Curable Compositions Containing UV Stabilizers

Abstract

The present invention relates to a curable composition comprising at least one compound of formula (1), [Formula 1] JPEG2022548487000063.jpg73165 where R is C1-C10 alkyl and R 1 -R 10 are each independently selected from the group consisting of hydrogen and C-C alkyl, with the proviso that R 1 -R 10 is alkyl, and wherein the residue R of each aromatic ring 1 -R 5 and R 6 -R 10 The substitution patterns formed by The present invention relates to cured compositions obtained from such curable compositions, mixtures of compounds of formula (I), the use of such compounds and mixtures of such compounds as UV stabilizers in curable compositions, and methods for the preparation of curable compositions comprising the UV stabilizer of formula (I).

Description

[Technical field]

[0001] The present invention relates to curable compositions comprising certain UV stabilizer compounds, mixtures of UV stabilizer compounds, and the use of such compounds and mixtures of compounds as UV stabilizers, as well as methods for making such curable compositions. [Background technology]

[0002] Organic plastic resins, film-forming materials, and molded or extruded plastic parts coated with traditional protective coatings will discolor, become brittle, and eventually deteriorate when exposed to sunlight. To avoid the harmful and damaging effects of sunlight on plastics and other materials, formulators incorporate UV stabilizers to minimize these adverse effects.

[0003] Diacylresorcinol derivatives used as UV absorbers in exterior coatings, such as acrylate-based coatings, have been used to try to improve weatherability. However, in general, their solubility in the coating matrix must be increased to be compatible with the coating matrix. Diacylresorcinol derivatives (e.g., dibenzoylresorcinol, DBR) are generally not highly soluble in organic matrices, such as the organic polymer matrix of a primer layer for a thermally cured hard coat. US 5,869,185 describes the application of dibenzoylresorcinol in a PMMA matrix, where a strong solvent is used to generate a primer and the primer is applied to a polycarbonate panel. [ka] DBR itself is not suitable as a UV absorber in organic acrylate coatings due to its poor compatibility with organic polymer matrices. The solubility of DBR in organic matrices, e.g. polymer coating compositions, can be increased by adding suitable organic solvents, such as strong alcohol solvents, but this is disadvantageous for general use of the coating when applied to sensitive polymer substrates like polycarbonates. Thus, the use of diacylresorcinol derivatives, especially in acrylate-based clearcoats, is limited. One approach to overcome this problem has been to introduce silane side groups into the diacylresorcinol core to increase solubility and compatibility with the coating matrix, e.g. for the application of 4,6-dibenzoyl-2-(3-triethoxysilylpropyl)resorcinol (SDBR) (see, e.g., US 5,990,188 and US 5,391,795). [ka]

[0004] However, when silane side groups are introduced to the diacylresorcinol core, -silylated diacylresorcinols are expensive because the trialkoxysilane side chains are introduced in a multi-step synthesis, thereby reducing the overall yield of the UV absorber synthesis; -trialkoxysilane groups are reactive to hydrolysis; sterically bulky side chains reduce the molar efficiency of the molecule and affect the mechanical properties of the coating matrix, for example by reducing the abrasion resistance of the coating layer; There are some drawbacks such as:

[0005] Thus, there remains a need for UV absorbers based on a diacylresorcinol core that enhance the solubility of the UV absorbers and are relatively easy to synthesize. Summary of the Invention

[0006] Detailed Description of the Invention The inventors have surprisingly found that by using a mixture of resorcinol derivatives, the solubility of the mixture in the coating matrix is ​​significantly increased in alcoholic solvents compared to the pure / isolated analogues of each of these resorcinol derivatives. Such a mixture can be obtained in a one-step synthesis starting from a mixture of 2-alkylresorcinols and alkylated benzoyl chlorides and optionally alkylated benzoyl chlorides different from the aforementioned alkylated benzoyl chlorides, which results in the formation of a statistical mixture of two symmetrical addition products and one asymmetrical derivative.

[0007] The present invention therefore provides an efficient route to weathering protective coatings using a class of diacylresorcinol derivative mixtures as UV absorbers. The use of low molecular weight mixtures of diacylresorcinol derivatives as UV absorbers in the coating matrix, obtained in a one-step synthesis, overcomes the inefficiencies of previous solutions due to high synthesis costs, low yields in multi-step manufacturing processes, and the required high concentrations (wt%) in the coating matrix.

[0008] In a first aspect, the present invention relates to a curable composition that is photostable and capable of absorbing ultraviolet radiation.

[0009] The present invention specifically relates to a curable composition comprising: at least one compound of formula (1): [ka] where R is C1-C10 alkyl, and R 1 -R 10 are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, with the proviso that R 1 -R 10 is C1-C10 alkyl, and wherein the residue R 1 -R 5 and R6 -R 10 The substitution patterns formed by are different from each other.

[0010] Curing composition The curable composition according to the present invention can be any composition capable of being cured, which refers to the strengthening or hardening of a polymeric material by crosslinking of polymer chains by a chemical process. The aforementioned curing process can be affected by heat, radiation, electron beam, or chemical additives, and is characteristically accompanied by an increase in viscosity or hardness. The term is also used when the monomers present in the composition have more than one site for polymerization, and crosslinking and polymerization of the monomers occur simultaneously. This is the case, for example, of polyacrylate monomers that contain several acrylate moieties that function as sites for polymerization and crosslinking.

[0011] Curable Compositions - Components and Polymers Furthermore, the curable composition according to the present invention refers to various types of compositions including mixtures of various organic polymers, organic polymers and monomers, or monomers, such as all kinds of polycarbonates, poly(meth)acrylates, polyolefins, polyurethanes, polyorganosiloxanes, as well as mixtures of various copolymers and polymeric compounds.

[0012] Monomers of the composition In one embodiment, the curable composition according to the present invention preferably comprises at least one acrylic monomer, where the term "acrylic monomer" generally includes esters and amides of acrylic acid, methacrylic acid, and their homologs and analogs, such as ethylacrylic, phenylacrylic, or chloroacrylic acid. The preferred acids are acrylic acid and methacrylic acid, with acrylic acid generally being the most preferred. The acrylic monomer is preferably an ester, and generally, the term "acrylate" or "acrylic" as used herein includes methacrylates, when the corresponding structural formula or chemical name so indicates. Other examples of acrylic monomers that can be used to modify the coating composition are dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, 1,6-hexanediol diacrylate, octanediol diacrylate, decanediol diacrylate, tetrahydrofurfuryl acrylate, octyl / decyl acrylate, isobornyl acrylate, cyclohexyl acrylate, N-vinylpyrrolidone, aliphatic urethane acrylate oligomer, and aliphatic polyester acrylate oligomer.Urethane acrylate is particularly preferred.

[0013] More preferably, at least a portion of the acrylic ester monomers present in the curable composition are silyl acrylates, which are used to prepare the silyl acrylate-modified colloidal silica. Suitable silyl acrylates include those of the formula: [ka] Here, R 15 is hydrogen or methyl, and R 16 is C alkylene, R 17 is C1-13 alkyl or aryl, R 18is C alkyl and a is 0 to 3. Particularly preferred are acrylates, where R 15 is methyl and R 16 is C2-4 alkylene and in particular trimethylene; R 18 is methyl and a is 0.

[0014] It is also generally preferred that the curable compositions according to the present invention include at least one multifunctional acrylic monomer. Such monomers include compounds of the formula: [ka] Here, R 15 is as previously defined, in which case it is preferably hydrogen, and R 19 is a polyvalent organic radical and b is an integer from 2 to 8. 19 The radical is most often an aliphatic radical having about 4 to 20 carbon atoms. Preferably, b is 5-6 and R 19 is alkylene, especially unbranched alkylene such as tetramethylene, hexamethylene or octamethylene. Examples of multifunctional acrylic monomers suitable for the present invention are dipentaerythritol monohydroxypentaacrylate (DiPePeta, SR-399, Sartomer Co.), hexafunctional polyurethane acrylate (PU, Ebecryl 1290, UCB Radcure Inc.), and hexafunctional polyester acrylate (PE, Ebecryl 830, UBC Radcure Inc.), and dipentaerythritol hexaacrylate.

[0015] Photoinitiator of the composition The curable composition according to the invention may further comprise one or more photoinitiators for ultraviolet light-induced curing of said composition. Many such photoinitiators are known in the art, and many are suitable for use according to the invention. The photoinitiator may be selected from the types disclosed in U.S. Pat. Nos. 4,478,876 and 5,318,850. Further examples include aromatic ketones, such as acetophenone, benzophenone, xanthone, benzoin compounds, and the like; tertiary amines, such as triethanolamine, methyldiethanolamine, and 4-dimethylaminobenzophenone; combinations of acyl phosphorus compounds, including triorganobenzoyl diaryl phosphine oxides, triorganobenzoyl diorgano phosphonates, and triorganobenzoyl diaryl phosphine sulfides. Acyl phosphorus compounds are preferred, with bis-(2,4,6-trimethylbenzoyl)phenylphosphine oxide being particularly preferred, which is available as Irgacure® 819 from BASF Corporation. Other photoinitiators are benzoin derivatives (2-benzoyl-2-propanol (Darocur® 1173), 1-hydroxy-cyclohexyl-phenyl ketone (Irgacure® 184), dimethoxyacetophenone (Irgacure® 651), substituted α-amino ketones (Irgacure® 907), and benzoyl oxime derivatives (Irgacure® OXE01).

[0016] Light stabilizer of the composition The curable compositions according to the present invention may contain, in addition to the resorcinol derivatives according to the present invention, one or more additional ultraviolet (UV) light stabilizers, which are present in the range of 0.2-2.0 weight percent to inhibit the type of UV degradation that leads to the formation of microcracks, delamination, and yellowing, but do not have a substantially inhibiting effect on the UV-induced curing of the composition.

[0017] The hindered amine light stabilizer (HALS) can be any hindered amine light stabilizer known to those skilled in the art that has a sufficiently low basicity to be compatible with the coating composition matrix. Examples include 2,2,6,6-tetramethylpiperidinyl derivatives Tinuvin 123 (BASF) or Hostavin 3058 (Clariant). Other low basicity HALS are also expected to be effective in the coating composition of the present invention.

[0018] Silica Compound of the Composition Also preferably, the curable composition according to the invention includes a silica compound used to provide abrasion resistance, which includes a silyl acrylate modified silica, where the silica has a median particle size (D50) measured by dynamic light scattering (DLS) in the range of about 5-80 nm, more preferably in particular about 15-30 nm, corresponding to the size of the colloidal silica. Colloidal silica is a dispersion of submicron-sized silica particles in an aqueous or other solvent medium, in which the silica concentration is typically in the range of about 15-50 weight percent. When an aqueous silica dispersion is used to prepare the composition of the invention, hydrolysis of at least a portion of the Si-O bonds of the silyl acrylate optionally present in the composition is possible or possible. Thus, the composition of the invention may include those that include the hydrolysis products of said silyl acrylate. Examples of silyl acrylate modified colloidal silica are described in U.S. Pat. No. 5,468,789. In general, the curable composition of the invention may include a surfactant, a leveling agent, or a mixture thereof. An example of a surfactant or leveling agent is the silicone hexaacrylate Ebecryl 1360, a product of Allnex.

[0019] Solvent for the composition The curable composition according to the present invention may contain one or more solvents, where the solvent used in these compositions is an organic solvent that dissolves acrylic polymer, is inert to solid substrates, and is easily volatilized.Some non-limiting examples of such solvents include hydroxyethers, alcohols, ketoalcohols, liquid aliphatic hydrocarbons, liquid alicyclic hydrocarbons, and mixtures thereof.It is further important that the solvent can sufficiently dissolve the compound of general formula (I).According to the present invention, alkanols and hydroxyl ethers are particularly preferred solvents.

[0020] Curable compositions according to the present invention may also include an emulsion of an acrylic polymer and water, which further includes a hydroxyl ether, an alkanol, or a mixture of a hydroxyl ether and an alkanol.

[0021] The hydroxyl ethers present in these emulsion compositions are compounds represented by the general formula: R 20 -OR 21 -OH Here, R 21 is a saturated divalent aliphatic radical, preferably containing from 1 to 6 carbon atoms, R 20 is an alkyl or alkoxyalkyl radical containing 1 to 6 carbon atoms.

[0022] The alkanols which may be present in the emulsion composition generally contain from 1 to 4 carbon atoms.

[0023] Further Additives for the Curable Composition In general, the curable compositions according to the invention may comprise further additives necessary for levelling of the polymer and compositions comprising the polymer during the application process of the coating composition, such as polyethersiloxane-copolymer surfactants and surface-active components (e.g. BYK310 (available from BYK Chemie)) or reactive surfactants and reactive surfactants, such as polyethersiloxane-copolymers with one or more reactive (meth)acrylate functional groups (e.g. Tegorad 2100, Tegorad 2200 from Evonik, or BYK UV3570 from BYK Chemie).

[0024] In general, the curable compositions according to the invention may comprise curing catalysts, such as di-tert.-butyl peroxide (DTBP), dicumyl peroxide (DCP) or 2,2'-azodi(isobutyronitrile) (AIBN), further additives necessary for levelling of the polymer and polymer-containing compositions during the application process of the coating composition, such as surfactants and surface-active components (e.g. BYK310 (available from BYK Chemie)) or reactive surfactants and reactive surfactants (e.g. Tegorad 2100 from Evonik).

[0025] Preferably, the curable composition according to the present invention comprises about 27-about 60% by weight of acrylate monomers, where aliphatic urethane polyacrylates: about 25-about 50% by weight, preferably about 30-about 40% by weight, and low viscosity aliphatic di- and triacrylates (e.g., HDDA): about 1-10% by weight, preferably about 2 to about 6% by weight; from about 1 to about 15% by weight, preferably from about 1 to about 9% by weight, more preferably from about 2 to about 7% by weight of a resorcinol-based UV absorber according to the present invention, from 0 to about 2% by weight, preferably from about 0.2 to about 0.8% by weight, of a further light stabilizer, 0 to about 4 wt. %, preferably about 1 to about 2.5 wt. %, of a photoinitiator: 0 to about 10% by weight, preferably about 2 to about 8% by weight, and most preferably about 2 to about 5% by weight of a silica component; from about 20 to about 80% by weight, preferably from about 32 to about 70% by weight, more preferably from about 35 to about 60% by weight of a solvent, and less than about 1 wt. % of additional additives, where the weight percentages add up to 100%, based on the total weight of the composition.

[0026] According to the present invention, the term "curable composition" refers to compositions for forming UV-curable and thermally curable hardcoats, especially UV-curable hardcoats.

[0027] Preparation and Processing of Curable Compositions The curable compositions according to the invention can be prepared by simply blending the various reagents in the desired ratios. If a solvent is present and / or colloidal silica is the source of the silicon compound, the volatiles can be removed by conventional operations such as vacuum stripping. The composition can then be applied to a substrate, which is often a polycarbonate, polyester, or acrylic resin such as poly(methyl)methacrylate, by conventional techniques such as dipping, brushing, spraying, roller coating, or flow coating. The coating thus formed preferably has a thickness ranging from about 3 to about 25 μm, typically from about 8 to 16 μm. After application, the composition is cured by exposure to suitable ultraviolet light. The curing temperature is not critical, but can be in the range of about 25-about 70° C. The process can be carried out as a batch process or a continuous line for coating and curing. The cured products of the curable compositions according to the invention are other aspects of the invention, which are further described below.

[0028] Organic Polymer Matrix of the Curable Composition According to the present invention, the term "organic polymer matrix" is used to refer to any type of polymer component of the curable composition according to the present invention after curing, where one or more types of polymers may constitute the organic polymer matrix of the curable composition after curing.

[0029] C1-C10 alkyl residue of the compound of the curable composition C1-C10 alkyl groups according to the present invention include straight-chain, branched and cyclic alkyl groups, including straight-chain or branched alkyl groups having a cyclic alkyl group as a substituent, and straight-chain or branched alkyl groups that contain a cyclic alkylene group in the carbon chain.

[0030] In a preferred embodiment, the C1-C10 linear alkyl groups are selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl groups, the branched alkyl groups are selected from isopropyl, sec-butyl, iso-butyl, tert-butyl, sec-pentyl, iso-pentyl, neopentyl, and 2-ethylhexyl groups, and the cyclic alkyl groups are selected from cyclopentyl and cyclohexyl groups. These alkyl groups are preferred C1-C10 alkyl groups according to the invention, and particularly preferred alkyl groups are methyl, ethyl, and tert-butyl.

[0031] In the curable composition according to the present invention, preferably R and R 1 -R 5 At least one of or R and R 6 -R 10 At least one of R is an alkyl group of the same type, more preferably R; 1 -R 5 At least one of and R 6 -R 10 At least one of the groups is an alkyl group of the same type.

[0032] In a preferred embodiment according to the present invention, the curable composition comprises at least one compound of formula (1), where R is methyl and R 1 -R 10 are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, 1 From R 10 At least one of R is C1-C10 alkyl, preferably R 1 From R 10 One of R is C1-C10 alkyl and the remaining R 1 From R10 with the proviso that the radical R is hydrogen and the residue R 1 -R 5 and R 6 -R 10 The condition is that the substitution patterns formed by

[0033] Therefore, the compound of the above formula (1) contained in the curable composition according to the present invention does not have a plane of symmetry perpendicular to the plane formed by the C atoms of the aromatic ring of the resorcinol group, and does not have an axis of symmetry in the plane formed by the C atoms of the aromatic ring of the resorcinol group.

[0034] In preferred embodiments according to the present invention, the amount of the compound of formula (1) in the curable composition ranges from about 1% to about 15% by weight, more preferably from about 1% to about 9% by weight, and most preferably from about 2% to about 7% by weight, based on the total weight of the curable composition.

[0035] In a preferred embodiment according to the present invention, the curable composition comprises at least one compound of formula (1), where R is methyl and R 1 -R 10 are each independently selected from the group consisting of hydrogen and methyl, with the proviso that R 1 From R 10 At least one of the residues R on each aromatic ring is methyl. 1 -R 5 and R 6 -R 10 The condition is that the substitution patterns formed by

[0036] More preferably, R 1 -R 10 One group of R is methyl, 1 -R 10 The remaining groups are hydrogen.

[0037] In a preferred embodiment according to the present invention, At least one compound of formula (1) is represented by formula (2): [ka] Here, R 13 is C1-C10 alkyl, R 11 and R 12 is selected from hydrogen and C1-C10 alkyl, where R 11 and R 12 At least one of R is C1-C10 alkyl; 11 and R 12 are different from each other.

[0038] Here, preferably, R 13 and R 11 or R 13 and R 12 represent the same type of C1-C10 alkyl group, more preferably R 11 =R 13 = C1-C10 alkyl groups of the same type and R 12 =H, or R 12 =R 13 = C1-C10 alkyl groups of the same type and R 11 =H.

[0039] Also preferably, R 13 is methyl, R 11 and R 12 At least one of R is C1-C10 alkyl, more preferably R 13 is methyl, R 11 and R 12 Only one group is C1-C10 alkyl.

[0040] It is noted that the structure represented by the general formula (2) defined above is a specific structure of the general formula (1) defined above, wherein the residue of the structure of the general formula (1) is R=R 13 =C1-C10 alkyl R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R8 , and R 10 is hydrogen, and R 2 =R 11 = C1-C10 alkyl or hydrogen, R 9 =R 12 =C1-C10 alkyl or hydrogen.

[0041] R 11 and R 12 The condition for the general formula (2) that R 1 -R 5 The substitution pattern formed by 6 -R 10 This corresponds to the condition for general formula (1) that the substitution pattern formed by

[0042] In general, at least one compound of formula (1) or formula (2) according to the present invention is a diacylresorcinol-based UV stabilizer compound that is compatible with the organic polymer matrix of the curable composition after curing.

[0043] According to the present invention, the term "compatibility" refers to the interaction of the polyaroylresorcinol of formula (1) or (2) with an organic polymer matrix. Phase separation of the polyaroylresorcinol from the organic polymer matrix will be detected by visible precipitation of the polyaroylresorcinol in the organic polymer matrix.

[0044] From this above definition, no limitations arise regarding the organic polymer matrix, preferably a transparent organic polymer matrix, that can be used in the present invention, other than that it must be compatible with the above polyaroylresorcinol of formula (1) or (2).

[0045] Illustrative examples of organic polymer matrices that can be used in the present invention include polyurethanes, polycarbonates, polystyrenes, acrylic or methacrylic polymers or copolymers, and mixtures thereof. As used herein, acrylic polymers are defined as acrylates, methacrylates, and copolymers and mixtures thereof.

[0046] The most preferred transparent polymeric matrices result from the curing of a combination of a polyacrylate having up to nine acrylate moieties with an aliphatic or urethane-based backbone and an additional acrylate monomer having up to three acrylate moieties.

[0047] The term organic polymer matrix typically includes compositions containing acrylic polymers and organic solvents, as well as emulsions of acrylic polymers and water and acrylic polymer in water compositions. When emulsions are used, the polybenzoylresorcinols are dispersed therein. Said mixtures of polyaroylresorcinols are obtained, for example, during the Friedel-Crafts acylation of 2-alkylresorcinols or by using a mixture of benzoyl chloride derivatives in the Fries rearrangement reaction, as shown below.

[0048] Such mixtures include mixtures containing compounds of formula (1) and in particular mixtures containing compounds of formula (2). When no emulsion is used, mixtures of compounds of formula (1) or especially formula (2) are also preferred.

[0049] As defined above, according to the present invention, at least two aryl rings of the compound of formula (1) are substituted with at least one C1-C10 alkyl group, where R is necessarily a C1-C10 alkyl group; similarly, the substituent R of the compound of formula (2) is 11 and R 12At least one of the C1-C10 alkyl groups is a C1-C10 alkyl group, which provides more hydrophobicity to the molecule. The presence of such C1-C10 alkyl groups in the compounds of formulas (1) and (2), and thus the increased hydrophobicity provided by the presence of alkyl groups, makes the compounds more compatible with the matrix of the curable composition, in contrast to DBR (dibenzoylresorcinol) (see structure above), which does not have an alkyl group on any of the aryl rings.

[0050] The compound of formula (1) or (2) has the effect of helping the curable composition to be a photostable composition and capable of absorbing ultraviolet light.

[0051] According to the present invention, the term "photostability" is defined as exhibiting resistance to weathering by solar radiation.

[0052] Furthermore, according to the invention, the term "capable of absorbing ultraviolet light" is understood as the property of a compound to undergo a photochemical reaction cycle that converts violet light into heat, under the preservation of its chemical structure.

[0053] In another preferred embodiment according to the present invention, the curable composition comprises at least one compound of formula (2), where R 13 is methyl, R 11 and R 12 is selected from hydrogen and methyl, where R 11 and R 12 At least one of R is methyl; 11 and R 12 are different from each other.

[0054] In a more preferred embodiment of the present invention, the curable composition comprises at least one compound of formula (1), where R is selected from the group consisting of propyl, ethyl, methyl, and R 1 -R 10 are each independently selected from the group consisting of hydrogen, methyl, ethyl, and propyl, with the proviso that R 1 -R 10At least one of the residues R on each aromatic ring is selected from the group consisting of methyl, ethyl, and propyl. 1 -R 5 and R 6 -R 10 are different from each other, and at least one compound of formula (2), where R 13 is selected from the group consisting of methyl, ethyl, and propyl, and R 11 and R 12 are each independently selected from the group consisting of hydrogen, methyl, ethyl, and propyl, with the proviso that R 11 and R 12 At least one of R is selected from the group consisting of methyl, ethyl, and propyl. 11 and R 12 are different from each other, Includes.

[0055] In an even more preferred embodiment of the present invention, the curable composition comprises at least one compound of formula (1), where R is methyl and R 1 -R 10 are each independently selected from the group consisting of hydrogen and methyl, with the proviso that R 1 -R 10 At least one of the residues R on each aromatic ring is methyl. 1 -R 5 and R 6 -R 10 are different from each other, and at least one compound of formula (2), where R 13 is methyl, R 11 and R 12 is selected from hydrogen and methyl, where R 11 and R 12 At least one of R is methyl; 11 and R 12 are different from each other, Includes.

[0056] Preferably, the molar ratio of the compound of formula (2) to the compound of formula (1), excluding the compound of formula (2), is from about 70:30 to about 30:70, more preferably from about 60:40 to about 40:60, and even more preferably about 50:50.

[0057] Also preferably, the total amount of compounds of formula (1) and (2) in the curable composition is up to about 15 wt.%, more preferably in the range of about 1 wt.% to about 9 wt.%, and most preferably in the range of about 2 wt.% to about 7 wt.%, based on the total weight of the curable composition.

[0058] A further embodiment according to the present invention comprises at least one compound of formula (1), wherein R is C1-C10 alkyl and R 1 -R 10 are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, with the proviso that R 1 -R 10 At least one of the residues R on each aromatic ring is C1-C10 alkyl. 1 -R 5 and R 6 -R 10 and at least one compound of formula (3): [ka] Here, R 14 is C1-C10 alkyl, preferably methyl; The present invention relates to a curable composition comprising a mixture containing:

[0059] wherein the at least one compound of formula (1) can be identified as described in each of the above embodiments.

[0060] In the structure of formula (3), C1-C10 alkyl is as defined in the general manner above.

[0061] By combining substituted and unsubstituted 2-alkylresorcinols, the solubility of the resorcinols present in such mixtures in organic solvents is significantly improved as compared to the solubility of the single specific resorcinols that make up such mixtures.

[0062] In a preferred embodiment according to the present invention, the curable composition comprises at least one compound of formula (1), where R is methyl and R 1 -R 10 are each independently selected from the group consisting of hydrogen and methyl, with the proviso that R 1 -R 10 At least one of the residues R on each aromatic ring is methyl. 1 -R 5 and R 6 -R 10 are different from each other, and at least one compound of formula (3), where R 14 is C1-C10 alkyl, preferably selected from the group consisting of methyl, ethyl and butyl, most preferably R 14 is methyl, Contains a mixture of.

[0063] Preferably, the total amount of the compounds of the combined formulas (1) and (3) in the curable composition ranges from about 1% to about 15% by weight, more preferably from about 1% to about 9% by weight, and most preferably from about 2% to about 7% by weight, based on the total weight of the curable composition.

[0064] Also preferably, the molar ratio of the compound of formula (3) to the compound of formula (1) is from about 1:10 to about 1:1, more preferably from about 1:8 to about 1:2.5, and even more preferably from about 1:5 to about 1:3.

[0065] A further preferred embodiment according to the present invention comprises at least one compound of formula (2): [ka] Here, R 13 is C1-C10 alkyl, R 11 and R 12 is selected from hydrogen and C1-C10 alkyl, where R 11 and R 12 At least one of R is C1-C10 alkyl; 11 and R 12 are different from each other, and At least one compound of formula (3), [ka] Here, R 14 is C1-C10 alkyl, preferably methyl; The present invention relates to a curable composition comprising a mixture containing:

[0066] A further preferred embodiment according to the present invention comprises: at least one compound of formula (2), where R 13 is selected from the group consisting of methyl, ethyl, or propyl, and where R 11 and R 12 is selected from hydrogen, methyl, ethyl, and propyl, where R 11 and R 12 At least one of R is selected from a methyl group, an ethyl group, or a propyl group; 11 and R 12 are different from each other, at least one compound of formula (3), where R 14 is selected from the group consisting of methyl, ethyl and propyl; The present invention relates to a curable composition comprising:

[0067] An even more preferred embodiment according to the present invention comprises: at least one compound of formula (2), where R 13 is methyl, R 11 and R 12 is selected from hydrogen and C1-C10 alkyl, where R11 and R 12 At least one of R is C1-C10 alkyl; 11 and R 12 are different from each other, and at least one compound of formula (3), where R 14 is methyl, The present invention relates to a curable composition comprising a mixture containing:

[0068] In a further preferred embodiment according to the present invention, the curable composition comprises a mixture containing at least one compound of formula (2) and at least one compound of formula (3), where R 13 and R 14 is methyl, R 11 and R 12 is selected from hydrogen and methyl, where R 11 and R 12 At least one of R is methyl; 11 and R 12 are different from each other.

[0069] Compounds of general formulae (2) and (3), respectively, bearing one or more methyl groups, are less expensive to produce than analogous compounds bearing the corresponding C2-C10 alkyl groups, such as ethyl, propyl or tert-butyl groups, and are therefore advantageous from an industrial point of view.

[0070] In general, R 11 Different from R 12 It is preferred when the molar ratio of the compound of formula (2) having the formula: to the compound of formula (3) is in the range of about 90:10 to about 50:50, more preferably in the range of about 85:15 to about 60:40, even more preferably in the range of about 80:20 to about 70:30, and most preferably when the molar ratio is in the range of about 77:23 to about 73:27.

[0071] In another preferred embodiment according to the present invention, the curable composition further comprises at least one compound of formula (1), where R is C1-C10 alkyl and R 1 -R10 are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, with the proviso that R 1 -R 10 At least two groups of are C1-C10 alkyl groups, and the residue R of each aromatic ring 1 -R 5 and R 6 -R 10 and preferably R is methyl and R 1 -R 10 is selected from the group consisting of hydrogen and methyl.

[0072] Preferably, the further compound of formula (1) above is a compound of general formula (2), where R 13 is C1-C10 alkyl, R 11 and R 12 is selected from C1-C10 alkyl, where R 11 and R 12 is the same, and preferably R 13 , R 11 and R 12 is methyl.

[0073] In a highly preferred embodiment according to the present invention, the curable composition comprises dibenzoyl acyl-2-methylresorcinol (DBMR). [ka] Benzoyltoluoylacyl-2-methylresorcinol (BTMR) [ka] and ditoluoyl acyl-2-methylresorcinol (DTMR) [ka] and preferably, the molar amount of each of DBMR and DTMR, relative to the molar amount of BTMR set at 2, is independently preferably in the range of 0.1 to 2.5, more preferably 0.2 to 2, even more preferably 0.5 to 1.5, and most preferably 0.75 to 1.25.

[0074] Although the above compounds DBMR, DTMR, and BTMR all exhibit UV stabilizing properties, their application as pure compounds as UV stabilizers in curable coating compositions is hindered by their low solubility and therefore poor compatibility with the organic matrix of the coating composition. Application as mixtures, preferably in the ratios mentioned above, improves the solubility of the compounds in the coating composition and therefore their compatibility with the coating matrix.

[0075] In a preferred embodiment according to the present invention, the curable composition is selected from a photocurable or a thermally curable composition.

[0076] According to the present invention, a photocurable composition is a composition that can be cured by photoinduced curing of monomeric, oligomeric, or polymeric substrates using light, primarily ultraviolet (UV) light. Examples of photocurable compositions according to the present invention are combinations and mixtures of monomeric and oligomeric (meth)acrylates having up to nine (meth)acrylate groups. Particularly preferred compositions are photocurable compositions that form hard coats upon UV curing, such as hard coats based on polyacrylate monomers.

[0077] In general, photocurable compositions according to the present invention may include one or more photosensitizers or photoinitiators necessary for photocuring the composition, and photocurable compositions according to the present invention may include one or more photoactivatable curing catalysts.

[0078] For the curing of the photocurable composition, in most cases lamps emitting light in the visible spectrum having a wavelength of about 380 nm to about 740 nm or UV lamps emitting UV light having a wavelength of about 210 to about 380 nm, more preferably UV lamps, are applied. Usually, the UV light sources used for curing are mercury lamps, mercury lamps with iron or gallium additives, fluorescent lamps, UV LEDs.

[0079] According to the present invention, a thermosetting composition is a composition that can be cured by applying an elevated temperature, thus resulting in the polymerization and / or crosslinking of the monomers and polymers present in the curable composition. An example of a thermosetting composition according to the present invention is a combination of (meth)acrylate monomers and poly(meth)acrylate oligomers.

[0080] To enable thermal curing, the presence of one or more thermal initiators, such as diorganoperoxides, may be required in the curable composition.

[0081] Preferably, the curable composition according to the present invention is a photocurable composition, even more preferably a UV-curable composition.

[0082] In a further preferred embodiment according to the present invention, the curable composition is a polymerizable composition.

[0083] According to the present invention, the term "polymerizable composition" applies to all compositions that contain monomers capable of forming a polymer. In this specification, a polymer is understood to be a substance composed of macromolecules, which consist of a plurality of repeat units. In it, the repeat units can be derived from one type of monomer or from several types of monomers to form copolymers, and when there are several types of repeat units in a polymer, the monomer sequence represented by the repeat units can alternate and be arranged in a periodic order, block by block, random or statistical arrangement. The term "polymer" explicitly includes polymers that require the presence of several compounds for polymerization, such as, for example, compositions containing polyisocyanates and polyols, or compositions containing dihydroxy compounds and phosgene or dimethyl carbonate for the formation of polycarbonates.

[0084] The term "polymerizable composition" according to the present invention does not impose any restrictions on the type of polymerization in which the polymerization of the monomers occurs, such as, for example, radical, anionic or cationic polymerization. The term explicitly includes compositions that can be polymerized by polycondensation or polyaddition reactions. The monomers can be small molecules with a relative molecular weight of less than about 1000 g / mol, but the polymerizable molecules can also be oligomers or preformed macromers with active polymerization sites.

[0085] Examples of polymerizable compositions are compositions comprising C-C-unsaturated compounds, especially compounds containing a C-C double bond such as acrylates, and compositions comprising polyisocyanates.

[0086] Preferred polymerizable compositions according to the present invention are aliphatic monoacrylates, diacrylates or triacrylates, as well as aliphatic acrylate oligomers having up to nine acrylate moieties, either alone or in combination.

[0087] In another preferred embodiment according to the present invention, the curable composition comprises at least one curable monomer.

[0088] According to the present invention, the term "curable monomer" refers to any monomer that allows polymerization involving said monomer in a chain reaction, where the formed polymeric material is usually strengthened or hardened by a crosslinking process. In most cases, this requires the presence of one or more active sites for crosslinking, such as, for example, a C-C double bond, a hydroxyl group, an amino group, a thiol group, an epoxy group, an isocyanate group or an alkoxysilyl group of the molecule of the curable monomer, which are present even after a single polymerization reaction involving the curable monomer.

[0089] In general, the curable monomers may be curable by heat, radiation, especially UV light, by the addition of additives, curing catalysts, or a combination thereof.

[0090] The curable monomers preferably contained in the curable composition according to the present invention are curable CC unsaturated monomers such as (meth)acrylate monomers, vinyl or allylic monomers.

[0091] In a further preferred embodiment according to the present invention, the curable composition comprises at least one curable acrylate monomer.

[0092] According to the present invention, the term "curable acrylate monomer" applies to any curable monomer that is an acrylate monomer as defined above. Acrylate monomers are compounds of acrylic acid and its derivatives, such as salts, esters, and conjugate bases of acrylic acid amides, further substituted at one or both vinyl C atoms. Preferred curable acrylate monomers are polyacrylates, i.e. diacrylates, triacrylates, tetraacrylates, pentaacrylates, and hexaacrylates, especially those polyacrylates with an aliphatic or urethane-based backbone.

[0093] Preferred curable acrylate monomers according to the present invention are 1,6-hexanediol diacrylate (HDDA), decanediol diacrylate, tripropylene glycol diacrylate (TPGDA), trimethylol-propane triacrylate (TMPTA), hydroxyl pivalicneopentyl glycol diacrylate (HPNDA), tricyclodecane dimethanol diacrylate (TCDDA), pentaerythritol triacrylate (PETIA).

[0094] In a further preferred embodiment according to the present invention, the curable composition comprises at least one curable aliphatic polyurethane acrylate monomer.

[0095] According to the present invention, the term "curable aliphatic polyurethane acrylate monomer" refers to any curable monomer as defined above that simultaneously contains one or more polyurethane moieties.

[0096] Preferred curable aliphatic polyurethane acrylate monomers according to the invention are, for example, hexafunctional Ebecryl 1290, Ebecryl 8254, difunctional Ebecryl 8402 or non-functional Ebecryl 8602 supplied by Allnex.

[0097] The present invention is also directed to a curable composition obtainable by curing a curable composition according to the present invention as described in the above embodiments.

[0098] According to the present invention, the cured composition can be obtained by any curing means suitable for curing the curable composition according to the present invention, which may require mixing the curable composition with a chemical curing agent. Thus, the cured composition according to the present invention can be obtained by curing induced by electron beam irradiation, induced by light irradiation, induced by heating, or induced by mixing with a curing agent including moisture, sulfur, organic peroxides and other radical initiators.

[0099] Preferably, the cured composition is obtained by photocuring, i.e. the curing of the curable composition is induced by light irradiation, or the cured composition is obtained by thermal curing, i.e. the curing is induced by heating. More preferably, the cured composition is obtained by photocuring, in particular by UV curing.

[0100] In a preferred embodiment according to the present invention, the cured composition as described in any of the above embodiments is obtained as a primer coating, hard coat or top coat on a solid substrate.

[0101] The curable composition according to the present invention is applied to the surface of a solid substrate as a coating or hard coat, thus producing a coated solid substrate having improved resistance to abrasion and especially to ultraviolet light. Such coated solid substrates are often referred to as weather-resistant substrates. Furthermore, there is no limitation as to the thickness of the hard coat applied to said solid substrate. However, they are often about 0.5 to about 50 μm thick, preferably about 3 to about 20 μm thick.

[0102] Solid substrates that can be used generally include polymeric substrates such as acrylic polymers including poly(methyl methacrylate), polyesters such as poly(ethylene terephthalate) and poly(butylene terephthalate), polyamides, polyimides, acrylonitrile-styrene copolymers, styrene-acrylonitrile-butadiene copolymers, polyvinyl chloride, polystyrene, blends of polystyrene and polyphenylene ether, butyrate, polyethylene, and the like. Additionally, said solid substrates may also include metal substrates, painted surfaces, glass, ceramics, and textiles. Thermoplastic substrates may be pigmented or unpigmented.

[0103] However, the curable composition of the present invention is preferably used to coat polycarbonates. The polycarbonates (homopolycarbonates or copolycarbonates) used in the present invention can be prepared by reacting bisphenols with a carbonic acid source such as phosgene or dimethyl carbonate using conventional techniques. These include melt polymerization, interfacial polymerization, and interfacial conversion with bischloroformates followed by polymerization. Chain terminators such as phenols can also be used.

[0104] The curable compositions according to the present invention can be applied to solid substrates such as polycarbonate by conventional techniques including dipping, brushing, roller coating, flow coating or digital ink jet printing.

[0105] After application, the curable compositions are cured by exposure to an ultraviolet light source, such as a medium or high pressure Hg lamp having a power of 80 W / cm to 40 W / cm.

[0106] The present invention also provides A) at least one compound of formula (1), where R is C1-C10 alkyl, and R 1 -R 10 are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, with the proviso that R 1 -R 10 is C1-C10 alkyl, and wherein the residue R 1 -R 5 and R 6 -R 10 The substitution patterns formed by B) at least one compound of formula (1), where R is C-C alkyl and R 1 -R 10 are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, where the residue R 1 -R 5 and R 6 -R 10The substitution pattern formed by The present invention relates to a mixture of compounds comprising:

[0107] Generally preferred is when the mixture of compounds according to the invention comprises a mixture of 2-alkyldiaroylresorcinols according to formula (1), where R and R 1 -R 10 can be C1-C10 alkyl or hydrogen, which is obtained from the Lewis acid catalyzed reaction of 2-alkylresorcinol with two different halogenated aryl oils (AX and BX, A and B represent different aroyl moieties, and X represents a halide residue), in which AX and BX are both alkylated aroyl halides or one of AX and BX is a benzoyl halide. Preferably, when the molar amount of 2-alkylresorcinol resulting from the above reaction having one aryl oil substituent A and B ("AB"), respectively, is set to 2, the value of 2-alkylresorcinol having the combination of substituents AA and BB in the molar ratio AA:AB:BB found in the mixture according to the present invention ranges from about 0.1 to about 2.5, more preferably from about 0.2 to about 2, even more preferably from about 0.5 to about 1.5, and most preferably from about 0.75 to about 1.25, where the values ​​of the molar amounts of AA and BB are independent of each other.

[0108] The relative amounts of 2-alkylresorcinols having aryloyl substitution patterns AA, AB and BB, e.g. DCMR, BTMR and DTMR, present in the mixtures according to the invention are 1 H-NMR or 13 C-NMR, optionally using an internal standard as a reference. Such procedures are known to those skilled in the art.

[0109] The reaction leading to the acylresorcinol-based mixture according to the present invention is preferably carried out in the presence of a Lewis acid catalyst.

[0110] According to the present invention, any Lewis acid, ie, any chemical species that contains a vacant orbital that can accept an electron pair from a Lewis base to form a Lewis adduct, is considered a Lewis acid catalyst according to the present invention.

[0111] Preferred Lewis acid catalysts are aluminum halides such as aluminum chloride, boron halides such as boron trifluoride, bismuth triflate, zinc halides. ZnCl2 is a particularly preferred Lewis acid catalyst.

[0112] In a preferred embodiment according to the present invention, the curable composition defined in the above embodiment comprises a mixture obtained as in the preceding embodiment comprising 2-alkylresorcinols having substitution patterns AA and BB, with the proviso that the molar amount of the 2-alkylresorcinols also present with substitution pattern AB is set to 2, their molar amount preferably ranging from about 0.1 to about 2.5, more preferably ranging from about 0.2 to about 2, even more preferably ranging from about 0.5 to about 1.5, most preferably ranging from about 0.75 to about 1.25, wherein the values ​​of the resorcinols with substitution pattern AA and the resorcinols with substitution pattern BB are independent of each other.

[0113] In a further preferred embodiment, the present invention comprises: A) at least one compound of formula (1), where R is C1-C10 alkyl, and R 1 -R 10 are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, with the proviso that R 1 -R 10 is alkyl, and wherein the residue R 1 -R 5 and R 6 -R 10 The substitution patterns formed by B) at least one compound of formula (3) [ka] Here, R 14 is C1-C10 alkyl, preferably methyl, and -C) preferably at least one further compound of formula (1), where R is C1-C10 alkyl and R 1 -R 10 are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, where the residue R 1 -R 5 and R 6 -R 10 The substitution pattern formed by 1 -R 10 At least two groups are C1-C10 alkyl; The present invention relates to a mixture comprising:

[0114] Generally preferably, in the mixtures according to the present invention, the molar ratio of compounds according to formula (1), especially formula (3), having the same substitution pattern at each aroyl group to compounds according to formula (1) having different substitution patterns at each aroyl group is in the range of from about 90:10 to about 90:10, more preferably in the range of from about 75:25 to about 25:75, even more preferably in the range of from about 60:40 to about 40:60, and most preferably in the range of from about 55:45 to about 45:55.

[0115] The preferred mixture according to the present invention is obtained in a one-step synthesis reaction by mixing a mixture of 1 equivalent of 2-methylresorcinol, 1 equivalent of benzoyl chloride and 1 equivalent of toluoyl chloride in the presence of zinc dichloride (ZnCl2). The above one-step synthesis reaction can be represented as follows: [ka] In the reaction shown above, esterification of the OH group of 2-methylresorcinol with the chloroacyl groups of benzoyl chloride and toluoyl chloride, followed by a Lewis acid catalyzed Fries rearrangement, allows for the preparation of acylphenols.

[0116] The above one-step synthesis reaction according to the present invention results in the formation of three products: Dibenzoyl acyl-2-methylresorcinol (DBMR) [ka] Benzoyltoluoylacyl-2-methylresorcinol (BTMR) [ka] and Ditoluoylacyl-2-methylresorcinol (DTMR) [ka]

[0117] The acylresorcinol-based mixture according to the invention thus obtained has a molar ratio of DBMR:BTMR:DTMR of 1:2:1.

[0118] This mixture is a particularly preferred mixture of the compounds according to the invention.

[0119] In general, the term "BTMR" herein applies to benzoyltoluoyl 2-methylresorcinol as a single compound, whereas the term "BTMR mixture" or "BTMR mixture" applies to mixtures of BBMR, BTMR and DTMR, particularly mixtures in which BTMR is the major component in terms of the molar ratio of the three components.

[0120] Depending on the reaction conditions selected, especially when the crude product is purified by recrystallization, the molar ratio of DBMR:BTMR:DTMR in the purified product may deviate from the expected 1:2:1 molar ratio.

[0121] Thus, when the molar amount of BTMR is set to 2, the amount of DBMR and DTMR in the ratio DBMR:BTMR:DTMR in the mixture according to the invention is preferably from 0.1 to 2.5, more preferably from 0.2 to 2, even more preferably from 0.5 to 1.5, and most preferably from 0.75 to 1.25, where the value of DBMR and the value of DTMR are independent of each other.

[0122] By using a mixture of resorcinol derivatives, the solubility of this mixture in alcoholic solvents is significantly increased compared to pure resorcinol, e.g. pure DBR, DBMR or DTMR, and compared to the ternary mixtures.

[0123] Consequently, in a preferred embodiment according to the present invention, the curable composition defined in the above embodiment comprises a mixture thus obtained containing DBMR and DTMR, with the proviso that the molar amount of DBMR and DTMR, set to 2, is preferably in the range of 0.1 to 2.5, more preferably in the range of 0.2 to 2, even more preferably in the range of 0.5 to 1.5, and most preferably in the range of 0.75 to 1.25, wherein the value of DBMR and the value of DTMR are independent of each other.

[0124] The above procedure for obtaining such a mixture of DBMR, BTMR and DTMR, which gives rise to a statistical mixture of two symmetrical addition products and one asymmetrical derivative, in a one-step synthesis starting from a mixture of 2-methylresorcinol and benzoyl and toluoyl chlorides, can be used to obtain a single compound of formula (1), where R is C1-C10 alkyl and R 1 -R 10 are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, with the proviso that R 1 -R 10 is alkyl, and wherein the residue R 1 -R 5 and R 6 -R 10The substitution patterns formed by are different from each other, and two different compounds of formula (1), where R is C1-C10 alkyl and R 1 -R 10 are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, where the residue R 1 -R 5 and R 6 -R 10 The above-mentioned general procedure for obtaining a mixture according to the invention is illustrated, in which the substitution pattern formed by the above-mentioned 2-(C1-C10-alkyl)-resorcinols is the same. 1 -R 5 and one type of halogenated aroyl having the substituent R defined above. 6 -R 10 can be obtained by carrying out a reaction with another type of halogenated aryl oil having the formula:

[0125] In this way, one compound of formula (3), where R 14 is C1-C10 alkyl, and two compounds of formula (2), wherein in one compound of formula (2), R 11 and R 12 is C1-C10 alkyl and the other group is hydrogen, and in other compounds of formula (2), R 11 and R 12 and are both C1-C10 alkyl groups, which are preferred mixtures according to the invention.

[0126] Here, R 11 and R 12 It is preferred that the groups, if they are C1-C10 alkyl groups, are C1-C10 alkyl groups of the same type. More preferably, R 14 The group may also be a C1-C10 alkyl group of the same type, or R 14 is R 11 and R 12 and independently are methyl groups.

[0127] In a highly preferred embodiment according to the present invention, Dibenzoylacyl-2-methylresorcinol (DBMR) [ka] Benzoyltoluoylacyl-2-methylresorcinol (BTMR) [ka] and ditoluoylacyl-2-methylresorcinol (DTMR), [ka] Preferably, the molar amount of each of DBMR and DTMR relative to the molar amount of BTMR set to 2 is independently preferably in the range of 0.1 to 2.5, more preferably 0.2 to 2, even more preferably 0.5 to 1.5, and most preferably 0.75 to 1.25; The present invention relates to a mixture comprising:

[0128] In an even more preferred embodiment according to the present invention, the invention relates to a mixture consisting of DBMR, BTMR, and DTMR, wherein the molar amount of each of DBMR and DTMR relative to the molar amount of BTMR set to 2, independently, is preferably in the range of from 0.1 to 2.5, more preferably from 0.2 to 2, even more preferably from 0.5 to 1.5, and most preferably from 0.75 to 1.25.

[0129] The present invention also relates to the use of any of the compounds as described in the above embodiments according to the present invention, or any of the mixtures of compounds as described in the above embodiments according to the present invention, as a UV stabilizer in a curable composition.

[0130] The use of such compounds or mixtures of compounds in the curable compositions according to the invention can help to improve the long-term stability of the coating, especially under outdoor conditions, because, unlike the prior art UV absorber SDBR, higher concentrations of compounds and mixtures as described present in the curable compositions according to the invention are accepted by the coating system without compromising the mar and adhesion properties, improving weathering conditions especially at lower coating thicknesses.

[0131] The present invention further relates to a method for making a curable composition containing the resorcinol-based UV stabilizer as described above.

[0132] In a preferred embodiment according to the present invention, a method for the preparation of a curable composition according to any of the above embodiments is provided, the method comprising: I) one or more compounds of formula (1) [ka] where R is C1-C10 alkyl, R 1 -R 10 are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, with the proviso that R 1 -R 10 is C1-C10 alkyl, and wherein the residue R 1 -R 5 and R 6 -R 10 The substitution patterns formed by and optionally one or more compounds of general formula (1), where R is C1-C10 alkyl, R 1 -R 10 are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, and wherein the residue R 1 -R 5 and R 6 -R 10 The substitution pattern formed by providing a UV stabilizing composition consisting of: II) adding the UV stabilizing component provided in step I) to a) one or more curable organic monomers, curable organic polymers, or curable mixtures of organic monomers and organic polymers; and b) optionally one or more photoinitiators; c) optionally one or more light stabilizers; d) optionally one or more silica compounds; e) optionally one or more solvents; f) optionally one or more additives such as leveling agents, surfactants and surface active compounds, curing catalysts, dyes and colorants; and mixing the composition with composition-forming ingredients comprising:

[0133] In a further preferred embodiment according to the invention, in the process according to the invention, at least one compound of formula (1) is represented by formula (2): [ka] Here, R 13 is C1-C10 alkyl, R 11 and R 12 is selected from hydrogen and C1-C10 alkyl, where R 11 and R 12 At least one of R is C1-C10 alkyl; 11 and R 12 are different from each other, Preferably here R 13 is methyl, R 11 and R 12 is selected from hydrogen and methyl.

[0134] In a further preferred embodiment according to the present invention, a method for producing a curable composition is provided, wherein the UV stabilizing component comprises one or more compounds of formula (2): [ka] Here, R 13 is C1-C10 alkyl, R 11 and R 12 is selected from hydrogen and C1-C10 alkyl, where R 11 and R 12 At least one of R is C1-C10 alkyl; 11 and R 12 are different from each other, one or more compounds of formula (2), where R 13 is C1-C10 alkyl, R 11 and R 12 is selected from C1-C10 alkyl, where R 11 and R 12 are the same, preferably methyl; and one or more compounds of formula (3) [ka] Here, R 14 is C1-C10 alkyl, preferably methyl; It is composed of a mixture of

[0135] In a highly preferred embodiment according to the invention, in the method of preparation of the curable composition according to the invention, the UV stabilizing component is dibenzoyl acyl-2-methylresorcinol (DBMR), [ka] Benzoyltoluoylacyl-2-methylresorcinol (BTMR), [ka] and ditoluoylacyl-2-methylresorcinol (DTMR) [ka] Preferably, the molar amount of each of DBMR and DTMR relative to the molar amount of BTMR set to 2 is independently preferably in the range of 0.1 to 2.5, more preferably 0.2 to 2, even more preferably 0.5 to 1.5, and most preferably 0.75 to 1.25; It is composed of a mixture of

[0136] In another preferred embodiment according to the invention, in the method according to the invention, the UV stabilizing component is provided by the reaction of 2-(C1-C10 alkyl)resorcinol with at least two different aroyl halides of general structure (4), [ka] Where X=Cl, Br And R 15 are each independently selected from hydrogen or C1-C10 alkyl, optionally followed by a purification step, preferably followed by recrystallization.

[0137] Preferably, therein, two halogenated aryl oils of general structure (4) are reacted with a 2-(C1-C10 alkyl)resorcinol, where each R 15 is a hydrogen atom of the first halogenated aryl oil, and one R of the second aryl oil 15 is C1-C10 alkyl, preferably methyl, and the remaining R of the second halogenated aryl oil 15 The group is hydrogen.

[0138] In another preferred embodiment according to the present invention, in the method of the present invention, the UV stabilizing component is comprised of about 1 to about 15 wt. %, preferably about 1 to about 9 wt. %, more preferably about 2 to about 7 wt. % of a resorcinol-based UV absorber according to the present invention, and the composition forming component is a) about 27 to 60% by weight of one or more curable organic monomers, curable organic polymers, or curable mixtures of organic monomers and organic polymers, preferably about 27 to about 60% by weight of an acrylate monomer, more preferably about 25 to about 50% by weight of an aliphatic urethane polyacrylate and about 1 to 10% by weight of a low viscosity aliphatic di- and triacrylate (e.g., HDDA), and most preferably about 30 to about 40% by weight of an aliphatic urethane polyacrylate and about 2 to about 6% by weight of a low viscosity aliphatic di- and triacrylate (e.g., HDDA); b) 0 to about 5 wt. %, preferably about 1 to 4 wt. %, more preferably about 1 to about 2.5 wt. % of one or more photoinitiators; c) 0 to about 2% by weight, preferably about 0.2 to about 0.8% by weight, of one or more additional light stabilizers; d) 0 to about 10% by weight, preferably about 2 to about 8% by weight, more preferably about 2 to about 5% by weight of one or more silica compounds; e) 0 to about 80% by weight, preferably 20 to about 80% by weight, more preferably about 32 to about 70% by weight, more preferably about 35 to about 60% by weight of one or more solvents; f) less than 5% by weight, preferably less than 2% by weight, more preferably less than 1% by weight, of one or more further additives such as leveling agents, surfactants and surface-active compounds and curing catalysts, dyes and colorants, The weight percentages of the UV stabilizing components and composition forming components elements herein add up to 100%, based on the total weight of the composition.

[0139] According to the present invention, the above UV stabilizing compounds and their mixtures are used by incorporating them into curable compositions and cured silicone compound-containing compositions. The compositions containing the above UV stabilizing compounds and their mixtures are coating compositions defined as hard coats or top coats.

[0140] Preferably, the UV stabilizing compound or mixture thereof according to the present invention as described above is incorporated into a UV curable acrylic coating composition. The coating composition is defined as a coating comprising the UV stabilizing compound or mixture thereof and a substantially transparent matrix composition. Generally, the matrix material comprises acrylic, urethane, melamine, or mixture thereof. U.S. Patent Application Serial No. 08 / 69,254, which is incorporated herein by reference, also describes a coating composition.

[0141] The following examples illustrate the preparation of UV stabilizer compounds according to the present invention and their application in the preparation of curable and cured compositions. EXAMPLES

[0142] The "BTMR mixture" according to the present invention can be obtained in a one-step synthesis reaction by mixing 1 equivalent of 2-methylresorcinol with a mixture of 1 equivalent of benzoyl chloride and 1 equivalent of toluoyl chloride in the presence of zinc dichloride (ZnCl2), as described in Example 1. The above one-step synthesis reaction can be represented as follows: [ka]

[0143] As shown above, the BTMR mixture is expected to have a molar ratio of DBMR to BTMR to DTMR of 1:2:1. Results may vary from this ideal ratio depending on the reaction and work-up conditions selected.

[0144] Example 1 - Synthesis of BTMR-based mixtures Into a 1 liter 3-neck flask equipped with a KPG stirrer, a dropping funnel, a condenser with a solvent trap (Bartlett trap) and a dry nitrogen line, 90 ml of technical toluene was introduced along with 38.3 g (308 mmol) of 2-methylresorcinol. Under an inert atmosphere, the mixture was heated to 90°C in a heating mantle. The funnel was equipped with a mixture of 45.5 g (324 mmol) of benzoyl chloride and 50.0 g (324 mmol) of m-toluoyl chloride. The chloride mixture was added slowly to maintain a gentle evolution of HCl gas. After the mixture was completely added and gas formation had ceased, the reaction mixture was allowed to cool to room temperature.

[0145] Into the second reaction flask, 6.3 g (46.2 mmol) of zinc chloride was introduced. The reaction mixture of the first flask was transferred before the reaction flask was heated to 150° C. The solvent was removed under vacuum (about 40 mbar) and collected in a solvent trap. After the solvent was removed, the mixture was heated to 150° C. for 2 hours. The reaction mixture was then cooled to 80° C. before 100 ml of toluene was added.

[0146] The warm solution was washed with HCl solution (1 wt%) followed by two washes with saturated NaCl solution. The organic layer was poured into 1 L of methanol. The mixture was cooled in an ice bath before filtering the precipitate that formed and rinsing with additional methanol to give 75 g of a reddish solid.

[0147] The crude product was recrystallized from 2-butanol to give 76 g (72%) of a BTMR-based mixture consisting of DBMR:BTMR:DTMR with a molar ratio of 22:52:26 (i.e., 0.85:2:1).

[0148] Preparation of test panels To investigate the adhesion, scratch resistance, or weatherability of coated polycarbonate (PC), test panels were prepared according to the following procedure. [Table 1A] [Table 1B] Step A): Formulation AH was formulated according to Table 1 in an opaque PP (polypropylene) bottle. The bottle was shaken to mix the ingredients. The formulation was stored at room temperature. Step B): The coating was applied by flow coating to a PC panel (Makrolon AL2647; 25x10cm 2 ;Thickness 3.2mm). Step C): Flash off at ambient temperature for 2 minutes. Step D): The coated parts were transferred to a convection oven and kept at 75°C for 5 minutes. Step E): After removal from the oven, the panel is directly transferred to a UV conveyor belt (UV conveyor belt: IST-Metz; 1 undoped medium pressure Hg-Lamp; 120W / cm), requirement: low energy (3J / cm 2 @200mW / cm 2 UVA EIT) or high energy (5J / cm 2 @300mW / cm 2 UVA EIT ) where the surface power density was determined by EIT's UV PowerPuck II (UVA range: 320-390 nm).

[0149] Xenon Weathering For xenon weathering testing, a Q-Sun instrument from Q-Lab was used. The established procedure for sample processing and parameter settings for the xenon instrument is shown in the following table. [Table 2] [Table 3]

[0150] Performance of BTMR-based mixtures in Example 1 The performance of UV hardcoats based on curable compositions according to the invention using UV stabilizers such as BTMR-based mixtures compared to UV hardcoats using the standard UV absorber 4,6-dibenzoyl-2-(3-triethoxysilylpropyl)resorcinol (SDBR) is described with a focus on adhesion, scratch resistance, and weatherability. Additionally, the dissolution properties of BTMR and mixtures of BTMR are presented.

[0151] Example 2 - Scratch and abrasion resistance UV-cured hardcoats were used to investigate the dependence of UV absorber concentration on the scratch and abrasion resistance of the coating system.

[0152] Equimolar amounts of both UV absorbers, SDBR and BTMR mixtures, were used for the analysis. Standard concentrations and double amounts of each UV absorber were used. Coated samples prepared from the various formulations were cured at low and high UV energy to further investigate the dependence of performance on this parameter. [Table 4]

[0153] The results obtained are generally better for samples cured with higher UV energy. At the same energy and concentration levels, the steel wool resistance observed is better for the BTMR mixture of Example 1 (DBMR to BTMR to DTMR molar ratio 0.85:2:1) compared to SDBR. Similar results were obtained in the Taber abrasion test. SDBR shows a significant increase in Δ-haze values ​​with increasing concentration of UVA, while the coating with the BTMR mixture of Example 1 does not show this effect. An increase in the SDBR concentration of the UV coating was found to affect the scratch resistance and the Taber abrasion resistance, while in the case of the BTMR mixture of Example 1, this effect was only observed in the scratch test with steel wool.

[0154] Example 3 - Gluing The adhesion of two different UV hardcoat families was tested depending on the nature and concentration of the UV absorber used in the formulation. Both coating families (Formulations AD and EH) using different concentrations of UV absorber (SDBR vs. BTMR mixture of Example 1 ((molar ratio DBMR:BTMR:DTMR 0.85:2:1) at 100% and 200% concentrations) were applied to polycarbonate panels by flow coating. The cured samples were tested according to automotive adhesion testing requirements using the Ford M80J6 specification for water immersion resistance (section 3.7.7) and the PSA D47 1309 specification for weather cycle resistance.

[0155] The water immersion adhesion of UV hardcoat formulations A, B, C, and D was tested using a tape pull test after immersing the test panels in water for 10 days at 60°C. The Karcher adhesion after 5CF climate cycles (5 cycles in a climate chamber: (85°C, 95% relative humidity, 15 hours); (-20°C, 3 hours); (85°C, dry, 6 hours)) was measured on parts coated with formulations E, F, G, and H, respectively. The results of both test series are shown in Tables 5 and 6. [Table 5] [Table 6]

[0156] Comparing the adhesion of Formulation F to Formulation H at 200 wt %, it can be seen that the adhesion is strong even without doubling the UV absorber content, and there is no detrimental effect on the concentration of UV absorber in the coating.

[0157] Example 4 - Xenon Weathering Xenon weathering tests with PV3930 (Volkswagen Florida Simulation) and PV3929 (Volkswagen Kalahari Simulation) on polycarbonate panels coated with formulation F (100% BTMR blend (Example 1) concentration), formulation H (200% BTMR blend concentration) and two intermediate concentrations, 120% and 150% BTMR blend UV absorber, under standard coating conditions and in the coating thickness range of 10-12 μm, showed no significant differences in weathering resistance. The occurrence of μ-cracks, adhesion, haze, etc. is similar for all coatings, regardless of the concentration of UV absorber.

[0158] Different results were obtained for lower coating thicknesses. For layer thicknesses of about 6 μm, a significant dependence of yellowing and adhesion performance was observed for PV3929 xenon weathering. Higher UV absorber concentrations help to reduce the tendency to yellowing and adhesion loss. The results are summarized in Tables 7 and 8. [Table 7] [Table 8]

[0159] Example 5 - Solubility of BTMR Product Mixtures Solubility Test To determine the solubility of the resorcinol products, the following procedure was used.

[0160] material Preparation of BTMR-based 0.9:1:1 mixture: 8.38 g of "BTMR mixture" synthesized as in Example 1 (molar ratio of BBMR:BTMR:DTMR 0:85:2:1, i.e., a mixture of 5.32 mmol DBMR, 12.52 mmol BTMR, 6.26 mmol DTMR); 2.00 g (6.05 mmol) DBMR; 2.17 g (6.05 mmol) DTMR were diluted with 50 ml 1-methoxy-2-propanol at 60°C. Afterwards, the solvent was evaporated again in vacuum. The remaining precipitate was mechanically mixed to obtain a dry powder.

[0161] procedure 0.50 g of the pre-dried product (45 min in oven at 75° C.) was combined with 5.00 ml of solvent (4.03 g of 2-butanol or 4.60 g of 1-methoxy-2-propanol). The mixture was treated in an ultrasonic bath for 1 min and then stored in a constant climate (20° C.) for 24 h.

[0162] The upper solution was carefully transferred with a pipette. The solids content of this solution was measured thermogravimetrically using a halogen moisture balance (Mettler Toledo). This test procedure was repeated three times. [Table 9] [Table 10]

[0163] The solubilities of various BTMR mixtures were compared to the solubilities of the single components of the mixtures, as shown in Table 11. [Table 11]

[0164] Both the 0.85:2:1 and 0.9:1:1 mixtures of DBMR, BTMR, and DTMR were found to exhibit improved solubility over the symmetric pure dibenzoyl DBMR and pure bitoloylic derivative DTMR. The 1:2:1 mixture DBMR, BTMR, and DTMR as in Example 1 exhibits the highest solubility, likely due to the increased amount of pure BTMR product in this mixture.

[0165] High concentrations of the prior art UV absorber SDBR in coating formulations reduce the scratch resistance of the coating, whereas with BTMR or BTMR-based mixtures the coating properties are not as adversely affected.

[0166] The good solubility of BTMR and BTMR-based blends allows for high loadings in coating formulations without compromising mar and adhesion properties, which helps improve weatherability at low coating thicknesses.

Claims

1. A curable composition comprising at least one compound of formula (1), 【Chemistry 1】 where R is C1-C10 alkyl and R １ -R １０ are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, １ -R １０ is C1-C10 alkyl, and wherein the residue R １ -R ５ and R ６ -R １０ The substitution patterns formed by the curable compositions are different from each other.

2. R is methyl and R １ -R １０ are each independently selected from the group consisting of hydrogen and methyl, with the proviso that R １ -R １０ The curable composition of claim 1 , with the proviso that at least one of is methyl.

3. At least one compound of formula (1) is represented by formula (2): 【Chemistry 2】 Here, R １３ is C1-C10 alkyl, and R １１ and R １２ is selected from hydrogen and C1-C10 alkyl, where R １１ and R １２ At least one of is C1-C10 alkyl, and R １１ and R １２ The curable composition of claim 1 , with the proviso that:

4. R １３ is methyl, and R １１ and R １２ is selected from hydrogen and methyl, where R １１ and R １２ The curable composition of claim 3, with the proviso that at least one of is methyl.

5. At least one compound of formula (3) 【Chemistry 3】 Here, R １４ is C1-C10 alkyl; The curable composition of claim 1 , further comprising:

6. At least one compound of formula (2) 【Chemistry 4】 Here, R １３ is C1-C10 alkyl, and R １１ and R １２ is selected from hydrogen and C1-C10 alkyl, where R １１ and R １２ At least one of is C1-C10 alkyl, and R １１ and R １２ are different from each other. and at least one compound of formula (3) 【Chemistry 5】 Here, R １４ is C1-C10 alkyl; The curable composition of claim 1 , comprising a mixture containing:

7. R １３ and R １４ The curable composition of claim 6 , wherein is methyl.

8. R １３ and R １４ is methyl, and R １１ is hydrogen, and R １２ The curable composition according to claim 6 or 7, wherein is methyl.

9. R is C1-C10 alkyl; R １ -R １０ are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, １ -R １０ At least two groups are C1-C10 alkyl groups, and the residue R １ -R ５ and R ６ -R １０ 9. The curable composition of claim 1, further comprising at least one compound of formula (1), with the proviso that the substitution pattern formed by

10. Further compounds of formula (1) include R １３ is C1-C10 alkyl, and R １１ and R １２ is selected from C1-C10 alkyl, where R １１ and R １２ The condition is that the formula (2) is the same. 【Chemistry 6】 The curable composition of claim 9, wherein the compound is

11. The composition comprises dibenzoyl acyl-2-methylresorcinol (DBMR). 【Chemistry 7】 Benzoyltoluoylacyl-2-methylresorcinol (BTMR) 【Chemistry 8】 and ditoluoylacyl-2-methylresorcinol (DTMR) 【Chemistry 9】 Including, 11. The curable composition of claim 1, wherein the molar amount of each of DBMR and DTMR relative to the molar amount of BTMR set at 2 is independently in the range of 0.1 to 2.

5.

12. The curable composition of claim 1 which is a photocurable or heat curable composition.

13. The curable composition of claim 1 which is a polymerizable composition.

14. 14. The curable composition of claim 1, further comprising at least one curable monomer.

15. 15. The curable composition of any of claims 1 to 14, further comprising at least one curable acrylate monomer.

16. 16. The curable composition of any of claims 1 to 15, further comprising at least one curable aliphatic polyurethane acrylate monomer.

17. A cured composition obtainable by curing the curable composition of any one of claims 1 to 16.

18. A) Formula (1) 【Chemistry 10】 where R is C1-C10 alkyl and R １ -R １０ are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, １ -R １０ is C1-C10 alkyl, and wherein the residue R １ -R ５ and R ６ -R １０ The substitution patterns formed by B) at least one compound of formula (1), where R is C1-C10 alkyl, and R １ -R １０ are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, and wherein the residue R １ -R ５ and R ６ -R １０ The substitution pattern formed by A mixture comprising:

19. A) at least one compound of formula (1), where R is C1-C10 alkyl, and R １ -R １０ are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, １ -R １０ is C1-C10 alkyl, and wherein the residue R １ -R ５ and R ６ -R １０ The substitution patterns formed by B) at least one compound of formula (3) 【Chemistry 11】 Here, R １４ is C1-C10 alkyl, and at least one further compound of formula (1), where R is C1-C10 alkyl, and R １ -R １０ are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, where the residue R １ -R ５ and R ６ -R １０ The substitution pattern formed by R １ -R １０ At least two groups are C1-C10 alkyl; 20. The mixture of claim 18, comprising:

20. The mixture is dibenzoyl acyl-2-methylresorcinol (DBMR) 【Chemistry 12】 Benzoyltoluoylacyl-2-methylresorcinol (BTMR) 【Chemistry 13】 and ditoluoylacyl-2-methylresorcinol (DTMR) 【Chemistry 14】 Including, the molar amount of each of DBMR and DTMR relative to the molar amount of BTMR set at 2 is independently in the range of 0.1 to 2.5; 20. The mixture according to claim 18 or 19.

21. 21. Use of a compound as defined in any one of claims 1 to 16 or a mixture as defined in any one of claims 18 to 20 as a UV stabilizer in a curable composition.

22. A method for the preparation of a curable composition according to any one of claims 1 to 16, comprising the steps of: I) One or more compounds of formula (1) 【Chemistry 15】 where R is C1-C10 alkyl and R １ -R １０ are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, １ -R １０ is C1-C10 alkyl, and wherein the residue R １ -R ５ and R ６ -R １０ The substitution patterns formed by and optionally one or more compounds of general formula (1), where R is C1-C10 alkyl, and R １ -R １０ are each independently selected from the group consisting of hydrogen and C1-C10 alkyl, and wherein the residue R １ -R ５ and R ６ -R １０ The substitution pattern formed by providing a UV stabilizing component consisting of II) adding the UV stabilizing component provided in step I) to a) one or more curable organic monomers, curable organic polymers, or curable mixtures of organic monomers and organic polymers; and b) Optionally, one or more photoinitiators c) optionally one or more light stabilizers d) optionally one or more silica compounds e) Optionally, one or more solvents f) optionally one or more further additives selected from leveling agents, surfactants and surface-active compounds, curing catalysts, dyes and colorants; mixing with a composition-forming component comprising A method comprising the steps of:

23. At least one compound of formula (1) is represented by formula (2): 【Chemistry 16】 Here, R １３ is C1-C10 alkyl, and R １１ and R １２ is selected from hydrogen and C1-C10 alkyl, where R １１ and R １２ At least one of is C1-C10 alkyl, and R １１ and R １２ are different from each other.

23. The method of claim 22.

24. The UV stabilizing component is one or more compounds of formula (2): 【Chemistry 17】 Here, R １３ is C1-C10 alkyl, and R １１ and R １２ is selected from hydrogen and C1-C10 alkyl, where R １１ and R １２ At least one of is C1-C10 alkyl, and R １１ and R １２ are different from each other, One or more compounds of formula (2), where R １３ is C1-C10 alkyl, and R １１ and R １２ is selected from C1-C10 alkyl, where R １１ and R １２ are the same, and one or more compounds of formula (3) 【Chemistry 18】 Here, R １４ is C1-C10 alkyl; Composed of a mixture of 24. The method of claim 22 or 23.

25. The UV stabilizing ingredient is dibenzoyl acyl-2-methylresorcinol (DBMR). 【Chemistry 19】 Benzoyltoluoylacyl-2-methylresorcinol (BTMR) 【Chemistry 20】 and ditoluoylacyl-2-methylresorcinol (DTMR) 【Chemistry 21】 It consists of a mixture of the molar amount of each of DBMR and DTMR relative to the molar amount of BTMR set at 2 is independently in the range of 0.1 to 2.5; 25. The method of any one of claims 22 to 24.

26. The UV stabilizing component is provided by the reaction of a 2-(C1-C10 alkyl)resorcinol with at least two different aroyl halides of general structure (4): 【Chemical 22】 Where X = Cl, Br And R １５ are each independently selected from hydrogen or C1-C10 alkyl, optionally followed by a purification step; 26. The method of any one of claims 22 to 25.

27. Two halogenated aryl oils of general structure (4) are reacted with a 2-(C1-C10 alkyl)resorcinol, where each R １５ is a hydrogen atom of the first halogenated aryl oil, and one R of the second aryl oil １５ is C1-C10 alkyl, and the remaining R of the second halogenated aryl oil １５ 27. The method of any one of claims 22 to 26, wherein the group is hydrogen.

28. The UV stabilizing component is comprised of 1 to 15% by weight of a resorcinol-based UV absorber according to the present invention, and the composition forming components are a) 27 to 60 wt. % of one or more curable organic monomers, curable organic polymers, or curable mixtures of organic monomers and organic polymers; b) 0 to 5 wt. % of one or more photoinitiators; c) 0 to 2% by weight of one or more further light stabilizers, d) 0 to 10 wt. % of one or more silica compounds; e) 0 to 80% by weight of one or more solvents; f) less than 5% by weight of one or more further additives selected from leveling agents, surfactants and surface-active compounds, curing catalysts, dyes and colorants; wherein the weight percentages of the UV stabilizing component and composition forming component elements add up to 100%, based on the total weight of the composition.

28. The method of any one of claims 22 to 27.

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