photoinitiator. The results (shown as % degree of polymerization over time) are reported in Table 2.

[0122] [Table 2] *: Comparative example These tests also prove that the compounds of formula (I) and (Ia) are highly active even in colored systems.

[0123] [Example 12.1.3.] tack-free in transparent formulation The photoinitiator and co-initiator, Esacure® A198 (IGM Resins B.V.), were used at a concentration of 4% by mass in Formulation A: Photomer® 6577 50% by mass, Photomer® 4335 15% by mass, Photomer® 4666 15% by mass, Photomer® 4172 20% by mass; Formulation B: Photomer® 3016 50% by mass, Photomer® 4335 15% by mass, Photomer® 4666 15% by mass, Photomer® 4172 20% by mass; Formulation C: Photomer® 5442 50% by mass, Photomer® 4335 15% by mass, Photomer® 4666 15% by mass, Photomer® 4172 20% by mass; Formulation D: 50% by mass of Photomer® 6628, 15% by mass of Photomer® 4335, 15% by mass of Photomer® 4666, 20% by mass of Photomer® 4172 By dissolving in, a photopolymerizable composition for testing was prepared. For the following composition: 50% by mass of Photomer® 5662, 15% by mass of Photomer® 4335, 15% by mass of Photomer® 4666, 20% by mass of Photomer® 4172, Formulation E was prepared by dissolving a photoinitiator at a concentration of 4% by mass. Using a K101 control coater, the photopolymerizable composition was coated on a paper support with a thickness of 6 μm, and then passed under an LED lamp at 395 nm (16 W / cm). The tack-free was measured. The results (displayed as m / min) are reported in Table 3. The greater the speed (m / min), the better the performance.

[0124] [Table 3] *: Comparative example For Formulation A, it was also exposed with an LED lamp at 365 nm (12 W / cm), the tack-free was measured, and the results (displayed as m / min) are reported in Table 4.

[0125] [Table 4] *: Comparative example These tests prove that the compounds of formula (I) and (Ia) are more reactive than the comparative examples at many different formulations and different LED wavelengths.

[0126] [Example 12.1.4.] through cure in cyan offset ink A photoinitiator and a co-initiator, Esacure® A198 (IGM Resins B.V.), were dissolved in a cyan offset ink at a concentration of 1.5% by mass to prepare a photopolymerizable composition for testing. The photopolymerizable composition was applied onto a paper support at a thickness of 1.5 μm and then passed under an LED lamp at 395 nm (16 W / cm) or 365 nm (12 W / cm). Through-curing was measured and the results (expressed as m / min) were reported in Table 5. The greater the speed (m / min), the better the performance.

[0127]

Table 5

Claims

1. (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 content of the composition excluding any water and solvent); (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 of formula (I) (based on the total content of the composition excluding any water and solvent); A photocurable composition comprising the same. Formula (I) 【Chemical 1】 (I) [Wherein, R 1 is a substituted or unsubstituted C1-C20 alkyl group, or a substituted or unsubstituted C1-C50 alkyl group (interrupted by one or more oxygens and may be terminated with a hydroxy group); Cou is a coumarin group of the formula 【Chemical 2】 (A) (Wherein, R 2 、R 3 、R 4 、and R 5 are, independently of one another, hydrogen, substituted or unsubstituted C1-C20 alkyl, -N(C1-C6 alkyl) 2 , piperidino, morpholino, piperazino, -O-R 7 or -S-R 7 wherein R 7 is hydrogen, substituted or unsubstituted C1-C20 alkyl, C2-C12 alkenyl, substituted or unsubstituted aryl, heteroaryl or C5-C6 cycloalkyl); R 6 is hydrogen, a hydroxy group, or a C1-C4 alkyl group) Or; Cou is a formula [Chemical 3] (B), 【Chemical Formula 4】 (C), or 【Chemical Formula 5】 (D) A substituted or unsubstituted naphtho-coumarin group of (wherein the asterisk indicates a carbon atom bonded to the keto group of formula (I)). ]

2. In formula (I), R 1 The photocurable composition according to claim 1, wherein 1 is a substituted or unsubstituted C1-C20 alkyl group.

3. In formula (I), Cou is a coumarin group of formula (A) (wherein at least one of R 2 , R 3 , R 4 , and R 5 is different from hydrogen). The photocurable composition according to claim 1 or 2.

4. In formula (I), Cou is (A) and R 6 is hydrogen, or the photocurable composition according to any one of claims 1 to 3, wherein Cou is (C).

5. In formula (I), Cou is a coumarin group of formula (A) (wherein R 6 is hydrogen, and at least two of R 2 , R 3 , R 4 and R 5 are -O-R 7 groups, and R 7 and R 1 are C1-C20 alkyl groups). The photocurable composition according to any one of claims 1 to 4.

6. Further, (c) 0.01 to 15% by mass of one or more photosensitizers (based on the total content of the composition excluding any water and solvent); and / or (d) 0.2 to 15% by mass of a promoter / co-initiator (based on the total content of the composition excluding any water and solvent); and / or (e) 0.5 to 15% by mass of one or more additional photoinitiators (based on the total content of the composition excluding any water and solvent); and / or (f) An additive The photocurable composition according to any one of Claims 1 to 5, comprising the same.

7. A compound of formula (Ia). Formula (Ia) 【Chemical Formula 6】 (Ia) [Wherein, R 1 is a substituted or unsubstituted C1-C20 alkyl group, or a substituted or unsubstituted C1-C50 alkyl group (interrupted by one or more oxygens and may be terminated with a hydroxyl group); Cou is a formula [Chemical Formula 7] (A) (Wherein, R 2 、R 3 、R 4 、and R 5 are, independently of one another, hydrogen, substituted or unsubstituted C1-C20 alkyl, -N(C1-C6 alkyl) 2 , piperidino, morpholino, piperazino, -O-R 7 or -S-R 7 wherein R 7 is hydrogen, substituted or unsubstituted C1-C20 alkyl, C2-C12 alkenyl, substituted or unsubstituted aryl, heteroaryl, or C5-C6 cycloalkyl); R 6 is hydrogen, a hydroxy group, or a C1-C4 alkyl group) Or a coumarin group of; Cou is a formula 【Chemical 8】 (B)、 【Chemical Formula 9】 (C), or 【Chemical 10】 (D) A substituted or unsubstituted naphtho-coumarin group of (wherein the asterisk indicates a carbon atom bonded to the keto group of formula (Ia)); Provided that, R 1 When R is methyl, 2 R 3 R 4 R 5 and R 6 at least one of which is different from hydrogen; R 1 When R is methyl or ethyl, 4 R is different from methyl; R 1 When R is methyl, 6 it is not hydroxy; R 1 When R is methyl or ethyl, 2 it is not methoxy; and R 1 When R is methyl or ethyl, 2 and R 4 are both not tertiary-butyl.]]

8. In formula (Ia), R 1 The compound according to claim 7, wherein 1 is a substituted or unsubstituted C1-C20 alkyl group.

9. In formula (Ia), Cou is a coumarin group of formula (A) (wherein R 3 is a substituted or unsubstituted C1-C20 alkyl, -O-R 7 or -S-R 7 wherein R 7 is C1-C20 alkyl). The compound according to claim 7 or 8.

10. In formula (Ia), Cou is formula (A) and R 6 is hydrogen, or the compound according to any one of claims 7 to 9, wherein Cou is formula (C).

11. In formula (Ia), Cou is a coumarin group of formula (A) (wherein R 6 is hydrogen, and at least two of R 2 , R 3 , R 4 , and R 5 are -O-R 7 groups, and R 7 and R 1 are C1-C20 alkyl groups). The compound according to any one of claims 7 to 10.

12. Formula 【Chemical 11】 [Wherein, R 1 is a substituted or unsubstituted C1-C20 alkyl group, or a substituted or unsubstituted C1-C50 alkyl group (interrupted by one or more oxygens and may be terminated with a hydroxy group); R 2 、R 3 、R 4 、and R 5 are, independently of one another, hydrogen, substituted or unsubstituted C1-C20 alkyl, -N(C1-C6 alkyl) 2 , piperidino, morpholino, piperazino, -O-R 7 or -S-R 7 wherein R 7 is hydrogen, substituted or unsubstituted C1-C20 alkyl, C2-C12 alkenyl, substituted or unsubstituted aryl, heteroaryl, or C5-C6 cycloalkyl); R 6 is hydrogen, a hydroxy group, or a C1-C4 alkyl group]] A process for producing a compound of, said process comprising the formula 【Chemical 12】 (Here, R 2 , R 3 , R 4 , and R 5 are as described above) the compound, in the presence or absence of a catalyst and in the presence or absence of a solvent, of the formula 【Chemical Formula 13】 A process comprising reacting a compound of (wherein R1 is as described above), wherein the catalyst is selected from acids (however, the catalyst is not FeCl 3 ), and the solvent is an organic solvent.

13. The process according to Claim 12, wherein the catalyst is an acid selected from acetic acid, formic acid, polyphosphoric acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, sulfuric acid, hydrochloric acid, phosphoric acid, hydrobromic acid, nitric acid, perchloric acid, hydrofluoric acid, nitrous acid, and mixtures thereof, or the catalyst is selected from trifluoromethanesulfonic anhydride, trifluoroacetic anhydride, and phosphorus pentoxide.

14. The process according to Claim 12, wherein the organic solvent is an aromatic solvent selected from benzene, toluene, o-xylene, m-xylene, p-xylene, xylene mixture, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, and mixtures thereof.

15. In a method for photocuring a photopolymerizable composition, (i) providing the photopolymerizable composition according to claim 1 or the photopolymerizable composition according to claim 6; (ii) photopolymerizing the composition of step (i) with a light source A method comprising:

16. The method according to claim 15, wherein the light source comprises UV light in at least one of the UVA, UVB, and UVC regions.

17. The method according to claim 15, wherein the light source is an LED light source that emits light in the region of 350 to 420 nm.

18. Furthermore, the method according to any one of claims 15 to 17, comprising a step of applying the photopolymerizable composition to a substrate before photopolymerization.

19. An industrial product obtained by three-dimensional printing according to the method according to any one of claims 15 to 18, or a mixture comprising the composition according to any one of claims 1 to 6 or the compound according to any one of claims 7 to 11.

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