UV light stabilizers

Abstract

The presently claimed invention is directed to a triazinyl acrylate compound or mixtures thereof obtainable by a process comprising the step of: a) reacting at least one compound of formula (I), (I) with at least one lactone or lactam, wherein R3 and R5 are, independently of each other, hydrogen or methyl; R4 is hydrogen, methyl or hydroxy; R6 is hydrogen, methyl, hydroxy, or phenyl; formula (II), (II); to obtain a compound of formula (III), (III) where R1 is a group of formula m is an integer from 0 – 10; X is -O- or -NH-; and R2 is hydrogen or a group of formula (III); b) reacting compound of formula (II) from step a) with a compound of formula (IV), (IV) wherein R7 is hydrogen or methyl; wherein at least 30% by weight of compound(s) of formula (II) from step a) reacting with compound of formula (IV) in step b) represent compound(s) of formula (II) with m > 0.

Description

[0001] UV LIGHT STABILIZERS

[0002] Field of Invention

[0003] The presently claimed invention is directed to triazinyl ultraviolet (UV) absorbing compounds and process for the preparation thereof.

[0004] Background of the Invention o-Hydroxyphenyl-s-triazine derivatives are useful as stabilizers for protecting organic material from photolytic, thermal and oxidative degradation, preferably for coatings, adhesives, sealants and printing ink applications and as plastic additives.

[0005] US3249608A relates to hydroxyphenyl-1 ,3,5-triazine, processes for its production and its uses.

[0006] WO2016 / 053662A1 relates to compounds that have ultraviolet light absorbing properties, and which can also have mesogenic properties, to compositions that include one or more such compounds, and to articles of manufacture that include one or more such compounds.

[0007] The literature is abundant on the use of such triazine-based stabilizers for ultraviolet stabilization. For instance, US2017 / 0349730A1 introduces a composition comprising hydroxyphenyl triazines and hindered amine stabilizers in combination with antioxidants and phosphite into molded articles to obtain suitable thermal and ultraviolet stabilization.

[0008] However, several challenges have been identified in this field. For instance, the low molecular weight of well-known stabilizers makes them highly incompatible with use in plastics and coatings, leading to high level of migration of these molecules towards the boundaries of the said material, thereby resulting in poor long-term stability of the material. This is countered in US20120243115A1 by the synthesis of stabilizer moieties bearing acrylate moieties. The compounds are also noted to display improved integration within the polymeric matrix, thereby resulting in improved stability.

[0009] US20120243115A1 describes the use of a phenyl-s-triazine UV absorber with a methacrylate group having the following structure:

[0010] (C-1 )

[0011] EP0711804A2 describes the use of a phenyl-s-triazine UV absorber also with a methacrylate group having the following structure:

[0012] While these improved UV absorbers are particularly designed to meet high performance and durability requirements, their role as additives in coatings, adhesives and the like introduces new challenges. As additives, the stability of these absorbers is highly dependent on their compatibility (or solubility) and distribution in the base material. As a consequence, said incompatibility with the coating composition can lead to inhomogeneity with unwanted characteristics such as reduction in gloss or milkiness. These properties of solubility are particularly relevant for thin film applications, where relatively high UV absorber dosages are needed for ensuring adequately high performance and durable protection.

[0013] Therefore, there is an unmet need to develop UV stabilizer compounds that are capable of maintaining important performance parameters such as high solubility, processability and stability, while remaining economically feasible.

[0014] Summary of the Invention

[0015] Surprisingly it was found that triazine-based UV absorbers bearing polymerizable acrylate groups can improve compatibility and loading of the UV absorbers into coatings, films, adhesives, sealants, among others. In particular, the presence of a spacer, which is introduced to the UV absorbers via the reaction with lactone / lactam of formula VII, provides surprising improvements in terms of solubility (compatibility) and application (high gloss, refer example section below).

[0016] Accordingly, the first aspect of the presently claimed invention is directed to a triazinyl acrylate compound or mixtures thereof obtainable by a process comprising the step of: a) reacting at least one compound of formula (I) with at least one lactone or lactam, wherein R3 and R5 are, independently of each other, hydrogen or methyl; R4 is hydrogen, methyl or hydroxy; R6 is hydrogen, methyl, hydroxy, or phenyl; to obtain a compound of formula where R1 is a group of formula (III), m is an integer from 0 - 10; n is independently selected from an integer from 2 - 5;

[0017] X is -O- or -NH-; and

[0018] R2 is hydrogen or a group of formula (III); b) reacting compound of formula (II) from step a) with a compound of formula

[0019] (IV), wherein R7 is hydrogen or methyl; and at least one compound of formula (II) reacting with compound of formula IV in step b) has m > 0.

[0020] The second aspect of the presently claimed invention is directed to process for obtaining the tria- zinyl acrylate compound or mixtures thereof according to the first aspect.

[0021] The third aspect of the presently claimed invention is directed to use of the triazinyl acrylate compound or mixtures thereof according to the first aspect as a UV absorber for preparing curable coating, ink adhesive or sealant.

[0022] Detailed description

[0023] Furthermore, the ranges defined throughout the specification include the end values as well i.e. a range of 1 to 10 implies that both 1 and 10 are included in the range.

[0024] In the following passages, different aspects of the presently claimed invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.

[0025] Reference throughout this specification to 'one embodiment' or 'an embodiment' means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the presently claimed invention. Thus, appearances of the phrases 'in one embodiment' or 'in an embodiment' in various places throughout this specification are not necessarily all referring to the same embodiment.

[0026] Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some, but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the presently claimed invention, and form different embodiments, as would be understood by those in the art. For example, in the appended claims, any of the claimed embodiments can be used in any combination.

[0027] In the context of the present invention, the product is useful as an ultraviolet (UV) stabilizer or light stabilizers. Said term, may be defined as products or compounds with ability to absorb light in the UVA and / or UVB. As mentioned above, the stabilizers are mainly used to curtail photodegradation (for instance in plastics or polymers) by playing a key role in suppressing the generation of radicals that cause plastic to degrade. Suitable stabilizers typically have at least one absorption maximum in the range between 280 to 420 nm.

[0028] Accordingly, the presently claimed invention is directed to a triazinyl acrylate compound or mixtures thereof obtainable by a process comprising the step of: a) reacting at least one compound of formula (I) with at least one lactone or lactam, wherein R3 and R5 are, independently of each other, hydrogen or methyl;

[0029] R4 is hydrogen, methyl or hydroxy;

[0030] R6 is hydrogen, methyl, hydroxy, or phenyl; to obtain a compound of formula (II), where R1 is a group of formula (III), n is independently selected from an integer from 2 - 5; m is an integer from 0 - 10;

[0031] X is -O- or -NH-; and

[0032] R2 is hydrogen or a group of formula (III); b) reacting compound of formula (II) from step a) with a compound of formula

[0033] (IV), wherein R7 is hydrogen or methyl; wherein at least 30% by weight of compound(s) of formula (II) from step a) reacting with compound of formula (IV) in step b) represent compound(s) of formula (II) with m > 0.

[0034] Preferably, R2, R3 and R5 in formula II are hydrogen.

[0035] Preferably, R4 in formula II is hydrogen or methyl.

[0036] Preferably R6 in formula II is methyl or phenyl, more preferably R6 is phenyl.

[0037] More preferably, R2, R3 and R5 are hydrogen; R4 is hydrogen or methyl; and R6 is methyl or phenyl.

[0038] More preferably, R2, R3, R4 and R5 in formula II are hydrogen.

[0039] Even more preferably, R2, R3, R4 and R5 are hydrogen and R6 is phenyl in formula II.

[0040] More preferably R7 in formula III is methyl.

[0041] Preferably, X in formula III is O.

[0042] Preferably, n in formula III is 3 to 5, more preferably 4 or 5, most preferably 5.

[0043] The compound of formula (II) obtained in step a) represents a mixture of a compound of formula (II), wherein m is 0 (= compound of formula (I) (non-reacted starting material)), and compound(s) of formula (II), wherein m is > 0. The amount of compound(s) of formula (II) with m is > 0 obtained in step a) is preferably at least 30% by weight, more preferably at least 40% by weight, most preferred at least 50% by weight of compound(s) of formula (II) with m is 0 and m is > 0 (i.e. compound(s) of formula (II), wherein m is an integer from 1 to 10).

[0044] Preferably, at least 40% by weight, more preferably at least 50 by weight of compound of formula (II) from step a) reacting with compound of formula IV in step b) represent compound(s) of formula (II) with m > 0.

[0045] The weight percentage of compound of formula (II) is measurable by known techniques, for instance LCMS. LCMS measurements may be carried out with reproducible accuracy by having accurate retention times pre-measured for known compounds (refer Table 1 below) and then subsequently analyzing aliquots of the reaction mixture.

[0046] More preferably, m in formula III is selected from 1 - 3, even more preferably m is selected from 1 - 2.

[0047] Most preferably, the compound of formula I is selected from 4-[4,6-bis([1 ,1 '-biphenyl]-4-yl)-1 ,3,5- triazin-2-yl]-1 ,3-benzenediol (CAS 182918-16-7), 2,4-di(2,4-dimethylphenyl)-6-(2,4-dihydroxy- phenyl)-triazine (CAS 1668-53-7), or 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1 ,3,5-triazine (CAS 38369-95-8).

[0048] More preferably, the compound of formula II is selected from a compound as described in Table 1 below.

[0049] The compound of formula (II) represents, for example, a mixture of a compound of formula (II), wherein m is 0 (= compound of formula (I) (non-reacted starting material)), and compound(s) of formula (II), wherein m is > 0, i.e. m is an integer of 1 to 5. The amount of compound(s) of formula (II) with m is > 0 is preferably at least 40% by weight, more preferably at least 50% by weight, based on compound(s) of formula (II) with m is 0 and m is > 0 (i.e. compound(s) of formula (II), wherein m is an integer from 1 to 5). Preferably, compound of formula (I) in step a) is reacted with at least one lactone or lactam of formula (VII), wherein n is an integer from 2 - 5 and X is -O- or -NH-.

[0050] More preferably, X in formula VII is -O-.

[0051] More preferably, n in formula VII is an integer from 3 - 5, more preferably from 4 or 5, most preferably 5.

[0052] Even more preferably, X in formula VII is -O- and n in formula VII is an integer from 3 - 5.

[0053] Most preferably, X in formula VII is -O- and n in formula VII is an integer from 4 - 5.

[0054] Preferably, the triazinyl acrylate is a compound of formula

[0055] (V), wherein R3 and R5 are, independently of each other, hydrogen or methyl;

[0056] R4 is hydrogen, methyl or hydroxy;

[0057] R6 is hydrogen, methyl, hydroxy, or phenyl; and

[0058] R2 is hydrogen or a group of formula

[0059] (VI); wherein in formula V or formula VI, n is independently selected from an integer from 2 - 5; m is independently selected from an integer from 0 - 10;

[0060] X is independently selected from -O- or -NH-; p is selected from 0 or 1 ;

[0061] R8 is independently selected from hydrogen, acrylate or methacrylate, and R7 is independently selected from hydrogen or methyl.

[0062] If R8 is acrylate or methacrylate, it may be, for example, a group of formula , or

[0063] More preferably, R4 in formula V is hydrogen or methyl.

[0064] More preferably R6 in formula V is methyl or phenyl, more preferably R6 is phenyl.

[0065] More preferably, R2, R3, R4, and R5 in formula V are hydrogen.

[0066] Even more preferably R2, R3, R4 and R5 are hydrogen and R6 is phenyl in formula V.

[0067] More preferably, R7 in formula V or VI is methyl.

[0068] Even more preferably R2, R3, R4, R5 and R7 are hydrogen and R6 is phenyl in formula V.

[0069] Most preferably, R8 in formula V or VI is hydrogen.

[0070] More preferably, R2 in formula V is hydrogen.

[0071] Most preferably, R2, R3 and R5 in formula II are hydrogen.

[0072] More preferably, X in formula V or VI is O.

[0073] More preferably, n in formula V or VI is independently selected from 3 to 5, more preferably from 4 or 5, most preferably 5.

[0074] More preferably, m in formula V or VI is independently selected from 1 - 3, even more preferably m is selected from 1 - 2.

[0075] More preferably, p in formula V or VI is 1. More preferably, the triazinyl acrylate is a phenyl-s- triazines acrylate of the formula described below in table 2.

[0076] The triazinyl acrylates of formula (V), wherein m is an integer from 1 - 10, especially from 1 - 5, are new and form a further object of the present application.

[0077] m = 0-5 (in the above table) means a mixture of compounds of formula (II) with m is 0-5 (m is 0, or an integer from 1 to 5), wherein the amount of compound(s) of formula (II) with m is > 0 is at least 30% by weight, preferably at least 40% by weight, more preferably at least 50% by weight based on compound(s) of formula (II).

[0078] Compounds of formula (VIII), such as, for example,

[0079] UV-5, UV-6, UV-8, UV-12, UV-14 and UV-16, are formed by transesterification.

[0080] Even more preferably, the triazinyl acrylate is a phenyl-s-triazines acrylate of the formula de- scribed below:

[0081] UV-4

[0082] UV-15.

[0083] The presently claimed invention is also directed to process for obtaining the triazinyl acrylate compound or mixtures thereof as described herein, said process comprising the step of a. reacting the compound of formula I with at least one lactone or lactam to obtain a compound of formula (II); b. reacting compound of formula (II) from step a) with a compound of formula (IV), wherein at least 30% by weight of compound(s) of formula (II) from step a) reacting with compound of formula (IV) in step b) represent compound(s) of formula (II) with m > 0.

[0084] Preferably, at least 40% by weight, more preferably at least 50% by weight of compound of formula (II) from step a) reacting with compound of formula IV in step b) represent compound(s) of formula (II) with m > 0.

[0085] More preferably, m in formula III is selected from 1 - 3, even more preferably m is selected from 1 - 2.

[0086] The step a) is noted to introduce a spacer group via the reaction with lactone / lactam of formula VII. The presence of said spacer, provides surprising improvements in terms of solubility (compatibility) and application (refer example section below).

[0087] Most preferably, the compound of formula I is selected from 4-[4,6-bis([1 ,1 '-biphenyl]-4-yl)-1 ,3,5- triazin-2-yl]-1 ,3-benzenediol (CAS 182918-16-7), 2,4-di(2,4-dimethylphenyl)-6-(2,4-dihydroxy- phenyl)-triazine (CAS 1668-53-7), or 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1 ,3,5-triazine (CAS 38369-95-8). Preferably, the tnazinyl acrylate obtained by the process described herein, is a compound of for- mula (V), wherein

[0088] R3 and R5 are, independently of each other, hydrogen or methyl;

[0089] R4 is hydrogen, methyl or hydroxy;

[0090] R6 is hydrogen, methyl, hydroxy, or phenyl; and

[0091] R2 is hydrogen or a group of formula (VII); wherein in formula V or formula VI, n is independently selected from an integer from 2 - 5; m is independently selected from an integer from 0 - 10;

[0092] X is independently selected from -O- or -NH-; p is selected from 0 or 1 ;

[0093] R7 is independently selected from hydrogen or methyl, and R8 is independently selected from hydrogen, acrylate or methacrylate.

[0094] More preferably, R4 in formula V is hydrogen or methyl.

[0095] More preferably R6 in formula V is methyl or phenyl.

[0096] More preferably, R2, R3, R4, R5, and R6 in formula V are hydrogen.

[0097] More preferably, R7 in formula V or VI is methyl.

[0098] Most preferably, R2, R3, R4, R5, R6 and R7 are hydrogen.

[0099] Most preferably, R8 in formula V or VI is hydrogen.

[0100] More preferably, R2 in formula V is hydrogen.

[0101] Most preferably, R2, R3 and R5 in formula II are hydrogen. More preferably, X in formula V or VI is O.

[0102] More preferably, n in formula V or VI is independently selected from 3 to 5, more preferably from 4 or 5, most preferably 5.

[0103] More preferably, m in formula V or VI is independently selected from 1 - 3, even more preferably m is selected from 1 - 2.

[0104] More preferably, p in formula V or VI is 1 .

[0105] Preferably, in the process described herein, the compound of formula (I) in step a) is reacted with at least one lactone or lactam of formula (VII), wherein n is an integer from 2 - 5 and X is -O- or -NH-.

[0106] More preferably, X in formula VII is -O-.

[0107] More preferably, n in formula VII is an integer from 3 - 5, more preferably from 4 or 5, most preferably 5.

[0108] Even more preferably, X in formula VII is -O- and n in formula VII is an integer from 3 - 5.

[0109] Most preferably, X in formula VII is -O- and n in formula VII is an integer from 4 - 5.

[0110] Preferably, the process step a) is as described in the scheme 1 below.

[0111] Scheme 1

[0112] Preferably, in the process described herein, the step a) is carried out in the presence of at least one first catalyst selected from sodium carbonate, potassium carbonate, or cesium carbonate, more preferably the first catalyst is potassium carbonate. Preferably, the catalyst in the reaction of the step a) is present in an amount in the range of 0.0001 to 30 wt.% based on total weight of compound(s) of formula (I), more preferably the catalyst in the reaction is present in a total amount in the range of 0.01 to 10 wt.% based on total weight of compound(s) of formula (I), even more preferably the catalyst in the reaction is present in a total amount in the range of 0.01 to 5 wt.% based on total weight of compound(s) of formula (I), most preferably the catalyst in the reaction is present in a total amount in the range of 0.01 to 3.0 wt.% based on total weight of compound(s) of formula (I), and in particular the catalyst in the reaction is present in a total amount in the range of 0.01 to 1 wt.% based on total weight of compound(s) of formula (I).

[0113] Preferably, the catalyst in the reaction of step a) is present in an amount in the range of 0.0001 to 2.0 mole equivalent based on compound(s) of formula (I), more preferably the catalyst in the reaction is present in a total amount in the range of 0.0001 to 1.0 mole equivalent based on compound^) of formula (I), even more preferably the catalyst in the reaction is present in a total amount in the range of 0.001 to 1 .0 mole equivalent based on compound(s) of formula (I), most preferably the catalyst in the reaction is present in a total amount in the range of 0.001 to 0.5 mole equivalent based on compound(s) of formula (I),, and in particular the catalyst in the reaction is present in a total amount in the range of 0.001 to 0.1 mole equivalent based on compound(s) of formula (I).

[0114] The process step a) can be carried out in presence of a solvent or in the absence of a solvent. The process may be performed in presence of a solvent or alternatively at high temperatures to ensure molten reaction conditions. When present, the solvent may be in a minimum quantity as would be necessary to ensure appropriate mixing. In context of the present invention, some light stabilizers are known to be obtainable commercially in the form of a suspension / solution, the solvent already present in such cases is sufficient and no added solvent is necessary. Preferably, the reaction mixture, in the process for obtaining the claimed product, is essentially free from any added liquid reactants or additives. Liquid additives comprise solvents, diluents and the like.

[0115] When the process is carried out in the presence of a solvent, the solvent is preferably selected from ethers, sulfones, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethylsulfoxide, N-methyl-pyrrolidone, N-ethyl-pyrrolidone, aromatic hydrocarbons, dichloroethane, halogenated aromatic hydrocarbon, or a combination of two or more thereof, more preferably the solvent is selected from ethers, ketones, water, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethylsulfoxide, N-methyl-pyrrolidone, N-ethyl-pyrrolidone, aromatic hydrocarbons, dichloroethane, halogenated aromatic hydrocarbon, or a combination of two or more thereof, even more preferably the solvent is selected from ethers, N, N-dimethylformamide, N-methyl-pyrrolidone, N-ethyl-pyrrolidone, aromatic hydrocarbons, dichloroethane, halogenated aromatic hydrocarbon, or a combination of two or more thereof, most preferably the solvent is selected from ethers, N, N-dimethylformamide, N-methyl-pyrrolidone, N-ethyl-pyrrolidone, aromatic hydrocarbons, halogenated aromatic hydrocarbon, or a combination of two or more thereof, and in particular the solvent is selected from ketones, ethers, aromatic hydrocarbons, halogenated aromatic hydrocarbon, water or a combination thereof More preferably, in the process described herein, the step a) is carried out in the presence of an inert solvent like polar solvent such as NMP, DMF, DMSO etc. or an ether solvent such as diethy- lenglycol diethylether, ethyleneglycol diethylether etc. Also, nitrile solvents such as benzonitrile are suitable. Aromatic solvents such as chlorobenzene or dichlorobenzene are also suitable. Most preferably, the solvent is NMP.

[0116] Preferably, the reaction of step a) is carried out in presence of a solvent in an amount in the range of 0.01 to 20 times based of total amount of compound(s) of formula (I) or (VI), more preferably the reaction is carried out in presence of a solvent in an amount in the range of 0.1 to 10 times based of total amount of compound(s) of formula (I), even more preferably the reaction is carried out in presence of a solvent in an amount in the range of 0.2 to 5.0 times based of total amount of compound^) of formula (I), most preferably the reaction is carried out in presence of a solvent in an amount in the range of 0.5 to 3.0 times based of total amount of compound(s) of formula (I), and in particular the reaction is carried out in presence of a solvent in an amount in the range of 0.5 to 2.0 times based of total amount of compound(s) of formula (I).

[0117] Preferably, in the process described herein, the step a) is carried out under anhydrous conditions at reaction temperatures of 100 - 300°C, more preferred are reaction temperatures of 120 - 250°C and even more preferred are reaction temperatures of 150 - 220°C.

[0118] Said process step a) may be conducted for 1 minute to 48 hours, more preferably for 1 minute to 12 hours, even more preferably from 30 minutes to 3 hours. The process may preferably be carried out in the presence of mechanical agitation such as stirring. The same may be performed by any known method using external mechanical shakers or by using magnetic stirring beads among others.

[0119] The triazinyl acrylates are available by the addition reaction of the intermediates of formula II with glycidyl ether of formula IV (as described herein in process step b). Preferably, the process of step b) is carried out as described in the scheme 2 below-

[0120] Scheme 2 The glycidyl ether of formula IV is used in an amount of not greater than 5 parts by weight, relative to 100 parts by weight of the intermediate of formula 11-1 . In certain embodiments, the glycidyl ether of formula IV is used in an amount of not greater than 2 parts, even not greater than 1 part, or not greater than 0.5 part by weight, relative to 100 parts by weight of the intermediate of formula 11-1 .

[0121] The addition reaction of step b) may be carried out in the presence of a catalyst. Suitable catalysts are for example ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride or quarternary ammonium compounds such as tetraethylammonium bromide. Also, basic catalysts such as 2-methylimidazole, pyridine or triethylamine might be suitable. Most preferably, the catalyst employed during step b) is ethyltriphenylphosphonium bromide.

[0122] Preferably, the catalyst in the reaction of the step b) is present in an amount in the range of 0.0001 to 30 wt.% based on total weight of compound(s) of formula (11-1 ), more preferably the catalyst in the reaction is present in a total amount in the range of 0.01 to 10 wt.% based on total weight of compound(s) of formula (11-1 ), even more preferably the catalyst in the reaction is present in a total amount in the range of 0.01 to 5 wt.% based on total weight of compound(s) of formula (11-1), most preferably the catalyst in the reaction is present in a total amount in the range of 0.01 to 3.0 wt.% based on total weight of compound(s) of formula (11-1 ), and in particular the catalyst in the reaction is present in a total amount in the range of 0.01 to 1 wt.% based on total weight of compound(s) of formula (11-1 ).

[0123] Preferably, the catalyst in the reaction of step b) is present in an amount in the range of 0.0001 to 2.0 mole equivalent based on compound(s) of formula (11-1 ), more preferably the catalyst in the reaction is present in a total amount in the range of 0.0001 to 1 .0 mole equivalent based on compound^) of formula (11-1), even more preferably the catalyst in the reaction is present in a total amount in the range of 0.001 to 1.0 mole equivalent based on compound(s) of formula (11-1 ), most preferably the catalyst in the reaction is present in a total amount in the range of 0.001 to 0.5 mole equivalent based on compound(s) of formula (11-1 ), and in particular the catalyst in the reaction is present in a total amount in the range of 0.001 to 0.1 mole equivalent based on compound(s) of formula (11-1 ).

[0124] The process step b) can be carried out in presence of a solvent or in the absence of a solvent. The process may be performed in presence of a solvent or alternatively at high temperatures to ensure molten reaction conditions. When present, the solvent may be in a minimum quantity as would be necessary to ensure appropriate mixing. In context of the present invention, some light stabilizers are known to be obtainable commercially in the form of a suspension / solution, the solvent already present in such cases is sufficient and no added solvent is necessary. Preferably, the reaction mixture, in the process for obtaining the claimed product, is essentially free from any added liquid reactants or additives. Liquid additives comprise solvents, diluents and the like.

[0125] When the process step b) is carried out in the presence of a solvent, the solvent is preferably selected from ethers, sulfones, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethylsulfoxide, N-methyl-pyrrolidone, N-ethyl-pyrrolidone, aromatic hydrocarbons, dichloroethane, halogenated aromatic hydrocarbon, or a combination of two or more thereof, more preferably the solvent is selected from ethers, ketones, water, N, N-dimethylformamide, N, N-di- methylacetamide, acetonitrile, dimethylsulfoxide, N-methyl-pyrrolidone, N-ethyl-pyrrolidone, aromatic hydrocarbons, dichloroethane, halogenated aromatic hydrocarbon, or a combination of two or more thereof, even more preferably the solvent is selected from ethers, N, N-dimethylformamide, N-methyl-pyrrolidone, N-ethyl-pyrrolidone, aromatic hydrocarbons, dichloroethane, halogenated aromatic hydrocarbon, or a combination of two or more thereof, most preferably the solvent is selected from ethers, N, N-dimethylformamide, N-methyl-pyrrolidone, N-ethyl-pyrrolidone, aromatic hydrocarbons, halogenated aromatic hydrocarbon, or a combination of two or more thereof, and in particular the solvent is selected from ketones, ethers, aromatic hydrocarbons, halogenated aromatic hydrocarbon, water or a combination thereof.

[0126] Preferably, the reaction of step b) is carried out in presence of a solvent in an amount in the range of 0.01 to 20 times based of total amount of compound(s) of formula (11-1 ) or (IV), more preferably the reaction is carried out in presence of a solvent in an amount in the range of 0.1 to 10 times based of total amount of compound(s) of formula (11-1 ), even more preferably the reaction is carried out in presence of a solvent in an amount in the range of 0.2 to 5.0 times based of total amount of compound(s) of formula (11-1 ), most preferably the reaction is carried out in presence of a solvent in an amount in the range of 0.5 to 3.0 times based of total amount of compound(s) of formula (II- 1 ), and in particular the reaction is carried out in presence of a solvent in an amount in the range of 0.5 to 2.0 times based of total amount of compound(s) of formula (11-1 ).

[0127] The addition reaction of step b) is carried out at temperatures of 20 - 150 °C, preferably at 40 - 130°C, most preferably at 80 - 120°C.

[0128] If the reaction of step b) is preferably carried out in an inert solvent, the temperature of the reaction mixture can be maintained in the boiling range (reflux) for the duration of the reaction. The reaction of step b) may be preferably carried out with the exclusion of oxygen, for example by flushing with an inert gas such as nitrogen or argon.

[0129] The reaction of step b) is carried out in the presence of a polymerization inhibitor or without the presence of a polymerization inhibitor. Examples of suitable polymerization inhibitors are TEMPO, TEMPOL, phenothiazine, 4-tert-butylcatechol (TBC), 4-methoxyphenol (MEHQ), butylated hydroxytoluene (BHT) and hydroquinone (HQ). The polymerization inhibitor should be present in a concentration effective to prevent unwanted polymerization of the acrylate and methacrylate groups. Preferably, the reaction of step b) is carried out in the presence of a polymerization inhibitor.

[0130] Said process step b) may be conducted for up 1 minute to 48 hours, more preferably for 1 minute to 12 hours, even more preferably from 30 minues to 3 hours. The process may preferably be carried out in the presence of mechanical agitation such as stirring. The same may be performed by any known method using external mechanical shakers or by using magnetic stirring beads among others.

[0131] Preferably, the product obtained according to presently claimed invention has weight average molecular weight in the range of 300 to 5000, preferably in the range of 400 to 3000, more preferred in the range of 500 to 2000, even more preferred in the range of 500 to 1200 as determined by GPC using polystyrene as internal standard.

[0132] When the reaction (as described in steps a or b) is complete, working-up can be carried out in accordance with customary methods.

[0133] The presently claimed invention is also directed to the use of the triazinyl acrylate compound or mixtures thereof as described herein, as a UV absorber for preparing curable coating, ink adhesive or sealant.

[0134] The use of the triazinyl acrylate compound or mixtures thereof as ultraviolet absorber or stabilizer may be in personal and home care such as in cosmetics, plastics or surface coatings (such as automotive coatings).

[0135] Preferably, the triazinyl acrylate compound or mixtures thereof are used as curable coatings, ink adhesives or sealant on a substrate is selected from metals, metal alloys, woods, plastics, or ceramics.

[0136] Preferably, the coatings are surface coatings. Preferably, the composition is an automotive coating composition.

[0137] The coating composition is preferably a laquer, in particular a stoving laquer which is used for coating automobiles (automobile finishing lacquers), for example stoving lacquers comprising al- kyd / melamine resins and alkyd / acrylic / melamine resins (see H. Wagner and H. F. Sarx, "Lack- kunstharze" (1977), pages 99-123), epoxy / carboxy resins, isocyanate crosslinked acrylic polyols or polyester polyols. Other crosslinking agents include glycoluril resinsor blocked isocyanates.

[0138] The coating composition preferably contains 0.01-10 parts by weight, especially 0.05-10 parts by weight, more especially 0.1 -5 parts by weight, of the product, or a salt thereof according to the invention per 100 parts by weight of a solid binder. The binders may in principle be any binders that are customary in the art, for example those described in Ullmann’s Encyclopedia of Industrial Chemistry, 5th ed., Vol. A18, pp. 368-426, VCH, Weinheim 1991. The binder will generally be a film-forming binder, based on a thermoplastic or thermosetting resin, predominantly on a thermosetting resin. Examples thereof are alkyd, acrylic, polyester, phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.

[0139] It may be a cold-curable or a hot-curable binder, and the addition of a curing catalyst may be advantageous. Suitable catalysts, which accelerate full curing of the binder, are described, for example, in Ullmann’s Encyclopedia of Industrial Chemistry, Vol. A18, p. 469, VCH Verlagsgesell- schaft, Weinheim 1991.

[0140] Multilayer systems are possible here as well, it being possible for the concentration of the stabilizers in the top layer to be higher, for example from 1 to 15 parts by weight, especially from 3 to 10 parts by weight, based on 100 parts by weight of solid binder. The presently claimed invention is also directed to a composition comprising the triazinyl acrylate compound or mixtures thereof, described hereinabove.

[0141] Preferably the composition may be solvent based or water based. Typical examples of organic solvents are aliphatic, aromatic or cycloaliphatic hydrocarbons, alcohols, glycols, esters, acetates and ketones.

[0142] The product obtained can be stabilized by the optional addition of polymerization inhibitors for preventing polymerization reactions of the acrylate and methacrylate groups during transport and storage. The polymerization inhibitor should be used in a concentration effective to prevent unwanted polymerization.

[0143] The presently claimed invention is also directed to a method of protecting a material or coating from light, wherein the method comprises a step of providing triazinyl acrylate compound or mixtures thereof obtained according to presently claimed invention as UV stabilizer. Said triazinyl acrylate compound or mixtures thereof is noted to provide long term stability comparable with commonly used industry standard UV absorber (for e.g., hydroxyphenyl benzotriazole class absorber).

[0144] Preferably, the composition may be solvent based or water based. Typical examples of organic solvents are aliphatic, aromatic or cycloaliphatic hydrocarbons, alcohols, glycols, esters, acetates and ketones.

[0145] Embodiments:

[0146] In the following, there is provided a list of embodiments to further illustrate the present disclosure without intending to limit the disclosure to the specific embodiments listed below.

[0147] 1. A triazinyl acrylate compound or mixtures thereof obtainable by a process comprising the step of: a) reacting at least one compound of formula (I) with at least one lactone or lactam, wherein R3 and R5 are, independently of each other, hydrogen or methyl;

[0148] R4 is hydrogen, methyl or hydroxy;

[0149] R6 is hydrogen, methyl, hydroxy, or phenyl; to obtain a compound of formula (II), where R1 is a group of formula (III), m is an integer from 0 - 10; n is independently selected from an integer from 2 - 5;

[0150] X is -O- or -NH-; and

[0151] R2 is hydrogen or a group of formula (III); b) reacting compound of formula (II) from step a) with a compound of formula wherein R7 is hydrogen or methyl; wherein at least 30% by weight of compound(s) of formula (II) from step a) reacting with compound of formula (IV) in step b) represent compound(s) of formula (II) with m > 0.

[0152] 2. The triazinyl acrylate compound or mixtures thereof claimed in embodiment 1 , wherein at least 40% by weight of compound of formula (II) from step a) reacting with compound of formula IV in step b) represent compound(s) of formula (II) with m > 0.

[0153] 3. The triazinyl acrylate compound or mixtures thereof claimed in any of the preceding embodiments, wherein at least 50% by weight of compound of formula (II) from step a) reacting with compound of formula IV in step b) represent compound(s) of formula (II) with m selected from 1 - 3.

[0154] 4. The triazinyl acrylate compound or mixtures thereof claimed in any of the preceding embodiments, wherein the triazinyl acrylate is a compound of formula

[0155] R2 is hydrogen or a group of formula (Vii); wherein m is an integer from 1 - 10 and R8 is selected from hydrogen, acrylate or methacrylate.

[0156] 5. The triazinyl acrylate compound or mixtures thereof claimed in any of the preceding embodiments, wherein n is an integer from 3 - 5; m is an integer from 1 - 5; p is 1 and X is -O-.

[0157] 6. The triazinyl acrylate compound or mixtures thereof claimed in any of the preceding embodiments, wherein R2 and R8 are hydrogen.

[0158] 7. The triazinyl acrylate compound or mixtures thereof claimed in any of the preceding embodiments, wherein R2, R3 and R5 are hydrogen; R4 is hydrogen or methyl; and R6 is methyl or phenyl.

[0159] 8. The triazinyl acrylate compound or mixtures thereof claimed in any of the preceding embodiments, wherein R7 is methyl.

[0160] 9. The triazinyl acrylate compound or mixtures thereof claimed in any of the preceding embodiments, wherein R2, R3, R4, R5, R6 and R7 are hydrogen.

[0161] 10. The triazinyl acrylate compound or mixtures thereof claimed in any of the preceding embodiments, wherein compound of formula (I) in step a) is reacted with at least one lactone or lactam of

[0162] 0 formula i -x(VI), wherein n is an integer from 2 - 5 and X is -O- or -NH-. 11 . The triazinyl acrylate compound or mixtures thereof claimed in embodiment 10, wherein X is -O- and n is an integer from 3 - 5.

[0163] 12. A process for obtaining the triazinyl acrylate compound or mixtures thereof according to any of the preceding claims, said process comprising the step of a. reacting the compound of formula I with at least one lactone or lactam to obtain a compound of formula (II); b. reacting compound of formula (II) from step a) with a compound of formula (IV), wherein at least 30% by weight of compound(s) of formula (II) from step a) reacting with compound of formula (IV) in step b) represent compound(s) of formula (II) with m > 0.

[0164] 13. The process of embodiment 12, wherein the step a) is carried out in the presence of at least one first catalyst selected from sodium carbonate, potassium carbonate, or cesium carbonate.

[0165] 14. The process according to embodiments 12 or 13, wherein the step b) is carried out in the presence of at least one second catalyst selected from ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, or quarternary ammonium compounds such as tetraethylammonium bromide, or from basic catalysts such as 2-methylimidazole, pyridine, or triethylamine.

[0166] 15. Use of the triazinyl acrylate compound or mixtures thereof according to embodiments 1 -11 , as a UV absorber for preparing curable coating, ink adhesive or sealant.

[0167] 16. The use claimed in embodiment 15, wherein the curable coating, ink adhesive or sealant is applied on a substrate selected from metals, metal alloys, woods, plastics, ceramics and another coatings.

[0168] The presently claimed invention is illustrated in detail by non-restrictive working examples which follow. More particularly, the test methods specified hereinafter are part of the general disclosure of the application and are not restricted to the specific working examples.

[0169] Examples

[0170] Example 1 : Synthesis of the intermediate of formula (ll-a)

[0171] A mixture of NMP (1030.0 g) and 4-[4,6-Bis([1 ,1 '-biphenyl]-4-yl)-1 ,3,5-triazin-2-yl]-1 ,3-benzenediol (355.0 g) are charged into a 1 .5 L-double-jacketed reactor with the necessary auxiliary equipment and heated up to 150°C under stirring. Potassium carbonate (99.5 g) is added into the reaction flask in portions. The reactor contents are stirred for 1 hour at 160°C. Then a vacuum of 300 mbar was applied for 3.5 hours while distilling off volatiles (382.0 g). The reaction mixture is heated to 180°C resulting in a dark red solution. e-Caprolactone (116.0 g) is added dropwise within 7.5 hours at 180°C and the reactor content is stirred for 4 hours at 180°C. After cooling to 50°C ethyl acetate (2250.0 g) and formic acid (350 g) are added. The reaction mixture is washed with water (1200 g each) twice. Ethyl acetate is removed at 80°C under vacuum. The residue is then dissolved in toluene (300 g) at 95°C, bleaching earth and activated carbon are added. The mixture is filtered off and a brownish filtrate (1177 g) is obtained (dry content: 37%). After diluting the filtrate with methanol (5700 g) a precipitate is obtained, which is filtered off and washed with methanol delivering the intermediate of formula (ll-a) as a beige product (415 g).

[0172] Similar products are obtained when using cesium carbonate or sodium carbonate instead of potassium carbonate.

[0173] Example 2: Synthesis of a triazine methacrylate UV-3

[0174] DMF (20.0 g), toluene (467 g), intermediate obtained in example 1 (199.0 g), hydroquinonemonomethyl ether (0.6 g) and ethyltriphenylphosphonium bromide (7.5 g) are charged into a reaction flask with the necessary auxiliary equipment and heated to 100°C under stirring. Glycidyl methacrylate (87.9 mL) is added dropwise within 7.5 hours. The mixture is stirred at 100°C for 4 hours. After cooling to 90°C the reaction mixture is extracted with water four times. The organic phase is treated with bleaching earth and activated carbon. The mixture is then filtered off and a reddish solution (720 g) is obtained. After diluting the filtrate with methanol (900 g) a precipitate is obtained, which is filtered off and washed with methanol (100.0 g), dried at 40°C under vacuum delivering the product UV-3 as a beige solid (190 g).

[0175] Example 3: Synthesis of a triazine acrylate methacrylate UV-3

[0176] Toluene (42 g), intermediate obtained in example 1 (19.9 g), hydroquinonemonomethyl ether (0.06 g) and ethyltriphenylphosphonium bromide (0.75 g) are charged into a reaction flask with the necessary auxiliary equipment and heated to 100-105°C. Glycidyl methacrylate (8.28 g) is added dropwise within 1 hour. The mixture is stirred for 3 hours. After addition of another portion of glycidyl methacrylate (1.2 g) the reaction mixture is stirred for 1.5 hours. After extracting the reaction mixture with 50 g of water twice, the organic phase is treated with bleaching earth and activated carbon. The mixture is then filtered off and a brownish solution is obtained. After distilling off the solvent the crude product (22.6 g) is diluted with tetrahydrofurane (420 g) the product precipitates, which is filtered off and washed with THF (100.0 g), dried at 50°C under vacuum delivering the product of the general formula of UV-3 as a brownish, highly viscous liquid (19.3 g).

[0177] Example 4: Synthesis of a triazine methacrylate UV-3 Example 4 is produced in the same manner as described in example 3 with the difference that no additional portion of glycidyl methacrylate and ethyltriphenylphosphonium bromide are added. Example 4 is obtained as light brownish, very viscous liquid (30.3 g).

[0178] Comparative Example 1 : Synthesis of triazine acrylate C-1

[0179] The synthesis is adapted from US 20120243115 A1. Xylene (146.0 g), 4-[4,6-Bis([1 , 1 '-biphenyl]- 4-yl)-1 ,3,5-triazin-2-yl]-1 ,3-benzenediol (69.0 g), 4-methoxyphenol (0.4 g) and ethyltriphenylphosphonium bromide (2.6 g) are charged into a 0.3 L-double-jacketed reactor with the necessary auxiliary equipment and heated up to 120°C under stirring. Glycidyl methacrylate (20.5 g) is added dropwise within 15 min. The mixture is stirred for 4 hours and another portion of glycidyl methacrylate (4.2 g) is added. The reaction mixture is stirred for 1 .5 hours and then cooled to 60°C. After extracting the reaction mixture with 100 g of water twice, the organic phase is diluted with xylene (200.0 g) and cooled to 20°C obtaining a beige suspension. The precipitate is then filtered off and dried in vacuum yielding 60.8 g of compound C-1 as a beige powder. The product is recrystallized in xylene (640.0 g) yielding 25.4 g of a light beige powder.

[0180] Comparative Example 2: Synthesis of triazine acrylate C-2

[0181] The synthesis is adapted from EP 0711804 A2. Xylene (130.0 g), 2,4-Di(2,4-dimethylphenyl)-6- (2,4-dihydroxyphenyl)-triazine (39.7 g), 4-methoxyphenol (0.3 g) and ethyltriphenylphosphonium bromide (1 .9 g) are charged into a 0.3 L-double-jacketed reactor with the necessary auxiliary equipment and heated up to 105°C under stirring. Glycidyl methacrylate (21.4 g) is added dropwise within 20 min. The mixture is stirred for 7 hours and cooled down to 25°C. After extracting the reaction mixture with 50 g of water twice, the organic phase is concentrated at 70°C under vacuum yielding a dark yellow product melt. N-Heptane (150.0 g) are added and the reaction mixture is cooled down to 20°C yielding a precipitate. The precipitate is then filtered off and dried in vacuum yielding 44.0 g of compound C-2 as a yellow powder. The product is recrystallized in xylene (100.0 g) yielding 13.8 g of a light yellow powder.

[0182] The triazine acrylate UV-absorbers according to the present invention (Example 2-4) show excellent UV radiation absorbing properties, solubility and high applicability in coating compositions versus the comparative examples C-1 and C-2 lacking the spacer group (no step a) involving reaction with lactone / lactam).

[0183] Table 1 : Characterization of inventive examples

[0184] Table 2: LC-MS of (UV-3) obtained in Examples 2 to 4

[0185] Application Tests:

[0186] The solubility and compatibility were tested in the following UV curable clear coat composition.

[0187] Table 3: Composition of the UV curable clear coat composition

[0188] 4% UV absorber was added to the composition (1 g UV absorber to 25 g composition) and mixed for 2 minutes together with glass beads in a speed-mixer (shaker) for appropriate incorporation. Afterwards it was visually inspected to ensure that all UV absorber material was dissolved in the formulation.

[0189] The composition was applied with a bar coater (50 pm) on a white coil coated panel and cured with UV lamps (Hg lamp 50% and Ga lamp 50%; 5m / min belt speed). After curing the gloss (85°) was determined by a glossmeter.

[0190] Table: Solubility and gloss

[0191] The tables above demonstrate that the examples have sufficient solubility and lead to desired high gloss of the coating film in comparison to the comparative example.

Claims

Claims1. A triazinyl acrylate compound or mixtures thereof obtainable by a process comprising the step of:a) reacting at least one compound of formula (I) with at least one lactone or lactam, wherein R3 and R5 are, independently of each other, hydrogen or methyl;R4 is hydrogen, methyl or hydroxy;R6 is hydrogen, methyl, hydroxy, or phenyl;to obtain a compound of formulawhere R1 is a group of formulam is an integer from 0 - 10;X is -O- or -NH-; n is independently selected from an integer from 2 - 5; andR2 is hydrogen or a group of formula (III); b) reacting compound of formula (II) from step a) with a compound of formula(IV), wherein R7 is hydrogen or methyl; wherein at least 30% by weight of compound(s) of formula (II) from step a) reacting with compound of formula (IV) in step b) represent compound(s) of formula (II) with m > 0.

2. The triazinyl acrylate compound or mixtures thereof claimed in claim 1 , wherein at least 40% by weight of compound(s) of formula (II) from step a) reacting with compound of formula IV in step b) represent compound(s) of formula (II) with m > 0.

3. The triazinyl acrylate compound or mixtures thereof claimed in any of the preceding claims, wherein the triazinyl acrylate is a compound of formulaand / or a compound of formulawherein R3 and R5 are, independently of each other, hydrogen or methyl;R4 is hydrogen, methyl or hydroxy;R6 is hydrogen, methyl, hydroxy, or phenyl; andR2 is hydrogen or a group of formula(VI); and wherein in formula V or formula VI or formula VIII, n is independently selected from an integer from 2 - 5; m is independently selected from an integer from 0 - 10;X is independently selected from -O- or -NH-; p is selected from 0 or 1 ;R7 is independently selected from hydrogen or methyl, andR8 is independently selected from hydrogen, acrylate or methacrylate.

4. The triazinyl acrylate compound or mixtures thereof claimed in any of the preceding claims, wherein n is an integer from 3 - 5; m is an integer from 1 - 5; p is 1 and X is -O-.

5. The triazinyl acrylate compound or mixtures thereof claimed in any of the preceding claims, wherein R8 is hydrogen.

6. The triazinyl acrylate compound or mixtures thereof claimed in any of the preceding claims, wherein R2, R3 and R5 are hydrogen; R4 is hydrogen or methyl; and R6 is methyl or phenyl.

7. The triazinyl acrylate compound or mixtures thereof claimed in any of the preceding claims, wherein R7 is methyl.

8. The triazinyl acrylate compound or mixtures thereof claimed in any of the preceding claims, wherein R2, R3, R4, R5, R6 and R7 are hydrogen.

9. The triazinyl acrylate compound or mixtures thereof claimed in any of the preceding claims, wherein compound of formula (I) in step a) is reacted with at least one lactone or lactam offormula (VII), wherein n is an integer from 2 - 5 and X is -O- or -NH-.

10. The triazinyl acrylate compound or mixtures thereof claimed in claim 9, wherein X in formula VII is -O- and n in formula VII is an integer from 3 - 5.

11. A process for obtaining the triazinyl acrylate compound or mixtures thereof according to any of the preceding claims, said process comprising the step of a. reacting the compound of formula I with at least one lactone or lactam; b. reacting compound of formula (II) from step a) with a compound of formula (IV) to obtain a compound of formula (II), wherein at least 30% by weight of compound(s) of formula (II) from step a) reacting with compound of formula (IV) in step b) represent compound(s) of formula (II) with m > 0.

12. The process of claim 11 , wherein the step a) is carried out in the presence of at least one first catalyst selected from sodium carbonate, potassium carbonate, or cesium carbonate.

13. The process according to claims 11 or 12, wherein the step b) is carried out in the presence of at least one second catalyst selected from ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, or quarternary ammonium compounds such as tetraethylammonium bromide, or from basic catalysts such as 2-methylimidazole, pyridine, or triethylamine.

14. Use of the triazinyl acrylate compound or mixtures thereof according to any one of the claims1 to 10 as a UV absorber for preparing curable coating, ink adhesive or sealant.

15. The use claimed in claim 14, wherein the curable coating, ink adhesive or sealant is applied on a substrate selected from metals, metal alloys, woods, plastics, ceramics and another coatings.wherein R3 and R5 are, independently of each other, hydrogen or methyl;R4 is hydrogen, methyl or hydroxy;R6 is hydrogen, methyl, hydroxy, or phenyl; andR2 is hydrogen or a group of formula(VI); and wherein in formula V or formula VI, n is independently selected from an integer from 2 - 5; m is independently selected from an integer from 1 - 10, especially 1 - 5;X is independently selected from -O- or -NH-; p is selected from 0 or 1 ;R7 is independently selected from hydrogen or methyl, andR8 is independently selected from hydrogen, acrylate or methacrylate.

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