Polymer-type (meth) acrylate photoinitiators

Abstract

The present invention relates to novel photoinitiators with improved reactivity and surface curing and / or yellowing after curing and to photopolymerizable compositions comprising said photoinitiators. The invention also relates to methods for photopolymerization of compositions comprising the photoinitiators, and their use in articles, including printing components, coated components, and manufacturing components.

Description

[0001] ***

[0002] Specification

[0003] Abstract

[0004] The present invention relates to novel photoinitiators having improved reactivity and surface curing and / or lower post-curing yellowing, and to photopolymerizable compositions comprising said photoinitiators. The present invention also relates to methods for photopolymerizing compositions comprising said photoinitiators, and to their use in articles including printing assemblies, coating assemblies and manufacturing assemblies. Background Art

[0005] In recent years, due to a large number of photoinitiators being disabled due to toxicity or reproductive toxicity, the design and development of novel photoinitiators (PIs) have received increasing attention.

[0006] Various attempts have been made to develop new photoinitiators that can mimic standard photoinitiators or overcome problems such as yellowing, higher line speeds, curing under LED lights, etc. Some examples are glyoxylic acid 3-coumarinone (WO2021070152), benzoyl phenyl telluride PI (Macromolecules, 2014, 47(16), 5526-5531), silicone-based PI (JP2010229169, Macromoleum, 2009, 42(16), 6031-6037, Macromoolecules 2007, 40(24), 8527-8530, Macromol. Rapid Commun. 2017, 38, 1600470, Macromolecules, 2017, 50(17), 6911–6923), fluorine-based PI (US2019 / 0155153). For sensitive applications such as food packaging, in addition to good reactivity and low yellowing, photoinitiators that can photoreact in the matrix are preferably used to avoid the possible migration of photoinitiators into food.

[0007] Unfortunately, when used in standard applications, these photoinitiators also show some limitations, such as low surface curing and post-curing yellowing, which makes the PIs unsuitable for polymerizable systems involving clear varnishes.

[0008] Therefore, there is a need for new technical solutions that can improve the surface curing of PIs without affecting the good reactivity of these products and / or limit post-curing yellowing.

[0009] WO2015 / 010729 discloses polymer-based photoinitiators containing biphenyl. We surprisingly found that the replacement of biphenyl by different organic moieties plus (meth)acrylate groups results in a significant improvement in the performance of the PI.

[0010] Object of the Invention

[0011] A first object of the present invention is to provide a novel polymeric PI, its use as a photoinitiator, and a photocurable composition comprising said novel polymeric PI.

[0012] Another object of the present invention is to provide a photocurable composition comprising the novel PI of the present invention.

[0013] Another object of the present invention is to provide a method for photocuring ethylenically unsaturated compounds using the novel PI of the present invention, and articles prepared by said method. Summary of the Invention

[0014] According to one aspect of the present disclosure, the present invention relates to a compound of formula (I):

[0015]

[0016] wherein

[0017] G is the residue of a monomeric, oligomeric or polymeric polyol G-(OH) which is optionally ethoxylated and / or propoxylated; m+q+p ;

[0018] m is from 1 to 7;

[0019] q is from 1 to 7;

[0020] p is from 0 to 6;

[0021] m + q + p is from 3 to 8;

[0022] R1 is CH2=CH-C(=O) or CH2=C(CH3)-C(=O);

[0023] R2 is selected from:

[0024]

[0025]

[0026] wherein

[0027] X is selected from: O, S, C(R4)(R5) and NR7;

[0028] Y is selected from: O, S, C(R4)(R5) and NR6;

[0029] R4 and R5 are each independently selected from H, C1-C12 alkyl, OH and C1-C10 alkoxy;

[0030] R6 is selected from H, C1-C8 alkyl;

[0031] R7 is H, C1-C8 alkyl or unsubstituted phenyl;

[0032] And, the wavy line represents the bond connected to the keto group of the compound of formula (I).

[0033] According to the present invention, G-(OH) m+q+p is selected from monomers, oligomers, polymeric polyols and mixtures thereof, which may be optionally ethoxylated or propoxylated.

[0034] Examples of suitable monomeric and oligomeric polyols are glycerol, diglycerol, triglycerol, triethanolamine, trimethylolpropane, bis(trimethylolpropane), pentaerythritol, dipentaerythritol, sugar alcohols (such as sorbitol, mannitol and xylitol) and mixtures thereof.

[0035] Examples of polymeric polyols are polyhydroxy polyethers (which may be aliphatic or aromatic), polyhydroxy polyesters, polyhydroxy polyamides, polyhydroxy polyimides, polyhydroxy polycarbonates, styrene-allyl alcohol copolymers.

[0036] To achieve the present invention, alkoxylated polyols are particularly preferred. Examples of such alkoxylated polyols are the above-mentioned monomers, oligomers and polymeric polyols that have been alkoxylated (such as ethoxylated and / or propoxylated and / or butoxylated). Other suitable examples are alkoxylated linear or branched polyamines, and polyalkoxylated diamines, such as ethoxylated ethylenediamine and ethoxylated 1,3-propanediamine. In the alkoxylated compounds of the present invention, each group reactive to alkylene oxide may carry 0 to 15 alkoxy units, preferably 1 to 6 alkoxy units.

[0037] In a preferred embodiment, G-(OH) m+q+p is selected from monomers and oligomeric polyols.

[0038] In a preferred embodiment, G-(OH) m+q+p is selected from monomers and oligomeric polyols that have been ethoxylated and / or propoxylated.

[0039] Preferably, G-(OH) m+q+p has the following number average molecular weight:

[0040] - not more than 1500 Da, more preferably not more than 1000 Da, and most preferably not more than 800 Da; and

[0041] - not less than 100 Da, preferably not less than 200 Da.

[0042] Preferably, G-(OH) m+q+pSelected from glycerol, ethoxylated and / or propoxylated glycerol, diglycerol, ethoxylated and / or propoxylated diglycerol, trimethylolpropane, ethoxylated and / or propoxylated trimethylolpropane, ditrimethylolpropane, ethoxylated and / or propoxylated ditrimethylolpropane, pentaerythritol, ethoxylated and / or propoxylated pentaerythritol, dipentaerythritol, ethoxylated and / or propoxylated dipentaerythritol, sorbitol, ethoxylated and / or propoxylated sorbitol, triethanolamine, and ethoxylated and / or propoxylated triethanolamine.

[0043] Preferably, m + q + p is from 3 to 8, and more preferably from 3 to 6, such as 3, 4, 5, or 6.

[0044] Preferably, m is from 1 to 6, and more preferably from 1 to 4, such as 1, 2, 3, or 4.

[0045] Preferably, q is from 1 to 6, and more preferably from 2 to 4, such as 2, 3, or 4.

[0046] Preferably, p is from 0 to 6, and more preferably from 0 to 3, such as 0, 1, 2, or 3.

[0047] When p is not equal to 0, the compound of formula (I) has a free alcohol group.

[0048] Mixtures of the compounds of formula (I) are also included within the scope of the present invention.

[0049] According to a preferred embodiment, R1 is a residue of acrylic acid (CH2=CH-C(=O)).

[0050] According to a preferred embodiment, R2 is (A), and X is S or O, preferably S.

[0051] According to a preferred embodiment, R2 is (A), and X is N-phenyl.

[0052] According to a preferred embodiment, R2 is (B), X is O, and Y is C(CH3)(CH3).

[0053] According to a preferred embodiment, R2 is (C), and X is CH2.

[0054] According to a preferred embodiment, R2 is (C), and X is N-alkyl.

[0055] When X is S, the form in which sulfur is oxidized to sulfone or sulfoxide is also included within the scope of protection of the present invention.

[0056] According to another preferred embodiment of the present invention:

[0057] ·q is from 1 to 4, more preferably from 2 to 4, such as 2, 3, or 4;

[0058] · p ranges from 0 to 3, more preferably from 0 to 2, such as 0, 1 or 2;

[0059] · m ranges from 1 to 6, more preferably from 2 to 4, such as 2, 3 or 4;

[0060] · m + q + p ranges from 3 to 6, more preferably from 3 to 5, such as 3, 4 or 5.

[0061] In this specification, the expression "alkyl" or "alkyl group", unless otherwise indicated, refers to a straight-chain or branched saturated alkyl chain containing a given number of carbon atoms, and includes all possible isomers of each number of carbon atoms in the alkyl group, i.e., for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tert-butyl; for five carbon atoms: n-pentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl and 2-methylbutyl, etc.

[0062] Preferably, the alkyl is a C1-C4 alkyl, such as, for example, methyl or ethyl.

[0063] The compounds of the present invention can be prepared according to any suitable method. For example, they can be prepared by Friedel-Crafts acylation and optional esterification according to Scheme 1 below:

[0064] Scheme 1

[0065]

[0066] The reaction can be carried out in a suitable solvent (the solvent is, for example, an aromatic solvent such as toluene), and in the presence of methanesulfonic acid and hypophosphorous acid. Then the compound of formula (I) obtained can be separated according to known methods.

[0067] In the above reaction, (meth)acrylic acid can be replaced / substituted by a halogenated derivative (such as its chlorinated derivative).

[0068] The reactants are known and / or commercially available, or they can be prepared according to known methods and / or as disclosed in the experimental part below.

[0069] According to another aspect of the present invention, the present invention relates to a method for preparing a compound of formula (I), which comprises carrying out the reaction according to Scheme 1 above.

[0070] Those skilled in the art are preferably able to carry out the chemical reactions of Scheme 1 according to known methods.

[0071] The details of the method of the present invention are described in the experimental part of this specification.

[0072] According to another aspect of the present disclosure, the present invention relates to a photopolymerizable composition, which comprises:

[0073] a) At least one ethylenically unsaturated compound in an amount of 50 to 99.9% by weight, preferably 70 to 98.9% by weight, based on the total content of the composition;

[0074] b) At least one compound of formula (I) as defined above in an amount of 1 to 40% by weight, preferably 3 to 35% by weight, more preferably 5 to 30% by weight, based on the total content of the composition; and

[0075] c) A promoter and / or co - initiator in an amount of 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0.2 to 15% by weight, based on the total content of the composition.

[0076] Preferably, the content of the at least one compound (b) is 5 to 30%, for example 10%, 15%, 20%, 25% or 30%.

[0077] According to the present invention, the terms "photocuring" and "photopolymerization" and related terms are synonyms.

[0078] The expression "based on the total content of the composition" herein means that the weight percentage of any component is calculated relative to the sum of the weights of all components in the composition (including any possible other additional components (other than a), b) and c) above)), but water and / or solvent that may be present in the composition are not considered when calculating the weight percentage.

[0079] According to another aspect of the present disclosure, the present invention relates to a method for photocuring a photopolymerizable composition, a coating, an adhesive and an ink, the method comprising:

[0080] i. Providing a photopolymerizable composition as defined above;

[0081] ii. Coating or printing the photopolymerizable composition onto a substrate, and

[0082] iii. Photocuring the coated or printed composition on the substrate with a light source.

[0083] According to another aspect of the present disclosure, the present invention relates to a method for three - dimensional printing, the method comprising photocuring a mixture comprising a composition as defined above with a light source.

[0084] According to another aspect of the present disclosure, the present invention relates to an article obtained by the method of the present invention.

[0085] The photopolymerizable composition of the present invention may further comprise one or more of the following components: (d) a sensitizer and / or (e) other photoinitiators and / or (f) conventional additives in addition to compounds (a), (b) and (c) (when present).

[0086] According to a preferred embodiment, the photopolymerizable composition for the method of the present invention comprises at least components (a), (b) and (c) defined above, and more preferably comprises at least components (a), (b), (c) and (d) defined above.

[0087] The photoinitiator of the present invention can be used in a photocurable composition comprising an ethylenically unsaturated compound (a). The unsaturated compound (a) may contain one or more ethylenic double bonds. They may be low molecular weight (monomers) or high molecular weight (oligomers) compounds.

[0088] Examples of suitable low molecular weight monomers (monomeric compounds) having one double bond are alkyl or hydroxyalkyl acrylates or methacrylates, such as methyl-, ethyl-, butyl-, 2-ethylhexyl-, 2-hydroxyethyl- or isobornyl acrylate; and methyl methacrylate or ethyl methacrylate. Other examples are resins modified with silicon or fluorine, such as silicone acrylates. Other examples of these monomers are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamides, styrene, alkylstyrenes and halostyrenes, vinyl esters (such as vinyl acetate), vinyl ethers (such as isobutyl vinyl ether, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride).

[0089] Examples of monomers having more than one double bond are ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate, bisphenol A diacrylate, 4,4'-bis-(2-acryloyloxyethoxy)-diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tri-(2-acryloylethyl) isocyanurate.

[0090] Examples of high molecular weight (oligomeric) polyunsaturated compounds are acrylated / acrylated epoxy resins, acrylated / acrylated or vinyl ether-containing or epoxy group-containing polyesters, acrylated / acrylated polyurethanes or acrylated / acrylated polyethers. Other examples of unsaturated oligomers are unsaturated polyester resins, which are generally prepared from maleic acid, phthalic acid and one or more diols and have a molecular weight of about 500 Da to 3,000 Da. Such unsaturated oligomers may also be referred to as prepolymers.

[0091] Examples of compounds (a) which 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 side groups, such as unsaturated polyesters, polyamides and polyurethanes and their copolymers, alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers having (meth)acrylic groups in the side chain, and mixtures thereof.

[0092] Illustrative examples of the unsaturated carboxylic acids or acid anhydrides used for preparing 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.

[0093] Examples of polyols which can also be esterified are aromatic, aliphatic and alicyclic polyols, preferably aliphatic and alicyclic polyols.

[0094] Aromatic polyols are, for example, hydroquinone, 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane and novolaks and resoles. The polyepoxides which can be esterified include those based on the above polyols, in particular the reaction products between aromatic polyols and epichlorohydrin. Also suitable as polyols are polymers and copolymers containing hydroxyl groups in the polymer chain or side groups, such as polyvinyl alcohol and its copolymers or polyhydroxyalkyl acrylates or their copolymers. Other suitable polyols are low molecular weight polyesters with hydroxyl end groups.

[0095] 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, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycol with a molecular weight preferably of 200 Da 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.

[0096] Other suitable ethylenically unsaturated compounds (a) are unsaturated polyamides obtained from unsaturated carboxylic acids and aromatic, aliphatic and cycloaliphatic polyamines preferably having 2-6, preferably 2-4 amino groups. Examples of such polyamines are: ethylenediamine, 1,2- or 1,3-propanediamine, 1,2-, 1,3- or 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, octanediamine, dodecanediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di-(β-aminoethyl) ether, diethylenetriamine, triethylenetetramine and di(β-aminoethoxy)-ethane and di(β-aminopropoxy)ethane. Other suitable polyamines are polymers and copolymers which may contain additional amino groups in the side chain, and oligomeric polyamides containing amino end groups.

[0097] Specific examples of such unsaturated polyamides are: methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriamine tris(methacrylamide), bis(methacrylamidopropoxy)ethane and N-[(β-hydroxyethoxy)ethyl]-acrylamide.

[0098] Unsaturated polyurethanes are also suitable as component (a) for carrying out the present invention, for example those derived from saturated or unsaturated diisocyanates and unsaturated or saturated diols. Polybutadiene and polyisoprene and their copolymers can also be used.

[0099] Suitable monomers include, for example, olefins such as ethylene, propylene, butene and hexene, (meth)acrylates, acrylonitrile, styrene and vinyl chloride.

[0100] Polymers having unsaturated (meth)acrylate groups in the side chain can also be used as component (a). These polymers can generally be reaction products of epoxy resins based on novolacs with (meth)acrylic acid; homopolymers or copolymers of vinyl alcohol or its hydroxyalkyl derivatives which have been esterified with (meth)acrylic acid; and homopolymers and copolymers of (meth)acrylates which have been esterified with hydroxyalkyl (meth)acrylates.

[0101] According to a preferred embodiment, the photocurable composition further comprises a co-initiator (c), also known as a promoter.

[0102] Examples of suitable promoters / co-initiators (c) are alcohols, thiols, thioethers, amines or ethers which have an active hydrogen bonded to a carbon adjacent to a phosphine, disulfide and heteroatom, as described, for example, in EP 438 123 and GB 2 180 358.

[0103] Suitable examples of amine accelerators / copolymer initiators include, but are not limited to, aliphatic, cycloaliphatic, aromatic, aryl-aliphatic, heterocyclic, oligomeric or polymeric amines. They can be primary, secondary or tertiary amines, such as 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 its derivatives.

[0104] Amine-modified acrylate compounds can be used as amine accelerators / copolymer initiators; examples of such amine-modified acrylates include acrylates modified by reaction with primary or secondary amines, as described in US 3,844,916, EP280222, US 5,482,649 or US 5,734,002.

[0105] Polyfunctional amines and polyamine derivatives are also suitable as copolymer initiators, some examples being those of IGM Resins B.V. ASA, those of Rahn A.G. AB-2, those of Lambson Limited 7040 or those described in US2013 / 0012611.

[0106] The photocurable composition of the present invention can also be formulated as a composition further comprising water and / or a solvent (such as an organic solvent).

[0107] Based on the total content of the composition, the amount of photosensitizer (d) present can be 0.01 to 15% by weight, preferably 0.01 to 10% by weight.

[0108] Examples of sensitizers are those commonly used in the art, aromatic carbonyl compounds such as benzophenones, thioxanthones, anthraquinones, coumarins and 3-acylcoumarin derivatives, terphenyls, stilbenones and 3-(aroylmethylene)-thiazolines, camphorquinone and eosin, rhodamine and erythrosine dyes.

[0109] 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-benzenesulfonylthioxanthone, 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-thioxanthone-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, or those described in patent application PCT / EP2011 / 069514, for example, n-dodecyl-7-methyl-thioxanthone-3-carboxylate and N,N-diisobutyl-7-methyl-thioxanthone-3-urea. Also suitable are polymeric thioxanthone derivatives (e.g., TX from IGM Resins TX-1 from Rahn A.G. 7010 from Lamson & Sessions Co., Ltd.).

[0110] 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-methylthiophenyl)benzophenone, 4-benzoyl-N,N,N-trimethylbenzenaminium 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]benzenaminium chloride, or those described in US9938231 (e.g., 991).

[0111] Also suitable are polymeric benzophenone derivatives (e.g., BP, 2702, and 682 from Rahn A.G., BP-2, and 7005 from Lamson Limited).

[0112] 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-isobutyrylcoumarin, 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-isobutyryl-1,7-dimethylaminocoumarin, 5,7-dimethoxy-3-(1-benzoyl)coumarin, 5,7-dimethoxy-3(1-benzoyl)-coumarin, 3-benzoylbenzo[f]coumarin, 7-diethylamino-3-thiophenoylcoumarin, 3-(4-cyanobenzoyl)-5,7-dimethoxycoumarin, or those described in EP2909243 and WO2017216699.

[0113] Examples of 3-(aroylmethylene)thiazolines are 3-methyl-1,2-benzoylmethylene-β-benzothiazoline, 3-methyl-2-benzoylmethylene-benzothiazoline, 3-ethyl-2-propionylmethylene-β-benzothiazoline.

[0114] Examples of other aromatic carbonyl compounds are acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzyl, such as those described in WO 2013 / 164394, 2-acetylnaphthalene, 2-naphthaldehyde, 9,10-anthraquinone, 9-fluorenone, dibenzocycloheptanone, 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-phenylthio-phthalimide, N-methyl-3,5-di(ethylthio)phthalimide.

[0115] Particularly preferred are thioxanthones, coumarins and 3-acylcoumarins.

[0116] It has been observed that the above-mentioned component (d) increases the activity of the photoinitiator (b) without shortening the shelf life of the composition. In addition, such compositions have the particular advantage that by a suitable choice of the sensitizer (d), the spectral sensitivity of the photoinitiator (b) can be shifted to any desired wavelength region. A person skilled in the art is able to select a suitable sensitizer (d) to make the photoinitiator (b) act in any desired wavelength region.

[0117] The amount of other possible photoinitiator (e) present may be from 0.5 to 15% by weight, preferably from 1 to 10% by weight of the total composition.

[0118] Examples of other suitable photoinitiators (e) are camphorquinone, benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, dialkoxyacetophenone, α-hydroxy ketones, α-amino ketones, 4-aroyl-1,3-dioxolanes, benzoin alkyl ethers and benzyl ketals such as benzyl dimethyl ketal, ketone sulfones such as 1-[4-[(4-benzoyl-phenyl)-thio]-phenyl]-2-methyl-2-[(4-methyl-phenyl)-sulfonyl]-propan-1-one ( 1001, from IGM Resins), 3-ketocoumarins such as phenylglyoxylic acid and its derivatives, diphenylglyoxylic acid, peresters such as benzophenone tetracarboxylic peresters as described, for example, in EP126 541, acylphosphine photoinitiators (selected from monoacylphosphine oxides, bisacylphosphine oxides, trisacylphosphine oxides and polyfunctional mono- or bisacylphosphine oxides), halomethyltriazines, hexaaryldiimidazole / cocatalyst systems such as the combination of o-chlorohexaphenyldiimidazole with 2-mercaptobenzothiazole, ferrocene compounds or titanocenes such as dicyclopentadienyl-bis(2,6-difluoro-3-pyrrolophenyl)titanium, O-acyl oxime ester photoinitiators.

[0119] Examples of α-hydroxy ketones and α-amino ketones are 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propanone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-1-propanone), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-phenoxy]-phenyl}-2-methyl-1-propanone, 2-methyl-1-(4-methylthiophenyl)-2-morpholin-1-butanone), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, and (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone).

[0120] Examples of O-acyl oxime ester photoinitiators are 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), acetophenone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] 1-(O-acetyl oxime) or those described in GB 2339571.

[0121] 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 trimers (TP from IGM Resins). TP).

[0122] Examples of photoinitiators based on halogenomethyltriazines 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, 2-methyl-4,6-bis-trichloromethyl[1,3,5]triazine.

[0123] When the photocurable composition according to the invention is used in a hybrid system (which in this context means a mixture of free radical and cationic curing systems), cationic photoinitiators can also be used as additional photoinitiators (e). Examples of suitable cationic photoinitiators are aromatic sulfonium salts, phosphonium salts or iodonium salts, as described, for example, in US 4,950,581, or cyclopentadienylarene-iron(II) complex salts, for example (η 6 -isopropylbenzene)(η 5 -cyclopentadienyl)iron(II) hexafluorophosphate or oxime-based photoacid generators, for example, as described in GB 2348644, US 4,450,598, US 4,136,055, WO 00 / 10972 and WO 00 / 26219.

[0124] The photocurable composition according to the invention can also contain conventional additives in an amount of 0 to 10% based on the total content of the composition. Additives (f) can be, for example, thermal initiators, binders, stabilizers and mixtures thereof.

[0125] The choice of additives depends on the field of use in question and the properties required in that field. The above additives (f) are known in the art and are used in amounts conventionally used in the art.

[0126] For example, especially in the case of the coloring composition, the composition may further contain, as an additional additive (f), a thermal initiator, i.e., a compound that forms free radicals upon heating, such as an azo compound, such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), a triazene, a diazosulfide, a pentazadiene, or a peroxide, such as a hydroperoxide or a peroxycarbonate, such as tert-butyl hydroperoxide, as described, for example, in EP245 639.

[0127] A binder can also be 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. Based on the total content of the composition (excluding possible water and solvents), the amount of the binder can be, for example, 5 to 60% by weight, preferably 10 to 50% by weight. The choice of the binder is made according to the field of use and its required properties, such as developability in aqueous and organic solvent systems, adhesion to the substrate, and oxygen sensitivity.

[0128] Suitable binders are, for example, polymers having a weight-average molecular weight (Mw) of about 5,000 Da to 2,000,000 Da, preferably 10,000 Da to 1,000,000 Da. Illustrative examples are: homopolymers and copolymers of acrylates and methacrylates, such as copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, poly(alkyl methacrylates), poly(alkyl acrylates); 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, chlorinated polyolefins, such as polyvinyl chloride, copolymers of vinyl chloride / vinylidene chloride, copolymers of vinylidene chloride with acrylonitrile, methyl methacrylate, and vinyl acetate, polyvinyl acetate, copoly(ethylene / vinyl acetate), polymers, such as polycaprolactam and poly(hexamethylene adipamide), polyesters, such as poly(ethylene glycol terephthalate) and poly(hexanediol succinate).

[0129] Suitable stabilizers are, for example, heat inhibitors such as hydroquinone, hydroquinone derivatives, p-methoxyphenol, β-benzol or sterically hindered phenols such as 2,6-di(tert-butyl)-p-cresol, which prevent premature polymerization. To increase the stability during dark storage, for example, copper compounds such as copper naphthenate, copper stearate or copper octanoate, phosphorus compounds such as triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite or tribenzyl phosphite, quaternary ammonium compounds such as tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives such as N,N-diethylhydroxylamine can be used. To exclude atmospheric oxygen during the polymerization, paraffin or similar waxy substances can be added, which are insoluble in the polymer, migrate to the surface at the beginning of the polymerization and form a transparent surface layer that prevents air from entering.

[0130] Light stabilizers such as UV absorbers such as hydroxyphenylbenzotriazole, hydroxyphenyldibenzophenone, oxalic acid amide or hydroxyphenyl-s-triazine can also be added. Such components can be used alone or in a mixture, with or without the use of sterically hindered amines (HALS).

[0131] The photocurable composition according to the invention can also contain a photoreductive dye as a further additive (f), such as xanthene, benzoxanthene, benzothioxanthene, thiazine, pyronine, porphyrin or acridine dyes, and / or a radiation-cleavable trihalomethyl compound. For example, these compounds are described in EP445624.

[0132] Depending on the intended use, other commonly used additives (f) are optical brighteners, fillers, pigments (white and colored pigments), colorants, antistatic agents, wetting agents or flow improvers. Additives commonly used in the art such as antistatic agents, flow improvers and adhesion enhancers can also be used.

[0133] In addition to the above components, other components can also be present in the composition according to the invention.

[0134] Chain transfer agents commonly used in the art can also be added to the composition according to the invention. Examples are thiols, amines and benzothiazoles.

[0135] The composition of the present invention may also contain colorants and / or colored pigments. Depending on the intended use, inorganic and organic pigments can be used. Such additives are well known to those skilled in the art; some examples are carbon black, iron oxides such as iron oxide yellow, iron oxide red, chrome yellow, chrome green, nickel titanium yellow, ultramarine blue, cobalt blue, bismuth vanadate, cadmium yellow and cadmium red. Examples of organic pigments are monoazo or bisazo pigments and their metal complexes, phthalocyanine pigments, polycyclic pigments such as perylene, anthraquinone, thioindigo, quinacridone or triphenylmethane pigments, and diketo-pyrrolo-pyrrole, isoindolinone such as tetrachloroisoindolinone, isoindoline, dioxazine, benzimidazolone and quinophthalone pigments. The pigments can be used alone or in combination in the formulation.

[0136] Depending on the intended use, the pigments can be added to the formulation in amounts commonly used in the art, for example, in amounts of 0.1 to 30% by weight or 10% to 25% by weight based on the total weight of the composition.

[0137] The composition may also contain, for example, a very wide variety of organic colorants. Such as azo dyes, methylene dyes, anthraquinone dyes and metal complex dyes. Based on the total weight of the composition, the conventional concentration is, for example, 0.1 to 20% by weight, especially 1 to 5% by weight.

[0138] The photocurable composition of the present invention may contain water.

[0139] The photocurable composition of the present invention is suitable for a variety of purposes, such as being used as printing inks (such as screen printing inks, flexographic printing inks, offset printing inks, and inkjet printing inks), as transparent coatings, as colored coatings (such as for wood or metal), as powder coatings, as coatings especially for paper, wood, metal or plastics, as daylight-curable coatings for marking structures and roads, for photographic reproduction processes, for holographic recording materials, for image recording processes or for the production of printing plates that can be developed using organic solvents or using aqueous alkaline media, for the production of screen printing masks, as dental filling compounds, as adhesives, as pressure-sensitive adhesives, as laminating resins, as photoresists (such as electroresists), as etching resists or permanent resists, liquid and dry films, as photo-structurable dielectrics, and as solder resists for electronic circuits, and as resists for the production or structuring of color filters for any type of display screen in the following processes: the manufacture of plasma displays and electroluminescent displays, the production of optical switches, gratings (interference gratings), the manufacture of three-dimensional articles by bulk curing (UV curing in a transparent mold) or according to the stereolithography process (as described, for example, in US 4,575,330), in the manufacture of composite materials (such as styrene polyesters that may include glass fibers and / or other fibers and other auxiliaries) and other three-dimensional printing methods well-known to those skilled in the art, the coating or sealing of electronic components, or as a coating for optical fibers.

[0140] The photocurable composition of the present invention is also suitable for the production of optical lenses (such as contact lenses or Fresnel lenses) for use in the manufacture of medical devices, aids or implants, or for dry film lacquers.

[0141] 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.

[0142] Articles containing the compound of formula (I) or containing the photocurable composition of the present invention represent another subject of the present invention.

[0143] The compounds and compositions according to the present invention can also be used as free radical photoinitiators or photoinitiator systems for radiation-curable powder coatings.

[0144] The photocurable composition according to the present invention is suitable for, for example, being used as a coating for a variety of substrates, such as wood, textiles, paper, ceramics, glass, plastics (such as polyester, polyethylene terephthalate, polyolefins and cellulose acetate, especially in the form of films), and metals (such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO2), on which a protective layer or an image is to be applied, for example by imaging exposure.

[0145] The method according to the invention can use a large number of different types of light sources, and the wavelength emitted by the light source is from about 200 nm to about 800 nm. Both point light sources and planar radiators (lamp carpets) are applicable. Examples are: carbon arc lamps, xenon arc lamps, medium-pressure mercury arc light radiation sources, high-pressure mercury arc light radiation sources and low-pressure mercury arc light radiation sources, lamps doped with metal halides (metal halide lamps) where appropriate, microwave-excited metal vapor lamps, excimer lamps, superactinic fluorescent tubes, fluorescent lamps, argon incandescent lamps, flash lamps, photographic floodlights, light-emitting diodes (LEDs), electron beams, X-rays and lasers.

[0146] According to one embodiment, the light source comprises UV light in at least one of the UVA, UVB and UVC ranges.

[0147] According to a preferred embodiment, the light source is an LED source, particularly preferably an LED light source emitting at a wavelength of 365 nm to 420 nm, and more preferably an LED light source emitting at wavelengths of 365 nm, 385 nm and 395 nm.

[0148] According to the invention, the distance between the lamp and the substrate to be exposed can vary depending on the intended use and the type and intensity of the lamp, for example from 0.1 cm to 150 cm, preferably from 1 cm to 50 cm.

[0149] The photocurable composition can also be applied to a substrate that already contains a coated or printed layer. After the photocurable composition is photocured with the light source, the photocurable composition can be overprinted or overcoated with one or more compositions suitable for printing or coating.

[0150] The photocurable composition is applied to the substrate by the coating or printing method, photocured by the light source, and the article is further processed with or without further coating or printing, and thus the obtained article represents another subject of the invention.

[0151] As described above, we surprisingly found that, compared with the prior art, the compound of formula (I) has very high reactivity at UVA, UVB and UVC wavelengths and maintains low yellowing after curing. The surface curing performance of the new compound has been significantly improved under LEDs and mercury lamps.

[0152] The present invention will be described in detail below by the following examples, which are illustrative and not restrictive.

[0153] Experimental section

[0154] Throughout this specification, if there is a discrepancy between the chemical name and the chemical formula, the latter shall prevail.

[0155] The term "r.t." means "room temperature".

[0156] In the following formula, each "n" value is independently selected from each other, that is to say, the n values in the same formula may also be different from each other.

[0157] In the following examples, the part of formula (I) within square brackets, that is,

[0158]

[0159] is referred to as the "q part".

[0160] Recorded with a Bruker Ascend 300MHz NMR spectrometer 1 1H-NMR spectrum.

[0161] Preparation Example 1

[0162]

[0163] To a 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 portionwise. The reaction mixture was stirred at room temperature for 1.5 h, then poured into ice / dilute hydrochloric acid. The mixture was extracted with ethyl acetate, and the organic layer was separated, washed with 1M hydrochloric acid, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under vacuum. The crude product was purified by crystallization from toluene to give 76.63 g of a white solid (yield 86%).

[0164] 1 1H-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).

[0165] Preparation Example 2

[0166]

[0167] To a 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, which was cooled in ice, 24.07 g (180.516 mmol) of anhydrous aluminum chloride was carefully added portionwise. The reaction mixture was stirred at room temperature for 1.5 h and then poured into ice / dilute hydrochloric acid. The resulting semi-solid product was treated with 270 mL of ethyl acetate, and the solid obtained was filtered off. Subsequently, the filtrate layer was separated, and the organic layer was further washed with 1 M hydrochloric acid, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under vacuum. The crude product was suspended in 200 mL of toluene together with the solid previously filtered off and washed under reflux with vigorous stirring for 30 min. Then, the mixture was cooled to room temperature (r.t.) and filtered to give 27.26 g of a white solid product (yield 96%).

[0168] 1 1H-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).

[0169] Preparation Example 3

[0170]

[0171] To a 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, which was cooled in ice, 23.50 g (176.241 mmol) of anhydrous aluminum chloride was carefully added portionwise. The reaction mixture was stirred at room temperature for 1.5 h and then poured into ice / dilute hydrochloric acid. The mixture was extracted with ethyl acetate, and the organic layer was separated, washed with 1 M hydrochloric acid, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under vacuum. The crude product was purified by crystallization from toluene to give 23.25 g of a white solid product (yield 83%).

[0172] 1 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).

[0173] Preparation Example 4

[0174]

[0175] To an ice-cooled mixture of 5.12 g (24.491 mmol) of 9,9-dimethylxanthene and 3.63 g (24.507 mmol) of phthalic anhydride in 85 mL of chlorobenzene was carefully added portionwise 6.53 g (48.973 mmol) of anhydrous aluminum chloride. The reaction mixture was stirred at room temperature for 1.5 h and then poured into ice / dilute hydrochloric acid. The mixture was extracted with ethyl acetate and the organic layer was separated, washed with 1 M hydrochloric acid, dried over anhydrous sodium sulfate, filtered. Another equivalent amount of 4-methoxyphenol was added and the solvent was removed by distillation under vacuum. The crude product was purified by crystallization from toluene to give 7.15 g of a white solid product (yield 81%).

[0176] 1 1H-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).

[0177] Preparation Example 5

[0178]

[0179] 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 was carefully added portionwise 5.12 g (38.398 mmol) of anhydrous aluminum chloride. The reaction mixture was stirred at room temperature for 1 h; then the reaction 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 successively. This operation was repeated again. Finally, the reaction mixture was poured into ice / dilute hydrochloric acid. The mixture was extracted with ethyl acetate and the organic layer was separated, washed with 1 M hydrochloric acid, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under vacuum. The crude product was suspended in 250 mL of toluene and washed under reflux with vigorous stirring for 30 min. The mixture was cooled to room temperature and the solid was collected by filtration. The latter was suspended in 200 mL of toluene and washed again under reflux with vigorous stirring for 24 h to give 7.61 g of a white solid product (yield 33%).

[0180] 11H-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).

[0181] Preparation Example 6

[0182]

[0183] To a 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 portionwise. The reaction mixture was stirred at room temperature for 1 hour, then the reaction 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 successively. This operation was repeated again. Finally, the reaction mixture was poured into 400 mL of ice / water. The mixture was extracted with ethyl acetate, and the organic layer was separated, 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 / ethyl acetate 50:50) to obtain 7.85 g of a yellow solid (yield 34%).

[0184] 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).

[0185] Example 1 (Total grafting rate 92.3% - q - part / acrylate 1:2.7)

[0186]

[0187] A mixture of 50.00 g of polyol 4640 (hydroxyl n° 634 / g, purchased from Perstorp) in toluene, 47.23 g (141.24 mmol) of the compound of 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 was stirred under reflux for 6 hours while removing water using a Dean - Stark apparatus. Subsequently, the mixture was brought to room temperature, 0.14 g of 4 - methoxyphenol was added, and then 40.30 g (559.26 mmol) of acrylic acid was added. Air was bubbled into the interior through a Pasteur pipette to induce reflux, and the mixture was stirred at 85 °C (internal temperature) while maintaining the temperature constant for 6 hours. Finally, the mixture was brought to room temperature, diluted with EtOAc (ethyl acetate) (150 mL), and washed with 0.25 M Na2CO3 (200 mL) and brine (200 mL). The organic layer was dried over Na2SO4 and filtered. Another equal amount of 4 - methoxyphenol was added, and the solvent was removed under reduced pressure to obtain 103.50 g of a pale yellow oily product (88% yield).

[0188] 1 1H - 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).

[0189] Example 2 (Total grafting rate 80.5% - q - part / acrylate 2.9:1)

[0190]

[0191] A mixture of 2.50 g (hydroxyl n° 364 / g) of polyol 3380 (purchased from PERSTORP) in toluene, 3.36 g (10.87 mmol) of the compound of Preparation Example 1, 0.09 g (0.66 mmol) of 70% aqueous methanesulfonic acid, and 0.07 g (0.55 mmol) of 50% aqueous hypophosphorous acid was stirred under reflux for 6 hours while removing water using a Dean-Stark apparatus. Subsequently, the mixture was brought to room temperature, 0.007 g of 4-methoxyphenol was added, and then 0.51 g (7.14 mmol) of acrylic acid was added. Air was bubbled into the interior through a Pasteur pipette to induce reflux, and the mixture was stirred at 85 °C (internal temperature) while maintaining the temperature constant for 6 hours. Finally, the mixture was brought to room temperature, diluted with EtOAc (ethyl acetate) (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic layer was dried over Na2SO4 and filtered. Another equal amount of 4-methoxyphenol was added, and the solvent was removed under reduced pressure to obtain 5.87 g of a colorless oily product (98% yield).

[0192] 1 1H-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).

[0193] Example 3 (Total grafting rate 70% - q - part / acrylate 2.5:1)

[0194]

[0195] A mixture of 2.50 g of sorbitol RE / 20 (hydroxyl n° 300 / g) in toluene (purchased from Lamberti SpA), 2.24 g (6.69 mmol) of the compound of Preparation Example 1, 0.08 g (0.55 mmol) of 70% aqueous methanesulfonic acid, and 0.06 g (0.45 mmol) of 50% aqueous hypophosphorous acid was stirred under reflux for 6 hours while removing water using a Dean-Stark apparatus. Subsequently, the mixture was brought to room temperature, 0.006 g of 4-methoxyphenol was added, and then 0.64 g (8.83 mmol) of acrylic acid was added. Air was bubbled into the interior through a Pasteur pipette to induce reflux, and the mixture was stirred at 85 °C (internal temperature) while maintaining the temperature constant for 6 hours. Finally, the mixture was brought to room temperature, diluted with EtOAc (ethyl acetate) (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic layer was dried over Na2SO4 and filtered. Another equal amount of 4-methoxyphenol was added, and the solvent was removed under reduced pressure to give 4.51 g of a colorless oily product (88% yield).

[0196] 1 1H-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).

[0197] Example 4 (Total grafting rate 96.8% - 1:2.8 q - fraction / acrylate)

[0198]

[0199] A mixture of 50.00 g of polyol 4640 (hydroxyl n° 634 / g, purchased from Perstorp) in toluene, 44.40 g (141.25 mmol) of the compound of 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 was stirred under reflux for 6 hours while removing water using a Dean-Stark apparatus. Subsequently, the mixture was brought to room temperature, 0.14 g of 4-methoxyphenol was added, and then 40.30 g (559.26 mmol) of acrylic acid was added. Air was bubbled into the interior through a Pasteur pipette to induce reflux, and the mixture was stirred at 85 °C (internal temperature) while maintaining the temperature constant for 6 hours. Finally, the mixture was brought to room temperature, diluted with EtOAc (ethyl acetate) (150 mL), and washed with 0.25 M Na2CO3 (200 mL) and brine (200 mL). The organic layer was dried over Na2SO4 and filtered. Another equal amount of 4-methoxyphenol was added, and the solvent was removed under reduced pressure to obtain 113.76 g of a pale yellow oily product (91% yield).

[0200] 1 1H-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).

[0201] Example 5 (Total grafting rate 90.0% - q - part / acrylate 1:1.5)

[0202]

[0203] A mixture of 2.50 g (hydroxyl n° 370 / g) of aionico GL / 609 (purchased from Lamberti SpA) in toluene, 1.86 g (5.44 mmol) of the compound of 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 was stirred under reflux for 6 hours while removing water using a Dean - Stark apparatus. Subsequently, the mixture was brought to room temperature, 0.006 g of 4 - methoxyphenol was added, and then 1.05 g (14.51 mmol) of acrylic acid was added. Air was bubbled into the interior through a Pasteur pipette to induce reflux, and the mixture was stirred at 85 °C (internal temperature) while maintaining the temperature constant for 6 hours. Finally, the mixture was brought to room temperature, diluted with EtOAc (ethyl acetate) (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic layer was dried over Na2SO4 and filtered. Another equal amount of 4 - methoxyphenol was added, and the solvent was removed under reduced pressure to obtain 4.58 g of a colorless oily product (89% yield).

[0204] 1 1H - 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).

[0205] Example 6 (Total grafting rate 87.5% - q - part / acrylate 1:2.5)

[0206]

[0207] A mixture of 2.50 g (hydroxyl n° 634 / g) of polyol 4640 (purchased from Perstorp) in toluene, 2.25 g (7.06 mmol) of the compound of Preparation Example 3, 0.16 g (1.16 mmol) of 70% aqueous methanesulfonic acid, and 0.13 g (0.96 mmol) of 50% aqueous hypophosphorous acid was stirred under reflux for 6 hours while removing water using a Dean-Stark apparatus. Subsequently, the mixture was brought to room temperature, 0.007 g of 4-methoxyphenol was added, and then 2.01 g (27.97 mmol) of acrylic acid was added. Air was bubbled into the interior through a Pasteur pipette to induce reflux, and the mixture was stirred at 85 °C (internal temperature) while maintaining the temperature constant for 6 hours. Finally, the mixture was brought to room temperature, diluted with EtOAc (ethyl acetate) (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic layer was dried over Na2SO4 and filtered. Another equal amount of 4-methoxyphenol was added, and the solvent was removed under reduced pressure to obtain 4.70 g of a colorless oil product (81% yield).

[0208] 1 1H-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).

[0209] Example 7 (Total grafting rate 58.3% - q - part / acrylate 1:2.5)

[0210]

[0211] A mixture of 3.00 g (hydroxyl n° 300 / g) of sorbitol RE / 20 in toluene (purchased from Lamberti SpA), 0.85 g (2.66 mmol) of the compound of Preparation Example 3, 0.09 g (0.66 mmol) of 70% aqueous methanesulfonic acid, and 0.07 g (0.55 mmol) of 50% aqueous hypophosphorous acid was stirred under reflux for 6 hours while removing water using a Dean-Stark apparatus. Subsequently, the mixture was allowed to reach room temperature, 0.004 g of 4-methoxyphenol was added, and then 1.27 g (17.59 mmol) of acrylic acid was added. Air was bubbled into the interior through a Pasteur pipette to induce reflux, and the mixture was stirred at 85 °C (internal temperature) while maintaining the temperature constant for 6 hours. Finally, the mixture was allowed to reach room temperature, diluted with EtOAc (ethyl acetate) (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic layer was dried over Na2SO4 and filtered. Another equal amount of 4-methoxyphenol was added, and the solvent was removed under reduced pressure to obtain 3.60 g of a colorless oily product (80% yield).

[0212] 1 1H-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).

[0213] Example 8 (Total grafting rate 87% - q - part / acrylate 1:2.4)

[0214]

[0215] A mixture of 2.50 g of polyol 4640 (hydroxyl n° 634 / g) in toluene (purchased from Perstorp), 2.52 g (7.06 mmol) of the compound of Preparation Example 4, 0.17 g (1.16 mmol) of 70% aqueous methanesulfonic acid, and 0.13 g (0.96 mmol) of 50% aqueous hypophosphorous acid was stirred under reflux for 6 hours while removing water using a Dean-Stark apparatus. Subsequently, the mixture was brought to room temperature, 0.007 g of 4-methoxyphenol was added, and then 1.69 g (23.44 mmol) of acrylic acid was added. Air was bubbled into the interior through a Pasteur pipette to induce reflux, and the mixture was stirred at 85 °C (internal temperature) while maintaining the temperature constant for 6 hours. Finally, the mixture was brought to room temperature, diluted with EtOAc (ethyl acetate) (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic layer was dried over Na2SO4 and filtered. Another equal amount of 4-methoxyphenol was added, and the solvent was removed under reduced pressure to obtain 5.98 g of a colorless oily product (96% yield).

[0216] 1 1H-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).

[0217] Example 9 (Total grafting rate 87.5% - q - part / acrylate 1:2.5)

[0218]

[0219] A mixture of 2.50 g of polyol 4640 (hydroxyl n° 634 / g) in toluene (purchased from Perstorp), 2.42 g (7.06 mmol) of the compound of Preparation Example 5, 0.16 g (1.16 mmol) of 70% aqueous methanesulfonic acid and 0.13 g (0.96 mmol) of 50% aqueous hypophosphorous acid was stirred under reflux for 6 hours while removing water using a Dean-Stark apparatus. Subsequently, the mixture was allowed to reach room temperature, 0.007 g of 4-methoxyphenol was added, and then 2.01 g (27.97 mmol) of acrylic acid was added. Air was bubbled into the interior through a Pasteur pipette to induce reflux, and the mixture was stirred at 85 °C (internal temperature) while maintaining the temperature constant for 6 hours. Finally, the mixture was allowed to reach room temperature, diluted with EtOAc (ethyl acetate) (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic layer was dried over Na2SO4 and filtered. Another equal amount of 4-methoxyphenol was added, and the solvent was removed under reduced pressure to give 5.64 g of a colorless oil product (95% yield).

[0220] 1 1H-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).

[0221] Example 10 (Total grafting rate 92% - q - part / acrylate 1:2.7)

[0222]

[0223] A mixture of 2.50 g of polyol 4640 (hydroxyl n° 634 / g) in toluene (purchased from Perstorp), 2.78 g (7.06 mmol) of the compound LFC4, 553 of Preparation Example 6, 0.16 g (1.16 mmol) of 70% aqueous methanesulfonic acid solution and 0.13 g (0.96 mmol) of 50% aqueous hypophosphorous acid solution was stirred under reflux for 6 hours while removing water using a Dean-Stark apparatus. Subsequently, the mixture was allowed to reach room temperature, 0.007 g of 4-methoxyphenol was added, and then 1.69 g (23.44 mmol) of acrylic acid was added. Air was bubbled into the interior through a Pasteur pipette to induce reflux, and the mixture was stirred at 85 °C (internal temperature) while maintaining the temperature constant for 6 hours. Finally, the mixture was allowed to reach room temperature, diluted with EtOAc (ethyl acetate) (50 mL), and washed with 0.25 M Na2CO3 (25 mL) and brine (25 mL). The organic layer was dried over Na2SO4 and filtered. Another equal amount of 4-methoxyphenol was added, and the solvent was removed under reduced pressure to obtain 5.70 g of a colorless oily product (89% yield).

[0224] 1 1H-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).

[0225] Comparative Test

[0226] The activity of a representative photoinitiator (PI) of the present invention was compared with that of photoinitiator Ebecryl LEO 10103 (sold by Allnex) (also referred to as COMP-1 herein).

[0227] Example 11

[0228] Tack-free and Yellowness Index (YI) in Transparent Preparation

[0229] A photopolymerizable composition for testing was prepared by dissolving 20 wt% of PI in a solution (50% of Photomer 3016 (bisphenol A epoxy diacrylate), 15% of Photomer 4335 (PETIA), 15% of Photomer 4666 (DPHA), 20% of Photomer 4172 (PPTTA)).

[0230] PI was tested alone (Table 1), or tested with the addition of 4 wt% of a co-initiator (Omnipol ASA) (Table 2), or tested with the addition of 4 wt% of a co-initiator (Omnipol ASA) and 0.5 wt% of a sensitizer Omnirad ITX (Tables 3 and 4).

[0231] The photopolymerizable composition was spread on a varnished cardboard with a thickness of 12 μm using a bar-coater, and then polymerized using the following methods:

[0232] a) A mercury lamp at a distance of 8 cm

[0233] b) An LED 395 nm lamp at a distance of 0.5 cm

[0234] c) An LED 365 nm lamp at a distance of 0.5 cm.

[0235] In some tests, YI was also evaluated.

[0236] The results are expressed in meters per minute, i.e., the maximum speed to reach dry to the touch.

[0237] The results using a 120 W / cm ultraviolet mercury lamp are recorded in Table 1.

[0238] Table 1

[0239] PI Tack-free m / min COMP-1 14 Example 1 34 Example 3 26 Example 6 19 Example 9 21

[0240] The results using a 12 W / cm 2 UV LED 365 lamp are recorded in Table 2.

[0241] (PI + co-initiator)

[0242] Table 2

[0243] PI Tack-free m / min COMP-1 Tack-free not achieved Example 1 15

[0244] The results using a 16 W / cm 2 UV LED 395 lamp are recorded in Table 3.

[0245] (PI + Co - initiator + Sensitizer)

[0246] Table 3

[0247] PI Tack-free m / min YI COMP-1 24 14.08 Example 1 26 10.97 Example 6 n.d. 8.79 Example 8 n.d. 9.04

[0248] n.d. = Not determined

[0249] The results using a 12W / cm 2 UV LED 365 lamp are recorded in Table 4.

[0250] (PI + Co - initiator + Sensitizer)

[0251] Table 4

[0252] PI Tack-free m / min COMP-1 20 Example 1 25 Example 3 25 Example 4 28

[0253] The above results indicate that whether using a UV mercury lamp or a UV LED lamp, the compounds of the present invention perform better than the control PI in the surface - dry test and / or the YI test.

Claims

1. A compound of formula (I): wherein G is the residue of a monomeric, oligomeric or polymeric polyol G-(OH) which is optionally ethoxylated and / or propoxylated; m+q+p of; m is from 1 to 7; q is from 1 to 7; p is from 0 to 6; m + q + p is from 3 to 8; R1 is CH2=CH-C(=O) or CH2=C(CH3)-C(=O); R2 is selected from: 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 a bond connected to the keto group of the compound of formula (I).

2. The compound according to claim 1, wherein G-(OH) m+q+p Selected from: monomeric polyols, oligomeric polyols and mixtures thereof, which may optionally be ethoxylated or propoxylated.

3. The compound according to claim 1 or 2, wherein G-(OH) m+q+p The number average molecular weight is not more than 1500 Da, more preferably not more than 1000 Da, and most preferably not more than 800 Da; and is not less than 100 Da, preferably not less than 200 Da.

4. The compound according to any one of claims 1 to 3, wherein ·q is from 1 to 4, more preferably from 2 to 4, such as 2, 3 or 4; ·p is from 0 to 3, more preferably from 0 to 2, such as 0, 1 or 2; ·m is from 1 to 6, more preferably from 2 to 4, such as 2, 3 or 4; ·m + q + p is from 3 to 6, more preferably from 3 to 5, such as 3, 4 or 5.

5. The compound according to any one of claims 1 to 4, wherein R2 is (A), and X is S or O, preferably S.

6. A photopolymerizable composition comprising: a) at least one ethylenically unsaturated compound in an amount of 50 to 99.9% by weight, preferably 70 to 98.9% by weight, based on the total content of the composition; b) from 1 to 40% by weight, preferably from 3 to 35% by weight, more preferably from 5 to 30% by weight, of at least one compound of formula (I) as claimed in any one of claims 1 to 5, based on the total content of the composition; and c) from 0 to 20% by weight, preferably from 0 to 15% by weight, more preferably from 0.2 to 15% by weight, of accelerator and / or co-initiator, based on the total content of the composition.

7. The photocurable composition according to claim 6, further comprising one or more of the following components: d) from 0.01 to 15% by weight of one or more sensitizers, based on the total content of the composition; and / or e) from 0.5% to 15% by weight of one or more additional photoinitiators, based on the total amount of the composition.

8. The photocurable composition according to claim 6 or 7, characterized in that The promoter and / or co-initiator is an amine, preferably a tertiary amine.

9. A method for photocuring a photopolymerizable composition, coating, adhesive and ink, the method comprising: i. Provide a photopolymerizable composition as described in any one of claims 6 to 8; ii. Coat or print the photopolymerizable composition onto a substrate; and iii. Photopolymerize the coated or printed composition on the substrate with a light source.

10. A method for three-dimensional printing, comprising providing a photopolymerizable composition according to any one of claims 6 to 8, and photocuring the composition with a light source.

11. The method according to claim 9 or 10, characterized in that The light source includes UV light in at least one range within the UVA, UVB and UVC ranges.

12. The method according to any one of claims 9 to 11, characterized in that The light source is an LED source.

13. The method according to any one of claims 9, 11 or 12, further comprising the step of applying the photopolymerizable composition to a substrate before photopolymerizing the photopolymerizable composition.

14. An article obtained by the method according to any one of claims 9 to 13, or by three-dimensional printing of the composition according to any one of claims 6 to 8.

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