Polymeric (meth)acrylate photoinitiators

Abstract

The present invention relates to novel photoinitiators and photopolymerizable compositions containing said photoinitiators that have improved reactivity and surface curability and / or reduced post-cure yellowing. The present invention also relates to methods for photopolymerizing compositions comprising said photoinitiators, as well as their use in products, including printed, coated, and assembled products.

Description

[Technical Field]

[0001] The present invention relates to novel photoinitiators and photopolymerizable compositions containing said photoinitiators that have improved reactivity and surface curability and / or reduced post-cure yellowing. The present invention also relates to methods for photopolymerizing compositions comprising said photoinitiators, as well as their use in products, including printed, coated, or assembled products. [Background technology]

[0002] In recent years, the design and development of new photoinitiators (PIs) has attracted attention due to the extensive use of photoinitiators that have been or are scheduled to be banned as toxic or reproductive toxicants.

[0003] Various attempts have been made to develop new photoinitiators that can mimic standard photoinitiators or overcome challenges such as yellowing, high line speeds, and curing under LED lamps. Some examples include glyoxylate 3-ketocoumarin (WO2021 / 070152), benzoylphenyl telluride PIs (Macromolecules, 2014, 47(16), 5526-5531), silicon-based PIs (JP 2010-229169, Macromolecules, 2009, 42(16), 6031-6037, Macromolecules 2007, 40(24), 8527-8530, Macromol. Rapid Commun. 2017, 38, 1600470, Macromolecules, 2017, 50(17), 6911-6923), and fluorine-based PIs (US2019 / 0155153). For delicate applications such as food packaging, in addition to good reactivity and lower yellowing, photoinitiators that can be photocrosslinked in the matrix are preferred to avoid possible migration of the photoinitiator into the food. Summary of the Invention [Problem to be solved by the invention]

[0004] Unfortunately, when used in standard applications, these photoinitiators also exhibit several limitations, such as poor surface curability and post-cure yellowing, which make them unsuitable for polymerizable systems, including clear varnishes.

[0005] Therefore, there is a need for new technical solutions that can improve the surface curability of PIs and / or limit post-cure yellowing without affecting the good reactivity of these products. [Means for solving the problem]

[0006] WO2015 / 010729 discloses polymeric photoinitiators containing biphenyl groups. The inventors surprisingly found that substitution of the biphenyl group with different organic moieties, along with the addition of (meth)acrylate groups, leads to significant improvements in the performance of the PIs.

[0007] A first object of the present invention is to provide novel polymeric PIs, their use as photoinitiators, and photocurable compositions comprising them.

[0008] Another object of the present invention is to provide a method for photocuring ethylenically unsaturated compounds using the novel PIs of the present invention, as well as products produced by said method. DETAILED DESCRIPTION OF THE INVENTION

[0009] According to one of its aspects, the present invention relates to compounds of formula (I): Formula (I): [ka] [In the formula, G is the residue of an optionally ethoxylated and / or propoxylated monomeric, oligomeric, or polymeric polyol G-(OH) m+q+p; m is 1 to 7; q is 1 to 7; p is 0 to 6; m+q+p is 3 to 8; R1 is CH2=CH-C(=O) or CH2=C(CH3)-C(=O); R2 is [ka] (A), [ka] (B), and [ka] (C) wherein X is selected from O, S, C(R4)(R5), and NR7; Y is selected from O, S, C(R4)(R5), and NR6; R4 and R5 are each independently selected from H, C1-C12 alkyl, OH, and C1-C10 alkoxy; R6 is selected from H, C1-C8 alkyl; R7 is H, C1-C8 alkyl, or unsubstituted phenyl; and the wavy line represents the bond connecting to the keto group of formula (I).

[0010] According to the present invention, G-(OH) m+q+p is selected from monomeric, oligomeric, polymeric polyols or mixtures thereof, optionally ethoxylated and / or propoxylated.

[0011] Examples of suitable monomeric and oligomeric polyols are glycerol, di-glycerol, tri-glycerol, triethanolamine, trimethylolpropane, di-trimethylolpropane, pentaerythritol, di-pentaerythritol, sugar alcohols (e.g., sorbitol, mannitol, xylitol), and mixtures thereof.

[0012] Examples of polymeric polyols are polyhydroxypolyethers (aliphatic or aromatic), polyhydroxypolyesters, polyhydroxypolyamides, polyhydroxypolyimides, polyhydroxypolycarbonates, and styrene-allyl alcohol copolymers.

[0013] Alkoxylated polyols are particularly preferred for the realization of the present invention. Examples of such alkoxylated polyols are the above-mentioned monomeric, oligomeric, or polymeric polyols, which are alkoxylated, for example, ethoxylated and / or propoxylated and / or butoxylated. Other suitable examples are linear or branched polyamines, alkoxylated and polyalkoxylated diamines, such as ethoxylated ethylenediamine and ethoxylated 1,3-propylenediamine. In the alkoxylated compounds of the present invention, each group reactive with alkylene oxide can have 0 to 15 alkoxy units, preferably 1 to 6 alkoxy units.

[0014] In a preferred embodiment, G-(OH) m+q+p is selected from monomeric and oligomeric polyols.

[0015] In other preferred embodiments, G-(OH) m+q+p is selected from ethoxylated and / or propoxylated monomeric and oligomeric polyols.

[0016] Preferably, G-(OH) m+q+p teeth, 1,500 Da or less, more preferably 1,000 Da or less, and most preferably 800 Da or less; and 100 Da or more, preferably 200 Da or more The number average molecular weight is

[0017] Preferably, G-(OH) m+q+pis selected from glycerol, ethoxylated and / or propoxylated glycerol, ethoxylated and / or propoxylated di-glycerol, trimethylolpropane, ethoxylated and / or propoxylated trimethylolpropane, di-trimethylolpropane, ethoxylated and / or propoxylated di-trimethylolpropane, pentaerythritol, ethoxylated and / or propoxylated pentaerythritol, di-pentaerythritol, ethoxylated and / or propoxylated di-pentaerythritol, sorbitol, ethoxylated and / or propoxylated sorbitol, triethanolamine, and ethoxylated and / or propoxylated triethanolamine.

[0018] Preferably, m+q+p is 3 to 8, more preferably 3 to 6, for example 3, 4, 5, or 6.

[0019] Preferably, m is 1 to 6, more preferably 1 to 4, for example 1, 2, 3, or 4.

[0020] Preferably, q is 1 to 6, more preferably 2 to 4, for example 2, 3, or 4.

[0021] Preferably, p is 0 to 6, more preferably 0 to 3, for example 0, 1, 2, or 3.

[0022] When p is not 0, the compound of formula (I) has a free alcohol group.

[0023] Mixtures of compounds of formula (I) are also included within the scope of the present invention.

[0024] According to a preferred embodiment, R1 is the residue of acrylic acid (CH2=CH-C(=O)).

[0025] According to a preferred embodiment, R2 is (A) and X is S or O, preferably S.

[0026] According to a preferred embodiment, R2 is (A) and X is N-phenyl.

[0027] According to a preferred embodiment, R2 is (B), X is O, and Y is C(CH3)(CH3).

[0028] According to a preferred embodiment, R2 is (C) and X is CH2.

[0029] According to a preferred embodiment, R2 is (C) and X is N-alkyl.

[0030] When X is S, the sulfur in the oxidized form to sulfone or sulfoxide also falls within the scope of protection of the present invention.

[0031] According to another preferred embodiment of the present invention, q is 1 to 4, more preferably 2 to 4, for example, 2, 3, or 4; p is 0 to 3, more preferably 0 to 2, for example, 0, 1, or 2; m is 1 to 6, more preferably 2 to 4, for example, 2, 3, or 4; m+q+p is 3 to 6, more preferably 3 to 5, for example 3, 4, or 5.

[0032] As used herein, unless otherwise indicated, the term "alkyl" or "alkyl group" means a straight or branched saturated alkyl chain having the specified number of carbon atoms, and includes all possible isomers for each number of carbon atoms in the alkyl group, e.g., 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.

[0033] Preferably, alkyl is C1-C4 alkyl, for example, methyl or ethyl.

[0034] The compounds of the present invention can be prepared according to any suitable method, for example, by Friedel-Crafts acylation and optional esterification according to Scheme 1 below. Scheme 1 [ka] + G-(OH) m+q+p + (meth)acrylic acid → formula (I)

[0035] The reaction is carried out in a suitable solvent, such as an aromatic solvent, for example toluene, in the presence of methanesulfonic acid and disulfite. The resulting compound of formula (I) is then isolated according to known methods.

[0036] In the above reaction, (meth)acrylic acid may be substituted by a halide derivative, such as its chloride derivative.

[0037] The reactants are known and / or commercially available or are prepared according to known methods and / or as disclosed in the experimental section below.

[0038] According to another aspect, the present invention also relates to a process for preparing a compound of formula (I) comprising carrying out the reaction according to Scheme 1 above.

[0039] The chemical reactions of Scheme 1 are fully capable of being carried out by those skilled in the art according to known methods.

[0040] Details of the process of the present invention are reported in the experimental section of this specification.

[0041] According to another aspect, the present invention provides a method for manufacturing a semiconductor device comprising: (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); (b) 1 to 40% by weight, preferably 3 to 35% by weight, and more preferably 5 to 30% by weight (based on the total content of the composition) of at least one compound of formula (I) as defined above; and (c) Accelerators and / or coinitiators: 0 to 20% by weight, preferably 0 to 15% by weight, and more preferably 0.2 to 15% by weight (based on the total content of the composition) The present invention relates to a photopolymerizable composition comprising:

[0042] Preferably, the at least one compound (b) is present in an amount of 5 to 30%, for example 10, 15, 20, 25, or 30%.

[0043] According to the present invention, the terms "photohardenable" and "photopolymerizable" and related terms are synonymous.

[0044] The expression "total content of the composition" means that the weight percent amount of any of the components is calculated relative to the sum of the weights of all components of the composition (including components (a), (b), and (c) above, plus possibly further additional components), but that possible water and / or solvents that may be present in the composition are not taken into account when calculating said weight percent amount.

[0045] According to another aspect, the present invention relates to a method for photocuring photopolymerizable compositions, coatings, adhesives, and inks, said method comprising: i. providing a photopolymerizable composition as defined above; ii. coating or printing the photopolymerizable composition onto a substrate; and iii. photo-curing the composition coated or printed on the substrate with a light source It comprises:

[0046] According to another aspect, the present invention relates to a three-dimensional printing method comprising photocuring a mixture comprising the composition as defined above with a light source.

[0047] According to another aspect, the present invention relates to the product obtained by the method of the present invention.

[0048] In addition to compounds (a), (b), and (c), if present, the photocurable compositions of the present invention may also comprise one or more of the following components: (d) sensitizers and / or (e) further photoinitiators and / or (f) general additives.

[0049] According to a preferred embodiment, the photopolymerizable composition used in the method of the present invention comprises at least components (a), (b), and (c), more preferably at least components (a), (b), (c), and (d) as defined above.

[0050] The photoinitiators of the present invention are used in photocurable compositions comprising ethylenically unsaturated compounds (a). The unsaturated compounds (a) can contain one or more olefinic double bonds. They can be low molecular weight (monomeric) or high molecular weight (oligomeric) compounds.

[0051] Suitable examples of low molecular weight monomers (monomer compounds) having one double bond include alkyl or hydroxyalkyl acrylates or methacrylates, such as methyl, ethyl, butyl, 2-ethylhexyl, 2-hydroxyethyl, or isobornyl acrylate; and methyl or ethyl methacrylate. Further examples include silicon- or fluorene-modified resins, such as silicone acrylates. Further examples of these 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.

[0052] Examples of monomers having two or more double bonds are 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, divinylsuccinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, or tris-(2-acryloylethyl)isocyanurate.

[0053] 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. Other 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 3000 Da. Such unsaturated oligomers are also called prepolymers.

[0054] Examples of compounds (a) that are particularly suitable for carrying out the present invention are esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers containing ethylenically unsaturated groups in the chain or in the side chain, such as unsaturated polyesters, polyamides, and polyurethanes, and copolymers thereof, alkyl resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers with (meth)acrylic groups in the side chain, and also mixtures thereof.

[0055] Illustrative examples of unsaturated carboxylic acids or anhydrides useful in preparing the esters are 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.

[0056] The polyols to be esterified are aromatic, aliphatic, and cycloaliphatic polyols, preferably aliphatic and cycloaliphatic polyols.

[0057] Aromatic polyols include, for example, hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl)propane, as well as novolaks and resols. Polyols to be esterified include the reaction products of the aforementioned polyols, especially aromatic polyols, with epichlorohydrin. Polymers and copolymers containing hydroxyl groups in the polymer chain or side groups, such as polyvinyl alcohol and its copolymers, or poly(hydroxyalkyl methacrylate esters) or its copolymers, are also suitable as polyols. Further suitable polyols are oligoesters with hydroxyl end groups.

[0058] Examples of aliphatic and alicyclic 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, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycol preferably having a molecular weight of 200 to 1500 Da, 1,3-cyclopentanediol, 1,2-, 1,3-, or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerin, tris(β-hydroxyethyl)amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol.

[0059] Further suitable ethylenically unsaturated compounds (a) are unsaturated polyamides derived 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 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, triethylenetetraamine, and di(β-aminoethoxy)- and di(β-aminopropoxy)ethane. Other suitable polyamines are polymers and copolymers containing additional amino groups in the side chains and oligoamides containing amino end groups.

[0060] Specific examples of such unsaturated polyamides are methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)ethane, and N-[(β-hydroxyethoxy)ethyl]-acrylamide.

[0061] Also suitable as component (a) in the practice of the present invention are unsaturated polyurethanes, such as those derived from saturated or unsaturated diisocyanates and unsaturated or saturated diols. Polybutadiene and polyisoprene and their copolymers are also useful. Suitable monomers include, for example, olefins such as ethylene, propylene, butene, and hexene, (meth)acrylates, acrylonitrile, styrene, and vinyl chloride.

[0062] Polymers having unsaturated (meth)acrylate groups in the side chains can also be used as component (a). These are generally reaction products of novolac epoxy resins with (meth)acrylic acid, homo- or copolymers of vinyl alcohol or its hydroxyalkyl derivatives esterified with (meth)acrylic acid, and homo- or copolymers of (meth)acrylates esterified with hydroxyalkyl (meth)acrylic acid.

[0063] According to a preferred embodiment, the photocurable composition may further comprise a co-photoinitiator (c) (also called accelerator).

[0064] Suitable examples of accelerators and / or co-photoinitiators (c) are alcohols, thiols, thioethers, amines or ethers having an available oxygen attached to the carbon adjacent to the heteroatom, disulfides, and phosphines, for example those disclosed in EP 438 123 and GB 2 180 358.

[0065] Suitable examples of amine accelerators / co-initiators include, but are not limited to, aliphatic, cycloaliphatic, aromatic, aryl-aliphatic, 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, dimethylaminobenzoic acid esters, Michler's ketone (4,4'-bis-dimethylaminobenzophenone), and its derivatives.

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

[0067] Also suitable as coinitiators are polyfunctional amines and polymeric amine derivatives, some examples of which are Omnipol® ASA (IGM Resins BV), Genopol® AB-2 (Rahn AG), Speedcure® 7040 (Lambson Limited), or those described in US 2013 / 0012611.

[0068] The photocurable compositions of the present invention may also be prepared as compositions comprising water and / or a solvent, such as an organic solvent.

[0069] The photosensitizer (d) can be present in an amount of 0.01 to 15% by weight (based on the total content of the composition), preferably 0.01 to 10% by weight.

[0070] Examples of sensitizers are those commonly used in the art: aromatic carbonyl compounds, such as benzophenone, thioxanthone, anthraquinone, coumarin, and 3-acylcoumarin derivatives, terphenyls, styryl ketones, and 3-(aroylmethylene)-thiazolines, camphorquinone, and eosin, rhodamine, and erythrosin dyes.

[0071] 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-cyclo-3-chlorothioxanthone. thioxanthone, 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-carboximide, N-(1,1,3,3-tetramethylbutyl)-thioxanthone-3,4-dicarboximide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone Thilthioxanthone, thioxanthone-2-polyethylene glycol ester, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy)-N,N,N-trimethyl-1-propaneammonium chloride, or those described in International Patent Application PCT / EP2011 / 069514, such as n-dodecyl-7-methyl-thioxanthone-3-carboxylate and N,N-diisobutyl-7-methyl-thioxanthone-3-carboxamide.Polymeric thioxanthone derivatives (e.g., Omnipol® TX (IGM Resins BV), Genopol® TX-1 (Rahn AG), Speedcure® 7010 (Lambson Limited)) are also suitable.

[0072] 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-trimethylbenzenemethane ammonium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propane ammonium chloride monohydrate, 4-(13-acryloyl-1,4,7,10,13-pentaoxatridecyl)benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyl)oxyethyl-benzenemethane ammonium chloride, or those described in US 9938231 (e.g., Omnirad® 991 (IGM Resins BV)).

[0073] Polymeric benzophenone derivatives (e.g., Omnipol® BP, Omnipol 2702, and Omnipol 682 (IGM Resins BV), Genopol® BP-2 (Rahn AG), and Speedcure® 7005 (Lambson Limited)) are also suitable.

[0074] 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-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-benzoyl)coumarin, 5,7-dimethoxy-3(1-benzoyl)-coumarin, 3-benzoylbenzo[f]coumarin, 7-diethylamino-3-thienoylcoumarin, 3-(4-cyanobenzoyl)-5,7-dimethoxycoumarin, or those described in EP2909243 and WO2017 / 216699.

[0075] Examples of 3-(aroylmethylene)thiazolines are 3-methyl-1,2-benzoylmethylene-β-benzothiazoline, 3-methyl-2-benzoylmethylene-benzothiazoline, 3-ethyl-2-propionylmethylene-β-benzothiazoline.

[0076] Examples of other aromatic carbonyl compounds are acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzil, such as those described in WO 2013 / 164394, 2-acetylnaphthalene, 2-naphthaldehyde, 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.

[0077] Thioxanthone, coumarin, and 3-acetylcoumarin are particularly preferred.

[0078] The component (d) has been observed to increase the activity of the photoinitiator (b) without shortening the shelf life of the composition. Furthermore, such compositions have the special advantage that the selection of an appropriate sensitizer (d) makes it possible to shift the spectral sensitivity of the photoinitiator (b) to various desired wavelength regions. Those skilled in the art can select a suitable sensitizer (d) to make the photoinitiator (b) function in various desired wavelength regions.

[0079] Furthermore, possible photoinitiators (e) may be present in an amount of 0.5 to 15% by weight of the composition (based on the total content of the composition), preferably 1 to 10% by weight.

[0080] Examples of other suitable photoinitiators (e) are 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 (Esacure® 1001 (IGM Resins) BV), 3-ketocoumarins (e.g., as described in EP 2909243 or WO 2017 / 216699), phenylglyoxylate and its derivatives, dimeric phenylglyoxylate, peresters such as benzophenonetetracarboxylic acid perester (e.g., as 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, hexaarylbisimidazole / coinitiator systems such as ortho-chlorohexaphenylbisimidazole in combination with 2-mercaptobenzothiazole, ferrocenium compounds or titanocenes such as dicyclopentadienyl-bis(2,6-difluoro-3-pyrrolo-phenyl)titanium, O-acyloxime ester photoinitiators.

[0081] Examples of α-hydroxyketones and α-aminoketones 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.

[0082] Examples of O-acyloxime ester photoinitiators are 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] 1-(O-acetyloxy), or those described in GB 2339571.

[0083] 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 triester (Omnipol® TP (IGM Resins BV)).

[0084] Examples of halomethyltriazine photoinitiators are 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, 2-methyl-4,6-bis-trichloromethyl[1,3,5]triazine.

[0085] If the photocurable composition according to the invention is used in a hybrid system (which in this respect means a mixture of free radically and cationically curable systems), a cationic photoinitiator is also used as the further photoinitiator (e). Examples of suitable cationic photoinitiators are aromatic sulfonium, phosphonium or iodonium salts, or cyclopentadienyl arene-iron(II) complex salts, such as (η 6 -isopropylbenzene)(η 5 -cyclopentadienyl)iron(II) hexafluorophosphate, or oxime-based photolatent acids, as described, for example, in GB 2 348 644, US Pat. No. 4,450,598, US Pat. No. 4,136,055, WO 00 / 10972 and WO 00 / 26219.

[0086] The photocurable composition according to the present invention may also contain 0 to 10% by weight (based on the total content of the composition) of common additives. The additives (f) are, for example, thermal initiators, binders, stabilizers, and mixtures thereof.

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

[0088] For example, particularly in the case of pigmented compositions, the composition may also comprise as additional additive (f) a thermal initiator (a compound which forms free radicals when heated), such as an azo compound (e.g., 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), triazenes, diazosulfides, pentazadiene), or a peroxy compound, such as a hydroperoxide or peroxycarbonate, such as tertiary-butyl hydroperoxide (as described, for example, in EP 245639).

[0089] A binder can also be 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 (based on the total content of the composition excluding water and solvents where possible), preferably 10 to 50% by mass. The binder is selected depending on the application and the properties required therefor, such as developability in aqueous and organic solvent systems, adhesion to substrates, and sensitivity to oxygen.

[0090] 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. Illustrative examples include homo- and copolymers of acrylates and methacrylates, such as methyl methacrylate / ethyl acrylate / methacrylic acid copolymers, 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, polypropylene oxide, polypropylene glycol ... Examples of suitable polymers include tetrahydrofuran, polystyrene, polycarbonate, polyurethane, chlorinated polyolefins such as polyvinyl chloride, vinyl chloride / vinylidene chloride copolymers, copolymers of vinylidene chloride with acrylonitrile, methyl methacrylate, vinyl acetate, polymers such as polyvinyl acetate, copoly(ethylene / vinyl acetate), polycaprolactam, and poly(hexamethylene adipamide), and polyesters such as poly(ethylene glycol terephthalate) and poly(hexamethylene glycol succinate).

[0091] Suitable stabilizers include, for example, thermal initiators that prevent premature polymerization, such as hydroquinone, hydroquinone derivatives, p-methoxyphenol, β-benzol, or sterically hindered phenols, such as 2,6-di(tert-butyl)-p-cresol. To enhance dark storage stability, copper compounds, such as copper naphthenate, stearate, or octoate, phosphorus compounds, such as triphenylphosphine, tributylphosphine, triethylphosphite, triphenylphosphite, or tribenzylphosphite, quaternary ammonium compounds, such as tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives, such as N,N-diethylhydroxylamine, can be used. To exclude atmospheric oxygen during polymerization, paraffin or similar wax-like substances can be added. These substances are insoluble in the polymer and migrate to the surface at the onset of polymerization, forming a transparent surface layer that prevents air from penetrating.

[0092] It is also possible to add light stabilizers, such as UV absorbers of the hydroxyphenylbenzotriazole, hydroxyphenylbenzophenone, oxalic acid amide or hydroxyphenyl-s-triazine type, such compounds being used alone or in mixtures with or without sterically hindered amines (HALS).

[0093] The photocurable compositions according to the invention may contain as further additives (f) photoreducible dyes, such as xanthene, benzoxanthene, benzothioxanthene, thiazine, pyronine, porphyrin, or acridine dyes, and / or radiation-cleavable trihalomethyl compounds, which are described, for example, in EP 445624.

[0094] Further customary additives (f) are, depending on the intended use, optical brighteners, fillers, pigments, white and colored pigments, colorants, antistatic agents, wetting agents, or flow improvers. Additives customarily used in the art, such as antistatic agents, flow improvers, and adhesion promoters, can also be used.

[0095] In addition to the above ingredients, other ingredients may also be present in the compositions of the present invention.

[0096] Chain transfer agents conventionally used in the art can also be added to the photocurable compositions according to the invention. Examples are mercaptans, amines, and benzothiazoles.

[0097] The compositions of the present invention can also contain colorants and / or white or colored pigments. Both inorganic and organic pigments can be used depending on the intended application. Such additives are well known to those skilled in the art; some examples are carbon black, iron oxide (e.g., 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 are mono- or bis-azo pigments and their metal complexes, phthalocyanine pigments, polycyclic azo pigments such as perylene, anthraquinone, thioindigo, quinacridone, or triphenylmethane pigments, and diketopyrrolopyrrole, isoindolinone, e.g., tetrachloroisoindolinone, isoindoline, dioxazine, benzimidazolone, and quinophthalone pigments. Pigments can be used alone or in mixtures in the formulation.

[0098] The pigments are added to the formulation in amounts conventionally used in the art, for example, 0.1 to 30% by weight (based on the total weight of the composition), or 10 to 25% by weight, depending on the intended use.

[0099] The compositions can also contain, for example, a wide variety of organic colorants. Examples are azo dyes, methine dyes, anthraquinone dyes, and metal complex dyes. Typical concentrations are, for example, 0.1 to 20% by weight (based on the total weight of the composition), in particular 1 to 5% by weight.

[0100] The photocurable composition of the present invention may also comprise water.

[0101] The photocurable compositions of the present invention can be used for various 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, as pigmented coats (e.g. for wood or metal), as powder coatings, as coating materials (e.g. for paper, wood, metal or plastics), as sun-curable paints for marking structures or roads, for photographic reproduction processes, for holographic recording materials, for image recording processes or in the manufacture of printing plates which are developed using organic solvents or using aqueous alkaline media, for the manufacture of masks for screen printing, as dental filling materials, as adhesives, as pressure-sensitive adhesives, as laminating resins, as photoresists (e.g. galvanoresists), etch resists or permanent resists (both liquid and dry film). They are suitable for use as photostructurable dielectrics and as solder masks for electronic circuits, in the manufacture of color filters for various display screens or in the formation of structures during the manufacture of plasma and electroluminescent displays, 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 (described, for example, in U.S. Pat. No. 4,575,330), in the manufacture of composite materials (e.g., styrene polyesters, which may contain glass fibers and / or other fibers and other adjuvants)) and in three-dimensional printing methods known to those skilled in the art, as resists in the coating or encapsulation of electronic components, or as coatings for optical fibers.

[0102] The photocurable compositions of the present invention are also suitable in dry film coatings in the manufacture of optical lenses, such as contact lenses or Fresnel lenses, in the manufacture of medical devices, aids or implants.

[0103] The photocurable compositions of the present invention are also suitable for the production of gels with thermotropic properties, such gels being described, for example, in DE 19700064 and EP 678534.

[0104] Various articles comprising a compound of formula (I) or comprising the photocurable composition of the present invention are further subjects of the present invention.

[0105] The compounds and compositions according to the invention are also used as free radical photoinitiators or photoinitiating systems for radiation-curable powder coatings.

[0106] The photocurable compositions according to the invention are suitable, for example, as coating materials for all kinds of substrates (on which a protective film is applied or on which an image is applied, for example by imagewise exposure) such as wood, textiles, paper, ceramics, glass, plastics (e.g. polyester, polyethylene terephthalate, polyolefins, and cellulose acetate, especially in film form), and metals (e.g. Al, Cu, Ni, Fe, Zn, Mg, or Co, and GaAs, Si, or SiO).

[0107] A large number of different light sources can be used in the method according to the invention, which emit light at wavelengths between about 200 and about 800 nm. Both point sources and platform radiators (lamp carpets) are suitable. Examples are carbon arc lamps, xenon arc lamps, medium-, high-, and low-pressure mercury arc radiators (optionally doped with metal halides) (metal halide lamps), microwave-excited metal vapor lamps, excimer lamps, super-photoactive fluorescent lamps, fluorescent lamps, argon incandescent lamps, flash lamps, photographic floodlight lamps, light-emitting diodes (LEDs), electron beams, X-rays, and lasers.

[0108] According to one embodiment, the light source comprises UV light in at least one of the UVA, UVB and UVC regions.

[0109] According to a preferred embodiment, the light source is an LED source, with LED light sources emitting at wavelengths between 365 and 420 nm, more preferably at 365 nm, 385 nm and 395 nm being particularly preferred.

[0110] According to the invention, the distance between the lamp and the substrate according to the invention to be exposed varies depending on the intended use and the type and power of the lamp and is, for example, from 0.1 to 150 cm, preferably from 1 to 50 cm.

[0111] The photopolymerizable composition may also be applied onto a substrate that already comprises a coated or printed layer, and after photopolymerization with the light source, the photopolymerizable composition may be overprinted or overcoated with one or more compositions suitable for printing or coating.

[0112] The article obtained by applying the photopolymerizable composition onto the substrate by the coating or printing means, photopolymerizing with the light source, and then carefully finishing the article by coating or printing, or without finishing, is a further subject of the present invention.

[0113] As mentioned above, it has been surprisingly found that the compounds of formula (I) have very high reactivity under UVA, UVB and UV wavelengths while maintaining low post-cure yellowing compared to those of the prior art. The new compounds have shown significant improvements in surface curing under LED and Hg lamps.

[0114] The present invention will now be described in more detail with reference to the following examples, which are illustrative and not limiting.

[0115] [Experimental section] In the present specification, if there is a discrepancy between a chemical name and a chemical formula, the latter shall prevail. The designation "rt" means room temperature. In the formula below, each "n" value is selected independently of the others, ie, each n value may be different from each other even within the same formula. In the examples below, the portion of formula (I) in square brackets, i.e. [ka] is referred to as the "q-portion." 1 1 H NMR spectra were recorded on a Bruker Ascend 300 MHz NMR spectrometer.

[0116] [Preparation Example 1] [ka] To an ice-cooled mixture of 50.00 g (268.43 mmol) of diphenyl sulfide and 39.76 g (268.43 mmol) of phthalic anhydride in 300 mL of chlorobenzene, 71.58 g (536.82 mmol) of anhydrous aluminum chloride was carefully added in small portions. The reaction mixture was stirred at room temperature for 1.5 hours and then poured into ice / dilute hydrochloric acid. The mixture was extracted with ethyl acetate, and the organic phase was separated, washed with 1 M hydrochloric acid, dried over anhydrous sodium sulfate, filtered, and the solvent removed by vacuum distillation. The crude product was purified by crystallization from toluene to give 76.63 g of a white solid (86% yield). 1 H-NMR (DMSO-d6, δ ppm): 7.24 (d, 2H), 7.40 (dd, 1H), 7.46-7.56 (m, 7H), 7.61-7.74 (m, 2H), 7.99 (dd, 1H)

[0117] [Preparation Example 2] [ka] To an ice-cooled mixture of 15.00 g (90.242 mmol) of fluorene and 13.36 g (90.197 mmol) of phthalic anhydride in 270 mL of chlorobenzene, 24.07 g (180.516 mmol) of anhydrous aluminum chloride was carefully added in small portions. The reaction mixture was stirred at room temperature for 1.5 hours and then poured into ice / dilute hydrochloric acid. The semi-solid product thus obtained was treated with 270 mL of ethyl acetate, and the resulting solid was filtered. The filtrate phase was then separated, washed with 1 M hydrochloric acid, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product, along with the previously filtered solid, was suspended in 200 mL of toluene and washed under reflux with vigorous stirring for 30 minutes. The mixture was then cooled to room temperature, yielding 27.26 g of a white solid, which was filtered (96% yield). 1 H-NMR (DMSO-d6, δ ppm): 3.99 (s, 2H), 7.38-7.48 (m, 3H), 7.60-7.76 (m, 4H), 7.86 (s, 1H), 7.98-8.04 (m, 3H)

[0118] [Preparation Example 3] [ka] To an ice-cooled mixture of 15.00 g (88.126 mmol) of diphenyl ether and 13.05 g (88.104 mmol) of phthalic anhydride in 250 mL of chlorobenzene, 23.50 g (176.241 mmol) of anhydrous aluminum chloride was carefully added in small portions. The reaction mixture was stirred at room temperature for 1.5 hours and then poured into ice / dilute hydrochloric acid. The mixture was extracted with ethyl acetate, and the organic phase was separated, washed with 1 M hydrochloric acid, dried over anhydrous sodium sulfate, filtered, and the solvent removed by vacuum distillation. The crude product was purified by crystallization from toluene to give 23.25 g of a white solid (83% yield). 1H-NMR (DMSO-d6, δ ppm): 7.03 (d, 2H), 7.14 (m, 2H), 7.25 (m, 1H), 7.38-7.49 (m, 3H), 7.62-7.75 (m, 4H), 7.98 (dd, 1H)

[0119] [Preparation Example 4] [ka] To an ice-cooled mixture of 5.15 g (24.491 mmol) of 9,9-dimethylxanthene and 3.63 g (24.507 mmol) of phthalic anhydride in 85 mL of chlorobenzene, 6.53 g (48.973 mmol) of anhydrous aluminum chloride was carefully added in small portions. The reaction mixture was stirred at room temperature for 1.5 hours and then poured into ice / dilute hydrochloric acid. The mixture was extracted with ethyl acetate, and the organic phase was separated, washed with 1 M hydrochloric acid, dried over anhydrous sodium sulfate, and filtered. An equal amount of 4-methoxyphenol was added, and the solvent was removed by vacuum distillation. The crude product was purified by crystallization from toluene to give 7.15 g of a white solid (81% yield). 1 H-NMR (DMSO-d6, δ ppm): 1.58 (s, 6H), 7.09-7.20 (m, 3H), 7.28 (m, 1H), 7.38-7.46 (m, 2H), 7.58 (dd, 1H), 7.62-7.78 (m, 2H), 7.93 (d, 1H), 8.00 (dd, 1H)

[0120] [Preparation Example 5] [ka] To an ice-cooled mixture of 15.00 g (76.817 mmol) of 9-ethylcarbazole and 5.69 g (38.415 mmol) of phthalic anhydride in 250 mL of chlorobenzene, 5.12 g (38.398 mmol) of anhydrous aluminum chloride was carefully added in small portions. The reaction mixture was stirred at room temperature for 1 hour. Then, the reaction mixture was cooled again, and an additional 2.84 g (19.174 mmol) of phthalic anhydride and 2.56 g (19.199 mmol) of anhydrous aluminum chloride were added sequentially. This procedure was repeated once more. Finally, the reaction mixture was poured into ice / dilute hydrochloric acid. The mixture was extracted with ethyl acetate, the organic phase was separated, washed with 1 M hydrochloric acid, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was suspended in 250 mL of toluene and stirred vigorously under reflux for 30 minutes. The mixture was cooled to room temperature, and the solid was collected by filtration. The solid was suspended in 200 mL of toluene and washed again with vigorous stirring under reflux for 24 hours to give 7.61 g of the product as a white solid (yield 33%). 1 H-NMR (DMSO-d6, δ ppm): 1.34 (t, 3H), 4.49 (q, 2H), 7.23 (t, 1H), 7.44-7.55 (m, 2H), 7.64-7.77 (m, 5H), 8.01 (dd, 1H), 8.20 (d, 1H), 8.50 (d, 1H)

[0121] [Preparation Example 6] [ka] To an ice-cooled mixture of 15.00 g (61.145 mmol) of triphenylamine and 4.53 g (30.583 mmol) of phthalic anhydride in 200 mL of chlorobenzene, 4.07 g (30.523 mmol) of anhydrous aluminum chloride was carefully added in small portions. The reaction mixture was stirred at room temperature for 1 hour. Then, the reaction mixture was cooled again, and an additional 2.27 g (15.325 mmol) of phthalic anhydride and 2.04 g (15.299 mmol) of anhydrous aluminum chloride were added sequentially. This procedure was repeated once more. Finally, the reaction mixture was poured into 400 mL of ice / water. The mixture was extracted with ethyl acetate, and the organic phase was separated, dried over anhydrous sodium sulfate, filtered, and the solvent removed by vacuum distillation. The crude product was purified by column chromatography on silica gel (toluene / ethyl acetate: 50 / 50) to give 7.85 g of the product as a yellow solid (34% yield). 1H-NMR (DMSO-d6, δ ppm): 6.83 (d, 2H), 7.10-7.28 (m, 6H), 7.33-7.43 (m, 5H), 7.49 (d, 2H), 7.56-7.71 (m, 2H), 7.97 (dd, 1H) [Example]

[0122] (Total grafting rate: 92.3%, q-moiety / acrylate: 1 / 2.7) [ka] [ka] A mixture of 50.00 g (hydroxyl number: 634 / g) of polyol 4640 (purchased from Perstorp), 47.23 g (141.24 mmol) of the compound from Preparation Example 1, 3.18 g (23.16 mmol) of 70% aqueous methanesulfonic acid, and 2.53 g (19.20 mmol) of 50% aqueous hypophosphorous acid in toluene was stirred under reflux for 6 h while removing water using a Dean-Stark apparatus. The mixture was then brought to RT, and 0.14 g of 4-methoxyphenol was added, followed by 40.30 g (559.26 mmol) of acrylic acid. The mixture was stirred at 85 °C (internal temperature) by bubbling air through a Pasteur pipette to induce reflux, while the temperature was maintained constant for 6 h. Finally, the mixture was brought to rt, diluted with EtOAc (150 mL), and washed with 0.25 M Na2CO3 (200 mL) and brine (200 mL). The organic phase was dried over Na2SO4 and filtered. An equal amount of 4-methoxyphenol was added, and the solvent was removed under reduced pressure to give 103.50 g of the product as a pale yellow oil (88% yield). 1 H-NMR (DMSO-d6, δ ppm): 8.00-7.96 (m, 1H), 7.75-7.32 (m, 12H), 6.23-6.40 (m, 5.3H), 5.98-5.83 (m, 2.7H), 4.22-4.02 (m, 2.8H), 4.26-3.88 (m, 7.4H), 3.68-3.27 (29.6H) [Example]

[0123] (Total grafting rate: 80.5%, q-moiety / acrylate: 2.9 / 1) [ka] [ka] A mixture of 2.50 g (hydroxyl number: 364 / g) of polyol 3380 (purchased from Perstorp), 3.36 g (10.87 mmol) of the compound from Preparation 1, 0.09 g (0.66 mmol) of 70% aqueous methanesulfonic acid, and 0.07 g (0.55 mmol) of 50% aqueous hypophosphorous acid in toluene was stirred under reflux for 6 h while removing water using a Dean-Stark apparatus. The mixture was then brought to RT, and 0.007 g of 4-methoxyphenol was added, followed by 0.51 g (7.14 mmol) of acrylic acid. The mixture was stirred at 85 °C (internal temperature) by bubbling air through a Pasteur pipette to induce reflux, while the temperature was maintained constant for 6 h. Finally, the mixture was brought to RT, diluted with EtOAc (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic phase was dried over Na2SO4 and filtered, and the same amount of 4-methoxyphenol was added and the solvent was removed under reduced pressure to give 5.87 g of the product as a colorless oil (98% yield). 1 H-NMR (DMSO-d6, δ ppm): 8.04-7.88 (m, 1.8H), 7.83-7.62 (m, 4H), 7.60-7.34 (m, 13.7H), 7.32-7.10 (m, 5.6H), 6.39-6.05 (m, 1.2H), 5.99-5.84 (m, 0.6H), 4.26-3.87 (m, 4.9H), 3.65-3.34 (m, 33.1H), 1.43-1.18 (m, 2H), 0.89-0.58 (m, 3H) [Example]

[0124] (Total grafting rate: 70%, q-moiety / acrylate: 2.5 / 1) [ka] [ka] A mixture of 2.50 g (hydroxyl value: 300 / g) of sorbilene RE / 20 (purchased from Lamberti SpA), 2.24 g (6.69 mmol) of the compound from Preparation 1, 0.08 g (0.55 mmol) of 70% aqueous methanesulfonic acid, and 0.06 g (0.45 mmol) of 50% aqueous hypophosphorous acid in toluene was stirred under reflux for 6 h while removing water using a Dean-Stark apparatus. The mixture was then brought to RT, and 0.006 g of 4-methoxyphenol was added, followed by 0.64 g (8.83 mmol) of acrylic acid. The mixture was stirred at 85 °C (internal temperature) by bubbling air through a Pasteur pipette to induce reflux, while the temperature was maintained constant for 6 h. Finally, the mixture was brought to RT, diluted with EtOAc (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic phase was dried over Na2SO4 and filtered, and the same amount of 4-methoxyphenol was added and the solvent was removed under reduced pressure to give 4.51 g of the product as a colorless oil (88% yield). 1 H-NMR (DMSO-d6, δ ppm): 7.94-7.77 (m, 1H), 7.76-7.03 (m, 12H), 6.31-5.96 (m, 0.8H), 5.91-5.77 (m, 0.4H), 4.17-3.98 (m, 7H), 3.70-3.27 (m, 85H) [Example]

[0125] (Total grafting rate: 96.8%, q-moiety / acrylate: 1 / 2.8) [ka] [ka] A mixture of 50.00 g (hydroxyl number: 634 / g) of polyol 4640 (purchased from Perstorp), 44.40 g (141.25 mmol) of the compound from Preparation Example 2, 3.18 g (23.16 mmol) of 70% aqueous methanesulfonic acid, and 2.53 g (19.20 mmol) of 50% aqueous hypophosphorous acid in toluene was stirred under reflux for 6 h while removing water using a Dean-Stark apparatus. The mixture was then brought to RT, and 0.14 g of 4-methoxyphenol was added, followed by 40.30 g (559.26 mmol) of acrylic acid. The mixture was stirred at 85 °C (internal temperature) by bubbling air through a Pasteur pipette to induce reflux, while the temperature was maintained constant for 6 h. Finally, the mixture was brought to rt, diluted with EtOAc (150 mL), and washed with 0.25 M Na2CO3 (200 mL) and brine (200 mL). The organic phase was dried over Na2SO4 and filtered. An equal amount of 4-methoxyphenol was added, and the solvent was removed under reduced pressure to give 113.76 g of the product as a pale yellow oil (91% yield). 1 H-NMR (DMSO-d6, δ ppm): 8.09-7.84 (m, 4H), 7.83-7.55 (m, 4H), 7.54-7.32 (m, 3H), 6.41-6.05 (m, 5.5H), 6.00-5.83 (m, 2.8H), 4.26-3.88 (m, 7.6H), 3.68-3.27 (29.4H) [Example]

[0126] (Total grafting rate: 90.0%, q-moiety / acrylate: 1 / 1.5) [ka] [ka] A mixture of 2.50 g (hydroxyl value: 370 / g) of Aionico GL / 609 (purchased from Lamberti SpA), 1.86 g (5.44 mmol) of the compound from Preparation Example 2, 0.09 g (0.68 mmol) of 70% aqueous methanesulfonic acid, and 0.07 g (0.56 mmol) of 50% aqueous hypophosphorous acid in toluene was stirred under reflux for 6 h while removing water using a Dean-Stark apparatus. The mixture was then brought to RT, and 0.006 g of 4-methoxyphenol was added, followed by 1.05 g (14.51 mmol) of acrylic acid. The mixture was stirred at 85 °C (internal temperature) by bubbling air through a Pasteur pipette to induce reflux, while the temperature was maintained constant for 6 h. Finally, the mixture was brought to rt, diluted with EtOAc (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic phase was dried over Na2SO4 and filtered. An equal amount of 4-methoxyphenol was added, and the solvent was removed under reduced pressure to give 4.58 g of the product as a colorless oil (89% yield). 1 H-NMR (DMSO-d6, δ ppm): 8.08-7.85 (m, 4H), 7.83-7.55 (m, 5H), 7.46-7.30 (m, 2H), 6.39-6.09 (m, 2.9H), 5.99-5.84 (m, 1.5H), 4.22-4.16 (m, 2H), 4.15-3.89 (m, 4.8H), 3.69-3.37 (32.2H) [Example]

[0127] (Total grafting rate: 87.5%, q-moiety / acrylate: 1 / 2.5) [ka] [ka] A mixture of 2.50 g (hydroxyl value: 634 / g) of polyol 4640 (purchased from Perstorp), 2.25 g (7.06 mmol) of the compound from Preparation 3, 0.16 g (1.16 mmol) of 70% aqueous methanesulfonic acid, and 0.13 g (0.96 mmol) of 50% aqueous hypophosphorous acid in toluene was stirred under reflux for 6 h while removing water using a Dean-Stark apparatus. The mixture was then brought to RT, and 0.007 g of 4-methoxyphenol was added, followed by 2.01 g (27.97 mmol) of acrylic acid. The mixture was stirred at 85 °C (internal temperature) by bubbling air through a Pasteur pipette to induce reflux, while the temperature was maintained constant for 6 h. Finally, the mixture was brought to RT, diluted with EtOAc (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic phase was dried over Na2SO4 and filtered, and the same amount of 4-methoxyphenol was added and the solvent was removed under reduced pressure to give 4.70 g of the product as a colorless oil (81% yield). 1 H-NMR (DMSO-d6, δ ppm): 8.04-7.95 (m, 1H), 7.80-7.67 (m, 4H), 7.55-7.7.40 (m, 3H), 7.29-6.95 (m, 5H), 6.40-6.13 (m, 5H), 6.02-5.82 (m, 2.5H), 4.23-4.08 (m, 7H), 3.67-3.30 (m, 21H) [Example]

[0128] (Total grafting rate: 58.3%, q-moiety / acrylate: 1 / 2.5) [ka] [ka] A mixture of 3.00 g (hydroxyl value: 300 / g) of sorbilene RE / 20 (purchased from Lamberti SpA), 0.85 g (2.66 mmol) of the compound from Preparation 3, 0.09 g (0.66 mmol) of 70% aqueous methanesulfonic acid, and 0.07 g (0.55 mmol) of 50% aqueous hypophosphorous acid in toluene was stirred under reflux for 6 h while removing water using a Dean-Stark apparatus. The mixture was then brought to RT, and 0.004 g of 4-methoxyphenol was added, followed by 1.27 g (17.59 mmol) of acrylic acid. The mixture was stirred at 85 °C (internal temperature) by bubbling air through a Pasteur pipette to induce reflux, while the temperature was maintained constant for 6 h. Finally, the mixture was brought to RT, diluted with EtOAc (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic phase was dried over Na2SO4 and filtered, and the same amount of 4-methoxyphenol was added and the solvent was removed under reduced pressure to give 3.60 g of the product as a colorless oil (80% yield). 1 H-NMR (DMSO-d6, δ ppm): 8.03-7.90 (m, 1H), 7.88-7.60 (m, 4H), 7.58-7.7.35 (m, 3H), 7.29-6.92 (m, 5H), 6.40-6.08 (m, 5H), 5.96-5.86 (m, 2.5H), 4.58-4.10 (m, 7H), 3.80-3.38 (m, 85H) [Example]

[0129] (Total grafting rate: 87%, q-moiety / acrylate: 1 / 2.4) [ka] [ka] A mixture of 2.50 g (hydroxyl number: 634 / g) of polyol 4640 (purchased from Perstorp), 2.52 g (7.06 mmol) of the compound from Preparation 4, 0.17 g (1.16 mmol) of 70% aqueous methanesulfonic acid, and 0.13 g (0.96 mmol) of 50% aqueous hypophosphorous acid in toluene was stirred under reflux for 6 h while removing water using a Dean-Stark apparatus. The mixture was then brought to RT, and 0.007 g of 4-methoxyphenol was added, followed by 1.69 g (23.44 mmol) of acrylic acid. The mixture was stirred at 85 °C (internal temperature) by bubbling air through a Pasteur pipette to induce reflux, while the temperature was maintained constant for 6 h. Finally, the mixture was brought to RT, diluted with EtOAc (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic phase was dried over Na2SO4 and filtered, and the same amount of 4-methoxyphenol was added and the solvent was removed under reduced pressure to give 5.98 g of the product as a colorless oil (96% yield). 1 H-NMR (DMSO-d6, δ ppm): 8.03-7.79 (m, 2H), 7.75-7.52 (m, 2H), 7.51-7.7.26 (m, 3H), 7.24-6.90 (m, 4H), 6.32-5.94 (m, 4.5H), 5.91-5.71 (m, 2.4H), 4.18-3.87 (m, 6.7H), 3.65-3.26 (m, 21.3H) [Example]

[0130] (Total grafting rate: 87.5%, q-moiety / acrylate: 1 / 2.5) [ka] [ka] A mixture of 2.50 g (hydroxyl value: 634 / g) of polyol 4640 (purchased from Perstorp), 2.42 g (7.06 mmol) of the compound from Preparation 5, 0.16 g (1.16 mmol) of 70% aqueous methanesulfonic acid, and 0.13 g (0.96 mmol) of 50% aqueous hypophosphorous acid in toluene was stirred under reflux for 6 h while removing water using a Dean-Stark apparatus. The mixture was then brought to RT, and 0.007 g of 4-methoxyphenol was added, followed by 2.01 g (27.97 mmol) of acrylic acid. The mixture was stirred at 85 °C (internal temperature) by bubbling air through a Pasteur pipette to induce reflux, while the temperature was maintained constant for 6 h. Finally, the mixture was brought to RT, diluted with EtOAc (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic phase was dried over Na2SO4 and filtered, and the same amount of 4-methoxyphenol was added and the solvent was removed under reduced pressure to give 5.64 g of the product as a colorless oil (95% yield). 1 H-NMR (DMSO-d6, δ ppm): 8.55-8.46 (m, 1H), 8.24-8.12 (m, 1H), 8.07-7.94 (m, 1H), 7.83-7.59 (m, 5H), 7.56-7.42 (m, 2H), 7.22-7.13 (m, 1H), 6.40-6.06 (m, 5H), 5.99-5.82 (m, 2.5H), 4.59-4.36 (m, 2H), 4.26-4.02 (m, 7H), 3.70-3.36 (m, 21H) [Example]

[0131] (Total grafting rate: 92%, q-moiety / acrylate: 1 / 2.7) [ka] [ka] A mixture of 2.50 g (hydroxyl number: 634 / g) of polyol 4640 (purchased from Perstorp), 2.78 g (7.06 mmol) of the compound from Preparation 6, 0.16 g (1.16 mmol) of 70% aqueous methanesulfonic acid, and 0.13 g (0.96 mmol) of 50% aqueous hypophosphorous acid in toluene was stirred under reflux for 6 h while removing water using a Dean-Stark apparatus. The mixture was then brought to RT, and 0.007 g of 4-methoxyphenol was added, followed by 1.69 g (23.44 mmol) of acrylic acid. The mixture was stirred at 85 °C (internal temperature) by bubbling air through a Pasteur pipette to induce reflux, while the temperature was maintained constant for 6 h. Finally, the mixture was brought to RT, diluted with EtOAc (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic phase was dried over Na2SO4 and filtered, and the same amount of 4-methoxyphenol was added and the solvent was removed under reduced pressure to give 5.70 g of the product as a colorless oil (89% yield). 1 H-NMR (DMSO-d6, δ ppm): 7.91-7.78 (m, 1H), 7.66-7.49 (m, 2H), 7.47-7.7.36 (m, 1H), 7.35-6.97 (m, 12H), 6.96-6.82 (m, 1H), 6.79-6.67 (m, 1H), 6.34-5.95 (m, 5.14H), 5.92-5.72 (m, 2.7H), 4.18-3.98 (m, 7.4H), 3.66-3.22 (m, 20.6H)

[0132] [Comparative Test] The activity of representative photoinitiators (PIs) of the present invention was compared to the photoinitiator Ebecryl LEO 10103 (commercially available from Allnex; herein referred to as COMP-1). [Example]

[0133] Tack-free and Yellowness Index (YI) in clear formulations Photopolymerizable compositions for testing were prepared by dissolving the PIs at a concentration of 20 wt% in a solution of 50% Photomer 3016 (bisphenol A epoxy diacrylate), 15% Photomer 4335 (PETIA), 15% Photomer 4666 (DPHA), and 20% Photomer 4172 (PPTTA). The PIs were tested alone (Table 1), or with the addition of a coinitiator (Omnipol ASA) at a concentration of 4 wt. % (Table 2), or with the addition of a coinitiator (Omnipol ASA) at a concentration of 4 wt. % and Omnirad ITX as a sensitizer at a concentration of 0.5 wt. % (Tables 3 and 4). The photopolymerizable composition was applied to a varnished cardboard sheet to a thickness of 12 microns using a bar coater, and then a) mercury lamp at a distance of 8 cm, b) LED 395 nm lamp at a distance of 0.5 cm; c) LED 365 nm lamp at a distance of 0.5 cm Photopolymerization was carried out using YI was assessed in several tests.

[0134] The results are expressed as the maximum speed reached tack-free in m / min.

[0135] Table 1 reports the results using a UV Hg lamp at 120 W / cm. [Table 1] TIFF2025533845000033.tif39153

[0136] Table 2 shows the UV LED 365 lamp 12W / cm 2 We report results using (PI + coinitiator). [Table 2] TIFF2025533845000034.tif23153

[0137] Table 3 shows the UV LED 395 lamp 16W / cm 2We report results using (PI + coinitiator + sensitizer). [Table 3] TIFF2025533845000035.tif34153 nd = not measured

[0138] Table 4 shows the UV LED 365 lamp 12W / cm 2 We report results using (PI + coinitiator + sensitizer). [Table 4] TIFF2025533845000036.tif34153

[0139] The above results show that the compounds of the present invention outperform conventional PIs in both the tack-free test and the YI test, as well as in the UV Hg lamp and UV LED lamp tests.

Claims

1. Formula (I) 【Chemical 1】 [In the formula, G is an optionally ethoxylated and / or propoxylated monomeric, oligomeric, or polymeric polyol G-(OH) m+q+p is a residue of m is 1 to 7; q is 1 to 7; p is 0 to 6; m+q+p is 3 to 8; R1 is CH 2 =CH-C(=O) or CH 2 =C(CH 3 )-C(=O); R2 is 【Chemistry 2】 (A)、 【Chemistry 3】 (B), and 【Chemistry 4】 (C) wherein X is selected from O, S, C(R4)(R5), and NR7; Y is selected from O, S, C(R4)(R5), and NR6; R4 and R5 are each independently selected from H, C1-C12 alkyl, OH, and C1-C10 alkoxy; R6 is selected from H, C1-C8 alkyl; R7 is H, C1-C8 alkyl, or unsubstituted phenyl; and the wavy line represents the bond connecting to the keto group of formula (I).

2. G-(OH) m+q+p 2. The compound according to claim 1, wherein is selected from monomeric, oligomeric, polymeric polyols or mixtures thereof, optionally ethoxylated or propoxylated.

3. G-(OH) m+q+p 2. The compound according to claim 1, characterized in that it has a number average molecular weight of 1,500 Da or less, more preferably 1,000 Da or less, and most preferably 800 Da or less; and 100 Da or more, preferably 200 Da or more.

4. q is 1 to 4, more preferably 2 to 4, for example 2, 3, or 4; p is 0 to 3, more preferably 0 to 2, for example 0, 1, or 2; m is 1 to 6, more preferably 2 to 4, for example 2, 3, or 4; m+q+p is 3 to 6, more preferably 3 to 5, for example 3, 4, or 5 The compound according to claim 1, characterized in that

5. 2. A compound according to claim 1, characterized in that R2 is (A) and X is S or O, preferably S.

6. a) 50 to 99.9% by weight, preferably 70 to 98.9% by weight (based on the total weight of the composition) of at least one ethylenically unsaturated compound; b) 1 to 40% by weight, preferably 3 to 35% by weight, and more preferably 5 to 30% by weight (based on the total weight of the composition) of at least one compound of formula (I) as defined in claim 1; and c) 0 to 20% by weight, preferably 0 to 15% by weight, and more preferably 0.2 to 15% by weight (based on the total weight of the composition) of accelerators and / or coinitiators A photopolymerizable composition comprising:

7. 7. The photopolymerizable composition of claim 6, further comprising one or more of the following components: d) 0.01 to 15 wt. % (based on the total weight of the composition) of one or more sensitizers; and / or e) 0.5 to 15 wt. % (based on the total weight of the composition) of one or more additional photoinitiators.

8. 8. Photopolymerizable composition according to claim 6 or 7, characterized in that the accelerator and / or coinitiator is an amine, preferably a tertiary amine.

9. 1. A method for photocuring photopolymerizable compositions, coatings, adhesives, and inks, said method comprising: i. providing a photopolymerizable composition according to claim 6 or 7; ii. coating or printing the photopolymerizable composition onto a substrate; and iii. photo-curing the composition coated or printed on the substrate with a light source A photocuring method comprising:

10. 8. A three-dimensional printing method comprising providing a photopolymerizable composition according to claim 6 or 7 and photocuring the composition with a light source.

11. 10. The method of claim 9, wherein the light source comprises UV light in at least one of the UVA, UVB, and UVC regions.

12. 11. The method of claim 10, wherein the light source comprises UV light in at least one of the UVA, UVB, and UVC regions.

13. 10. The method of claim 9, wherein the light source is an LED source.

14. 11. The method of claim 10, wherein the light source is an LED source.

15. 11. The method of claim 10, further comprising applying the photopolymerizable composition to a substrate prior to photocuring the photopolymerizable composition.

16. A product obtained by the method of claim 9.

17. A product obtained by the method of claim 10.

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