Method for forming a matte coating

Abstract

The present invention relates to a method for coating a surface, comprising the steps of applying a layer of a curable composition to the surface, irradiating the curable composition with a first radiation having a wavelength of 100 to 280 nm to obtain a partially cured composition, and irradiating the partially cured composition with a second radiation having at least one wavelength longer than the wavelength of the first radiation and / or an electron beam to obtain a cured composition, wherein the curable composition comprises at least one compound curable by actinic radiation and at least one polyamide particle. The present invention also relates to a coating layer obtained by such a method, and to an object comprising a surface covered with such a coating layer.

Description

[Technical Field]

[0001] The present invention relates to a method for coating a surface based on a curable composition that produces a matte appearance, and to the coatings obtained by such a method. [Background technology]

[0002] Actinically curable or crosslinkable compositions are commonly used to form coatings on surfaces, particularly because they eliminate the need for solvents and allow for rapid crosslinking.

[0003] In certain applications, a matte coating is desirable. "Matte coating" refers to a coating that has a specular gloss at 85° of less than 15 GU.

[0004] One known option for obtaining such a matte coating is to add a matting agent to the curable composition in an amount sufficient to cause some of the matting agent to appear at the surface of the coating, thereby creating roughness on the surface. Alternatively, matte can be obtained without the use of a matting agent by irradiating the coating composition with successive radiations of different wavelengths to first crosslink only a very low thickness at the surface of the coating layer, creating folds, and then crosslinking the remainder of the layer in a second step.

[0005] However, this latter technique typically results in a non-uniform surface roughness due to alternating wrinkled and non-wrinkled regions or fan-shaped wrinkle orientation. The resulting coating exhibits a non-uniform appearance, including matte and glossy regions, distorting the coating's appearance. Furthermore, these non-uniform coatings exhibit poor stain resistance because the fan-shaped wrinkled regions retain dirt and grime.

[0006] US Patent Application Publication No. 2014 / 0371384 documents a method for matting a surface, which includes three irradiation steps to crosslink a coating applied to a substrate.

[0007] US Patent Application Publication No. 2016 / 0145449 is a document describing a photocrosslinkable composition comprising a crosslinkable component, a filler, a UV stabilizer, a photoinitiator, and a component selected from a non-swelling filler and a swellable or soluble polymer.

[0008] US Patent Application Publication No. 2020 / 0024439 documents a crosslinked product produced by subjecting an acrylic composition to three irradiation steps.

[0009] There is a real need to provide a method by which matte coatings can be obtained that are uniform, are characterized by improved stain resistance and can be used with a wide variety of crosslinkable components. Summary of the Invention

[0010] The present invention first provides a method for coating a surface, comprising the steps of: - applying a layer of a curable composition to said surface; - irradiating the curable composition with a first radiation having a wavelength of 100 to 280 nm to obtain a partially cured composition; and - irradiating the partially cured composition with a second radiation having at least one wavelength longer than the wavelength of the first radiation and / or with an electron beam to obtain a cured composition. Includes; wherein the curable composition comprises at least one compound curable by actinic radiation and particles of at least one polyamide. Regarding the method.

[0011] In some embodiments, the curable composition comprises from 0.01 wt % to 2 wt % of particles of at least one polyamide, preferably from 0.01 wt % to 1.5 wt % of particles of at least one polyamide, based on the total weight of the composition.

[0012] In some embodiments, the particles of at least one polyamide have a volume median diameter Dv50 of 20 μm or less, preferably 1 to 20 μm.

[0013] In some embodiments, the polyamide is selected from the group consisting of polyamide 12, polyamide 11, polyamide 10, polyamide 6, polyamide 6.10, polyamide 6.12, polyamide 6.6, polyamide 10.10, polyamide 10.12, and combinations thereof.

[0014] In some embodiments, the at least one compound curable by actinic radiation is an ethylenically unsaturated compound, preferably a compound containing at least one group selected from acrylate, methacrylate, cyanoacrylate, acrylamide, methacrylamide, styrene, maleic acid, fumaric acid, itaconate, allyl, propenyl, vinyl, methylidene malonate, and combinations thereof, more preferably a compound containing at least one functional group selected from acrylate, methacrylate, and vinyl, and even more preferably a compound containing at least one functional group selected from acrylate and methacrylate.

[0015] In some embodiments, the curable composition preferably comprises at least one photoinitiator selected from the group consisting of benzoin, benzoin ether, acetophenone, benzil, benzil ketal, anthraquinone, phosphine oxide, α-hydroxyketone, phenylglyoxylate, α-aminoketone, benzophenone, thioxanthone, xanthone, acridine derivatives, phenazene derivatives, quinoxaline derivatives, triazine derivatives, and combinations thereof.

[0016] In some embodiments, the first radiation has a wavelength of 150 to 250 nm, preferably 150 to 200 nm, more preferably 168 to 180 nm, and more preferentially 172 to 175 nm.

[0017] In some embodiments, exposing the curable composition to the first radiation is carried out using an excimer lamp.

[0018] In some embodiments, the second radiation has a wavelength spectrum in the range of 100 to 900 nm, preferably in the range of 180 to 500 nm.

[0019] In some embodiments, the second radiation comprises at least one wavelength in the range of 285 to 900 nm, preferably in the range of 300 to 500 nm.

[0020] In some embodiments, the second radiation is emitted by an undoped mercury lamp, a doped mercury lamp, or an LED lamp, preferably at a wavelength in the range of 350-405 nm.

[0021] In some embodiments, the layer of curable composition applied to a surface has a thickness of 100 μm or less, preferably 50 μm or less, and more preferably 20 μm or less.

[0022] The present invention also relates to a coating layer obtainable by such a method.

[0023] The present invention also relates to an object comprising a surface covered with a coating layer as described above.

[0024] The present invention also relates to a composition comprising at least one compound curable by actinic radiation and 0.01% to 2% by weight of particles of at least one polyamide, preferably 0.01% to 1.5% by weight of particles of at least one polyamide, relative to the total weight of the composition.

[0025] The present invention also relates to a coating layer based on the above composition.

[0026] The present invention also relates to the use of an excimer lamp for at least partially curing a curable composition comprising at least one compound curable by actinic radiation and particles of at least one polyamide.

[0027] The present invention serves to meet the above-mentioned needs. More specifically, the present invention provides a method for coating a surface, which allows for the formation of coatings characterized by a uniform and enhanced matte finish, having an improved appearance, particularly a uniform appearance, and exhibiting increased stain resistance, increased abrasion resistance, and increased chemical resistance. Furthermore, the method according to the present invention makes it possible to obtain these advantageous properties for a wide variety of curable compounds.

[0028] This is achieved by incorporating polyamide particles into the curable composition and by using a method for curing said composition that includes a first irradiation step to partially cure the composition, followed by a second irradiation step to continue crosslinking the composition. Without wishing to be bound by theory, the inventors believe that the polyamide particles dispersed in the curable composition create wrinkle initiation and endpoint points at the surface of the layer of curable composition, and that these points are created during the first irradiation step, allowing for more effective control over wrinkles, resulting in better uniformity of surface wrinkles and therefore better uniformity of coating gloss.

[0029] Furthermore, the above advantages can be achieved even with very small amounts of polyamide particles, and therefore, in advantageous embodiments, polyamide particles can be used in the curable composition in very small amounts, more particularly in amounts that are lower than those conventionally employed for matting agents. [Brief explanation of the drawings]

[0030] [Figure 1] 1 shows a photomicrograph obtained by scanning electron microscopy (SEM) of a coating obtained from curable composition A described in the examples below. [Figure 2] 1 shows a photomicrograph obtained by scanning electron microscopy of a coating obtained from curable composition 3 described in the example below. DETAILED DESCRIPTION OF THE INVENTION

[0031] Detailed Description The invention is explained in more detail and in a non-limiting manner in the following description.

[0032] Unless otherwise specified, all percentages regarding amounts are percentages by weight.

[0033] As used herein, an amount given for a given species is applicable to that species according to all of its definitions (as referred to herein), including more limited definitions.

[0034] In the context of the present invention, the terms "cure" and "crosslink" have the same meaning.

[0035] curable composition The curable compositions used in the present invention are preferably liquid at 25° C. The curable compositions may alternatively be in gel form at 25° C. but in liquid form at higher temperatures (e.g., 120° C.).

[0036] The curable compositions used in the present invention comprise at least one compound curable by actinic radiation and at least one polyamide particle. "Actinic radiation" traditionally refers to any electromagnetic and / or ionizing radiation capable of inducing a chemical reaction in a material exposed to the radiation, and more specifically refers to radiation including ultraviolet (UV) radiation, visible light, and electron beam radiation.

[0037] The curable composition is advantageously a homogeneous dispersion. "Homogeneous dispersion" refers to a dispersion of polyamide particles in a liquid matrix containing the curable compound. The homogeneity of the dispersion is therefore characterized by macroscopic homogeneity (meaning that the dispersion is uniform in appearance when observed with the naked eye) and the absence of a particulate or phase-separated appearance of the dispersion.

[0038] The curable composition may have a viscosity at 25°C of 100,000 mPa s or less, preferably 50,000 mPa s or less, more preferably 25,000 mPa s or less, more preferably 10,000 mPa s or less, and even more preferably 5,000 mPa s or less, as measured using a Brookfield DV-II viscometer employing a 27 spindle (spindle speed varies depending on viscosity, typically between 20 and 200 rpm).

[0039] Actinic radiation curable compounds The curable compositions according to the present invention comprise one or more compounds that are curable by actinic radiation. The compounds that are curable by actinic radiation that are incorporated into the curable compositions according to the present invention are collectively referred to as actinically curable components.

[0040] Compounds curable by actinic radiation are particularly intended to be polymerized by radical polymerization reactions.

[0041] The compound that can be cured by actinic radiation can be, in particular, an ethylenically unsaturated compound. In the sense of the present invention, "ethylenically unsaturated compound" means a compound that contains a polymerizable carbon-carbon double bond. A polymerizable carbon-carbon double bond is a carbon-carbon double bond that can react with another carbon-carbon double bond in a polymerization reaction. The carbon-carbon double bond in a phenyl ring is not considered to be a polymerizable carbon-carbon double bond.

[0042] The ethylenically unsaturated compound may be, in particular, a compound containing at least one group selected from acrylate, methacrylate, cyanoacrylate, acrylamide, methacrylamide, styrene, maleic acid, fumaric acid, itaconate, allyl, propenyl, vinyl, methylidene malonate, and corresponding combinations, more preferably a compound containing at least one functional group selected from acrylate, methacrylate, vinyl, and combinations thereof, and even more preferably a compound containing at least one functional group selected from acrylate, methacrylate, and combinations thereof.

[0043] The actinically curable component may, in particular, comprise (or be a) (meth)acrylate-functionalized compound. The actinically curable component may comprise (or be a) mixture of (meth)acrylate-functionalized compounds.

[0044] As used herein, the term "(meth)acrylate-functionalized compound" refers to a compound containing at least one (meth)acryloyloxy group, more specifically, an acryloyloxy group. The term "(meth)acryloyloxy group" encompasses acryloyloxy groups (-O-CO-CH=CH2) and methacryloyloxy groups (-O-CO-C(CH3)=CH2).

[0045] The total amount of (meth)acrylate-functionalized compounds in the component curable with actinic radiation can be 20% to 100% by weight, in particular 30% to 100% by weight, preferably 40% to 100% by weight, preferably 50% to 100% by weight, preferably 60% to 100% by weight, preferably 70% to 100% by weight, preferably 80% to 100% by weight, and more preferably 90% to 100% by weight, based on the total weight of the component curable with actinic radiation. According to some embodiments, the component curable with actinic radiation does not contain any polymerizable compounds other than the (meth)acrylate-functionalized compounds.

[0046] The component curable by actinic radiation may comprise or be a (meth)acrylate-functionalized compound selected from, in particular, (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, and mixtures thereof. More specifically, the component curable by actinic radiation may comprise or be at least one (meth)acrylate-functionalized monomer and / or at least one (meth)acrylate-functionalized oligomer. Particularly advantageously, the component curable by actinic radiation comprises at least one (meth)acrylate-functionalized monomer and at least one (meth)acrylate-functionalized oligomer.

[0047] The actinically curable component may in particular comprise at least one (meth)acrylate-functionalized monomer or may be at least one (meth)acrylate-functionalized monomer. The actinically curable component may comprise (or be a mixture of) (meth)acrylate-functionalized monomers.

[0048] The (meth)acrylate functionalized monomer may have a molecular weight of less than 600 g / mol, particularly from 70 g / mol to less than 550 g / mol, more particularly from 80 g / mol to 450 g / mol, and even more particularly from 90 g / mol to 350 g / mol.

[0049] The (meth)acrylate-functionalized monomer may contain 1 to 6 (meth)acryloyloxy groups, especially 1 to 4 (meth)acryloyloxy groups.

[0050] The (meth)acrylate-functionalized monomer may comprise a mixture of (meth)acrylate-functionalized monomers having different functionalities. For example, the (meth)acrylate-functionalized monomer may comprise or be a mixture of one (or at least one) (meth)acrylate-functionalized monomer containing a single acryloyloxy or methacryloyloxy group per molecule (referred to herein as a "mono(meth)acrylate-functionalized monomer") and one (or at least one) (meth)acrylate-functionalized monomer containing two or more, preferably 2 to 6, acryloyloxy and / or methacryloyloxy groups per molecule (referred to herein as a "poly(meth)acrylate-functionalized monomer").

[0051] The component curable by actinic radiation may in particular comprise at least one mono(meth)acrylate-functionalized monomer or may be at least one mono(meth)acrylate-functionalized monomer. The component curable by actinic radiation may in particular comprise a mixture of mono(meth)acrylate-functionalized monomers or may be a mixture of mono(meth)acrylate-functionalized monomers. The mono(meth)acrylate-functionalized monomer may advantageously function as a reactive diluent, reducing the viscosity of the curable composition according to the present invention.

[0052] Examples of suitable mono(meth)acrylate-functionalized monomers include, but are not limited to, (meth)acrylic acid, mono(meth)acrylate esters of aliphatic alcohols (the aliphatic alcohols may be linear or branched and may be mono-, di-, or polyalcohols, provided that only one hydroxyl group is esterified with (meth)acrylic acid); mono(meth)acrylate esters of alicyclic or heterocyclic alcohols; mono(meth)acrylate esters of aromatic alcohols (such as phenols, including alkylated phenols); mono(meth)acrylate esters of alkylaryl alcohols (such as benzyl alcohol); mono(meth)acrylate esters of oligomeric and polymeric glycols (such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol); mono(meth)acrylate esters of monoalkyl ethers of glycols and oligoglycols; caprolactone mono(meth)acrylate; and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof.

[0053] The components curable by actinic radiation are, in particular, (meth)acrylic acid; methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; isopropyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-pentyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; isodecyl (meth)acrylate; n -Dodecyl (meth)acrylate;Tridecyl (meth)acrylate;Tetradecyl (meth)acrylate;Hexadecyl (meth)acrylate;2-Hydroxyethyl (meth)acrylate;2-Hydroxypropyl (meth)acrylate;3-Hydroxypropyl (meth)acrylate;4-Hydroxybutyl (meth)acrylate;2-Methoxyethyl (meth)acrylate;2-Ethoxyethyl (meth)acrylate;2-Ethoxypropyl (meth)acrylate;3-Ethoxypropyl (meth)acrylate;Tetrahydrosulfur 2-(2-Ethoxyethoxy)ethyl (meth)acrylate;Cyclohexyl (meth)acrylate;Glycidyl (meth)acrylate;Benzyl (meth)acrylate;2-Phenoxyethyl (meth)acrylate;Phenol (meth)acrylate;Nonylphenol (meth)acrylate;Cyclic trimethylolpropane formal (meth)acrylate;Isobornyl (meth)acrylate;Tricyclodecanemethanol (meth)acrylate;tert-Butylcyclohexyl (meth)acrylate;Tricyclodecane Trimethylcyclohexyl (meth)acrylate;Diethylene glycol monomethyl ether (meth)acrylate;Diethylene glycol monobutyl ether (meth)acrylate;Triethylene glycol monoethyl ether (meth)acrylate;Polyethylene glycol monomethyl ether (meth)acrylate;Hydroxyethylbutylurethane (meth)acrylate;3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate;(2,2-dimethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate;The mono(meth)acrylate functionalized monomer may be selected from (2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl (meth)acrylate; 1,3-dioxan-5-yl (meth)acrylate; (1,3-dioxolan-4-yl)methyl (meth)acrylate; glycerol carbonate (meth)acrylate; and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof, and mixtures thereof;

[0054] The actinic radiation curable component preferably comprises or is a mono(meth)acrylate functionalized monomer selected from cyclohexyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, nonylphenol acrylate, cyclic trimethylolpropane formal acrylate, isobornyl acrylate, tricyclodecane methanol acrylate, tert-butylcyclohexyl acrylate, trimethylcyclohexyl acrylate, and mixtures thereof.

[0055] The actinically curable component may, inter alia, include or be at least one poly(meth)acrylate-functionalized monomer.

[0056] Examples of poly(meth)acrylate functionalized monomers include acrylate and methacrylate esters of polyols (organic compounds containing two or more hydroxyl groups per molecule; for example, 2 to 6 hydroxyl groups per molecule).Examples of suitable polyols are: ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 1,3- or 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, Neopentyl glycol, 2,4-diethyl-1,5-pentanediol, cyclohexanediol, cyclohexane-1,4-dimethanol, norbornene dimethanol, norbornane dimethanol, tricyclodecanediol, tricyclodecane dimethanol, bisphenol A, B, F or S, hydrogenated bisphenol A, B, F or S, trimethylolmethane, trimethylolethane, trimethylolpropane, di(trimethylolpropane), triethylolpropane, pentaerythritol, di(pentaerythritol) glycerol, di-, tri- or tetraglycerol, polyglycerol, di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol, di-, tri- or tetrabutylene glycol, one or more polyethylene glycols, one or more polypropylene glycols, one or more polytetramethylene glycols, one or more poly(ethylene glycol-co-propylene glycols), one or more alditols (more specifically, erythritol, threitol, arabitol, xylitol , ribitol, mannitol, sorbitol, galactitol, fucitol or iditol), one or more dianhydrohexitols (more specifically isosorbide, isomannide or isoidide), tris(2-hydroxyethyl) isocyanurate, one or more polybutadiene polyols and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives, derivatives obtained by ring-opening polymerization of lactones (e.g., ε-caprolactone) initiated with one of the above-mentioned polyols, and mixtures thereof.Such polyols may be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.), provided that they contain at least two (meth)acryloyloxy functional groups per molecule.

[0057] More specifically, the component curable by actinic radiation may be, inter alia, bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate. TETRAPROPYLENE GLYCOL DI(METH)ACRYLATE;POLYPROPYLENE GLYCOL DI(METH)ACRYLATE;POLYTETRAMETHYLENE GLYCOL DI(METH)ACRYLATE;1,2-BUTANEDIOL DI(METH)ACRYLATE;2,3-BUTANEDIOL DI(METH)ACRYLATE;1,3-BUTANEDIOL DI(METH)ACRYLATE;1,4-BUTANEDIOL DI(METH)ACRYLATE;1,5-PENTANEDIOL DI(METH)ACRYLATE;1,6-HEXANEDIOL DI(METH)ACRYLATE;1,8-OCTANEDIOL DI(METH)ACRYLATE;1,9-NONANEDIOL DI(METH)ACRYLATE DI(METH)ACRYLATE;1,10-DECANEDIOL DI(METH)ACRYLATE;1,12-DODECANEDIOL DI(METH)ACRYLATE;3-METHYL-1,5-PENTANEDIOL DI(METH)ACRYLATE;NEOPENTYL GLYCOL DI(METH)ACRYLATE;2-METHYL-2,4-PENTANEDIOL DI(METH)ACRYLATE;POLYBUTADIENE DI(METH)ACRYLATE;CYCLOHEXANE-1,4-DIMETHANOL DI(METH)ACRYLATE;TRICYCLODECANDIMEHANOL DI(METH)ACRYLATE;GLYCEROL DI(METH)ACRYLATE;GLYCEROL TRI(METH)ACRYLATE ) acrylate;Trimethylolethane tri(meth)acrylate;Trimethylolethane di(meth)acrylate;Trimethylolpropane tri(meth)acrylate;Trimethylolpropane di(meth)acrylate;Pentaerythritol di(meth)acrylate;Pentaerythritol tri(meth)acrylate;Pentaerythritol tetra(meth)acrylate;Di(trimethylolpropane) di(meth)acrylate;Di(trimethylolpropane) tri(meth)acrylate;Di(trimethylolpropane) tetra(meth)acrylate;The poly(meth)acrylate functionalized monomer may comprise or be selected from sorbitol penta(meth)acrylate; di(pentaerythritol) tetra(meth)acrylate; di(pentaerythritol) penta(meth)acrylate; di(pentaerythritol) hexa(meth)acrylate; tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate; and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof.

[0058] The actinic radiation-curable component preferably comprises or is a poly(meth)acrylate-functionalized monomer selected from 1,6-hexanediol diacrylate, 1,10-decanediol acrylate, 3-methyl-1,5-pentanediol diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, di(trimethylolpropane)tetraacrylate, pentaerythritol tetraacrylate, di(pentaerythritol)pentaacrylate, and mixtures thereof.

[0059] The actinically curable component may comprise from 0 wt% to 100 wt%, specifically from 5 wt% to 100 wt%, more specifically from 10 wt% to 100 wt%, more specifically from 15 wt% to 100 wt%, more specifically from 20 wt% to 95 wt%, more specifically from 25 wt% to 95 wt%, more specifically from 30 wt% to 95 wt%, more specifically from 35 wt% to 90 wt%, more specifically from 40 wt% to 90 wt%, more specifically from 50 wt% to 90 wt% of the (meth)acrylate-functionalized monomer, based on the weight of the actinically curable component. Thus, the actinically curable component may comprise from 0% to 60% by weight, preferably from 5% to 60% by weight, preferably from 10% to 60% by weight, preferably from 15% to 60% by weight, preferably from 20% to 60% by weight, preferably from 25% to 60% by weight, preferably from 30% to 60% by weight, preferably from 35% to 60% by weight, preferably from 40% to 60% by weight, more preferably from 45% to 60% by weight of (meth)acrylate functionalized monomer, based on the weight of the actinically curable component. Alternatively, the actinically curable component may comprise 60% to 100% by weight, preferably 65% ​​to 100% by weight, preferably 70% to 100% by weight, preferably 75% to 100% by weight, preferably 80% to 100% by weight, preferably 85% to 100% by weight, preferably 90% to 100% by weight, more preferably 95% to 100% by weight of (meth)acrylate functionalized monomer, based on the weight of the actinically curable component.

[0060] The actinically curable component may in particular comprise or be at least one (meth)acrylate-functionalized oligomer. The actinically curable component may comprise or be a mixture of (meth)acrylate-functionalized oligomers.

[0061] The (meth)acrylate-functionalized oligomer may be selected to enhance the flexibility, strength and / or modulus, among other properties, of the product obtained by polymerizing the curable composition according to the present invention.

[0062] The (meth)acrylate-functionalized oligomer may have 1 to 18 (meth)acryloyloxy groups, particularly 2 to 6 (meth)acryloyloxy groups, and more particularly 2 to 6 acryloyloxy groups.

[0063] The (meth)acrylate-functionalized oligomer may have a number average molecular weight of 600 g / mol or more, particularly 800 to 15,000 g / mol, and more particularly 1,000 to 5,000 g / mol. The number average molecular weight of the (meth)acrylate-functionalized oligomer can be measured by gel permeation chromatography (GPC).

[0064] In particular, the actinically curable component may comprise or be a (meth)acrylate-functionalized oligomer selected from (meth)acrylate-functionalized urethane oligomers, (meth)acrylate-functionalized epoxy oligomers, (meth)acrylate-functionalized polyether oligomers, (meth)acrylate-functionalized polyester oligomers, (meth)acrylate-functionalized (meth)acrylic oligomers, (meth)acrylate-functionalized polydiene oligomers, (meth)acrylate-functionalized polycarbonate oligomers, (meth)acrylate-functionalized polyamide oligomers, and mixtures thereof.

[0065] (Meth)acrylate-functionalized urethane oligomers suitable for use in the curable composition of the present invention include urethanes based on at least one polyol, at least one polyisocyanate, and at least one hydroxyl-functionalized and (meth)acrylate-functionalized compound (also referred to as hydroxyl-functionalized (meth)acrylate). (Meth)acrylate-functionalized urethane oligomers can be prepared by reacting a polyisocyanate (e.g., an aliphatic, cycloaliphatic, heterocyclic, or aromatic diisocyanate or triisocyanate) with a polyol (especially a polyester polyol, a polyether polyol, a polycarbonate polyol, a polycaprolactone polyol, a polyorganosiloxane polyol, a polydiene polyol such as a polybutadiene polyol, or a corresponding combination) to form an isocyanate-terminated oligomer, which can then be reacted with a hydroxyl-functionalized (meth)acrylate (e.g., hydroxyethyl (meth)acrylate) to obtain a terminal (meth)acrylate group. For example, a (meth)acrylate-functionalized urethane oligomer may contain two, three, four, or more (meth)acrylate functional groups per molecule. Other addition orders may also be used to prepare a (meth)acrylate-functionalized urethane oligomer. For example, a hydroxyl-functionalized (meth)acrylate may be first reacted with a polyisocyanate to give an isocyanate-functionalized (meth)acrylate, which may then be reacted with a polyol. Alternatively, all components may be combined and reacted simultaneously.

[0066] Examples of suitable (meth)acrylate-functionalized epoxy oligomers include the reaction product of (meth)acrylic acid (or a corresponding synthetic equivalent such as an acid chloride, alkyl ester, or anhydride) with an epoxy resin containing at least one epoxide group (particularly at least one group selected from glycidyl ethers, glycidyl esters, and combinations thereof).Epoxy resins include, in particular, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resins, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecalcine. carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide , ethylene glycol bis(3,4-epoxycyclohexylmethyl) ether, ethylene bis(3,4-epoxycyclohexanecarboxylate), 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycidyl ethers of polyether polyols obtained by the addition of one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerol, diglycidyl esters of long-chain aliphatic dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of phenol, cresol, butylphenol, or polyether alcohols obtained by the addition of alkylene oxides to these compounds, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy butyl stearic acid, epoxy octyl stearic acid, epoxidized linseed oil, epoxidized polybutadiene, etc.

[0067] Suitable (meth)acrylate-functionalized polyether oligomers include, but are not limited to, the reaction product of (meth)acrylic acid (or corresponding synthetic equivalents such as acid chlorides, alkyl esters, or anhydrides) with at least one polyetherol corresponding to a polyether polyol (such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or copolymers thereof). Suitable polyetherols can be linear or branched materials containing ether linkages and terminal hydroxyl groups. Polyetherols can be prepared by ring-opening polymerization of cyclic ethers such as tetrahydrofuran or alkylene oxides (e.g., ethylene oxide and / or propylene oxide) with starter molecules. Suitable starter molecules include water, polyhydroxy-functionalized materials, polyester polyols, and amines.

[0068] Examples of (meth)acrylate-functionalized polyester oligomers include the reaction product of (meth)acrylic acid (or corresponding synthetic equivalents, such as acid chlorides, alkyl esters, or anhydrides) with a hydroxyl-terminated polyester polyol. The reaction process can be carried out so that all or essentially all of the hydroxyl groups of the polyester polyol are (meth)acrylated, especially when the polyester polyol is difunctional. The polyester polyol can be prepared by the polycondensation reaction of a polyhydroxy-functionalized component (particularly a diol) with a poly(carboxylic acid)-functionalized compound (particularly a dicarboxylic acid and anhydride). The polyhydroxy-functionalized component and the poly(carboxylic acid)-functionalized component can each have a linear, branched, alicyclic, or aromatic structure and can be used individually or as a mixture.

[0069] Suitable (meth)acrylate-functionalized (meth)acrylic oligomers (sometimes known in the art as "acrylic oligomers") include oligomers that can be described as materials having a (meth)acrylic backbone functionalized with one or more (meth)acrylate groups, which can be at the end of the oligomer or pendant to the (meth)acrylic backbone. The (meth)acrylic backbone can be a homopolymer, random copolymer, or block copolymer composed of repeating units of a (meth)acrylic monomer. The (meth)acrylic monomer can be any monomeric (meth)acrylate, such as a C1-C6 alkyl (meth)acrylate, and / or a functionalized (meth)acrylate, such as a (meth)acrylate bearing a hydroxyl, carboxylic acid, and / or epoxy group. (Meth)acrylate-functionalized (meth)acrylic oligomers can be prepared using any procedure known in the art, such as, for example, oligomerizing monomers at least some of which are functionalized with hydroxyl groups, carboxylic acid groups, and / or epoxy groups (e.g., hydroxyalkyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate) to obtain a functionalized oligomeric intermediate, and then reacting this intermediate with one or more (meth)acrylate group-containing reactants to introduce the desired (meth)acrylate functionality.

[0070] Exemplary (meth)acrylate-functionalized polydiene oligomers include the reaction product of (meth)acrylic acid (or corresponding synthetic equivalents such as acid chlorides, alkyl esters, or anhydrides) with hydroxyl-terminated polydiene polyols, particularly hydroxyl-terminated polybutadiene polyols.

[0071] Exemplary (meth)acrylate-functionalized polycarbonate oligomers include the reaction product of (meth)acrylic acid (or the corresponding synthetic equivalent, such as the acid chloride, alkyl ester, or anhydride) with a hydroxyl-terminated polycarbonate polyol.

[0072] Exemplary (meth)acrylate-functionalized polyamide oligomers include the reaction product of (meth)acrylic acid (or the corresponding synthetic equivalent, such as the acid chloride, alkyl ester, or anhydride) with a hydroxyl-terminated polyamide polyol.

[0073] The actinic radiation-curable component preferably comprises or is a (meth)acrylate-functionalized oligomer selected from (meth)acrylate-functionalized urethane oligomers, (meth)acrylate-functionalized epoxy oligomers, (meth)acrylate-functionalized polyester oligomers, and mixtures thereof. Particularly preferred (meth)acrylate-functionalized oligomers for the present invention include those sold by Sartomer under the following trade names: CN9200, CN9210, CN9276, CN9301, CN963B80, CN964A85, CN965, CN981, CN991, CN996, CN998B80, CN104, CN203, CN2203EU, CN2295EU, CN2303EU, CN2505, and mixtures thereof.

[0074] The actinically curable component may comprise from 0% to 100% by weight, specifically from 5% to 100% by weight, more specifically from 10% to 100% by weight, more specifically from 15% to 100% by weight, more specifically from 20% to 95% by weight, more specifically from 25% to 95% by weight, more specifically from 30% to 95% by weight, more specifically from 35% to 90% by weight, more specifically from 40% to 90% by weight, more specifically from 50% to 90% by weight of the (meth)acrylate-functionalized oligomer, based on the weight of the actinically curable component. In particular, the actinically curable component may comprise from 0% to 60% by weight, preferably from 5% to 60% by weight, preferably from 10% to 60% by weight, preferably from 15% to 60% by weight, preferably from 20% to 60% by weight, preferably from 25% to 60% by weight, preferably from 30% to 60% by weight, preferably from 35% to 60% by weight, preferably from 40% to 60% by weight, more preferably from 45% to 60% by weight of the (meth)acrylate-functionalized oligomer, based on the weight of the actinically curable component. Alternatively, the actinically curable component may comprise 60% to 100% by weight, preferably 65% ​​to 100% by weight, preferably 70% to 100% by weight, preferably 75% to 100% by weight, preferably 80% to 100% by weight, preferably 85% to 100% by weight, preferably 90% to 100% by weight, more preferably 95% to 100% by weight of the (meth)acrylate-functionalized oligomer, based on the weight of the actinically curable component.

[0075] The actinic radiation curable component advantageously comprises: - 10% to 90% by weight, preferably 20% to 80% by weight, more preferably 30% to 70% by weight, and even more preferentially 40% to 60% by weight of (meth)acrylate-functionalized monomers; and - 10% to 90% by weight, preferably 20% to 80% by weight, more preferably 30% to 70% by weight and even more preferentially 40% to 60% by weight of (meth)acrylate-functionalized oligomers Includes; Here, weight percent is expressed relative to the weight of the actinically curable component.

[0076] The amount of components curable by actinic radiation in the curable composition is preferably 50% to 99.99% by weight, more preferentially 80% to 99.99% by weight, preferentially 90% to 99.99% by weight, even more preferentially 95% to 99.99% by weight.

[0077] Polyamide particles The curable composition comprises particles of at least one polyamide. The polyamide particles are in particular a powder.

[0078] According to one embodiment, the particles consist of one or more polyamides.

[0079] The polyamide may be a homopolyamide and / or a copolyamide, it may consist solely of polyamide or it may also comprise one or more blocks of another type, for example chosen from polyether blocks, polyester blocks, polysiloxane blocks such as polydimethylsiloxane (or PDMS) blocks, polyolefin blocks, polycarbonate blocks, and mixtures thereof.

[0080] The term "polyamide" is intended to mean a polymer comprising at least one polymerization product of one or more monomers selected from the following: - amino acid or aminocarboxylic acid type monomers, preferably α,ω-aminocarboxylic acids; - optionally substituted lactam-type monomers containing 3 to 18 carbon atoms in the main ring; - "diamine-diacid" type monomers derived from the reaction between aliphatic diamines containing from 2 to 36 carbon atoms, preferably from 4 to 18 carbon atoms, and dicarboxylic acids containing from 4 to 36 carbon atoms, preferably from 4 to 18 carbon atoms; and - in the case of mixtures of amino acid type monomers and lactam type monomers, their mixtures with monomers having different carbon numbers.

[0081] In this specification, the term "monomer" should be interpreted as meaning "repeating unit." Indeed, a special case is when the repeating unit of a polyamide (PA) consists of a combination of a diacid and a diamine. The equivalent of a monomer is considered to be the combination of a diamine and a diacid, i.e., a diamine-diacid pair (equimolar amounts). This is explained by the fact that the diacid or diamine individually are merely structural units and are not sufficient by themselves to polymerize.

[0082] When the polyamide is a homopolyamide, it comprises the polymerization product of a single monomer as defined above. When the polyamide is a copolyamide, it comprises the polymerization product of at least two different monomers as defined above. Examples of copolyamides formed from the various types of monomers mentioned above include copolyamides resulting from the condensation of at least two α,ω-aminocarboxylic acids, or two lactams, or one lactam and one α,ω-aminocarboxylic acid. Also included are copolyamides resulting from the condensation of at least one α,ω-aminocarboxylic acid (or lactam), at least one diamine, and at least one dicarboxylic acid. Also included are copolyamides resulting from the condensation of an aliphatic diamine, an aliphatic dicarboxylic acid, and at least one other monomer selected from aliphatic diamines and aliphatic diacids other than those mentioned above.

[0083] Amino acid type monomers: Examples of α,ω-amino acids include those containing 4 to 18 carbon atoms, such as aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, N-heptyl-11-aminoundecanoic acid, and 12-aminododecanoic acid.

[0084] Lactam-type monomers: Examples of lactams include optionally substituted lactams containing 3 to 18 carbon atoms in the main ring, such as β,β-dimethylpropiolactam, α,α-dimethylpropiolactam, amylolactam, caprolactam (also known as lactam 6), capryllactam (also known as lactam 8), oenantholactam, and lauryllactam (also known as lactam 12).

[0085] "Diamine-diacid" type monomers: Examples of dicarboxylic acids include acids having 4 to 36 carbon atoms, preferably 4 to 18 carbon atoms, such as adipic acid, sebacic acid, azelaic acid, suberic acid, isophthalic acid, butanedioic acid, 1,4-cyclohexyldicarboxylic acid, terephthalic acid, sodium or lithium salts of sulfoisophthalic acid, dimerized fatty acids (these dimerized fatty acids have a dimer content of at least 98% by weight and are preferably hydrogenated), and dodecanedioic acid HOOC-(CH2). 10 Mention may be made of —COOH and tetradecanedioic acid.

[0086] The term "fatty acid dimer" or "dimerized fatty acid" is more particularly understood to mean the product of the dimerization reaction of fatty acids (generally containing 18 carbon atoms, often a mixture of oleic acid and / or linoleic acid), which is preferably a mixture comprising 0-15% by weight of C18 monoacids, 60%-99% by weight of C36 diacids, and 0.2%-35% by weight of triacids or polyacids of C54 or higher.

[0087] Examples of diamines include aliphatic diamines having 2 to 36 carbon atoms, preferably 4 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms, which may be aryl and / or saturated cyclic. Examples include hexamethylenediamine, piperazine (abbreviated as "Pip"), aminoethylenepiperazine, tetramethylenediamine, octamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, 1,5-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, diamine polyol, isophoronediamine (IPD), methylpentamethylenediamine (MPMD), bis(aminocyclohexyl)methane (BACM), bis(3-methyl-4-aminocyclohexyl)methane (BMACM), meta-xylenediamine, and bis-p-aminocyclohexylmethane.

[0088] The term "diamine-diacid" more particularly refers to those resulting from the condensation of 1,6-hexamethylenediamine with dicarboxylic acids having 6 to 36 carbon atoms, particularly the following monomers: 6.6, 6.10, 6.11, 6.12, 6.14, and 6.18, and those resulting from the condensation of 1,10-decamethylenediamine with diacids having 6 to 36 carbon atoms, particularly the following monomers: 10.10, 10.12, 10.14, and 10.18. As is conventional, in the numerical notation XY, X represents the number of carbon atoms derived from the diamine residue and Y represents the number of carbon atoms derived from the diacid residue.

[0089] The polyamide preferably comprises at least one of the following monomers: 4.6, 4.T, 5.6, 5.9, 5.10, 5.12, 5.13, 5.14, 5.16, 5.18, 5.36, 6, 6.6, 6.9, 6.10, 6.12, 6.13, 6.14, 6.16, 6.18, 6.36, 6.T, 9, 10.6, 10.9, 10.10, 10.12, 10.13, 10.14, 10.16, 10.18, 10.36, 10.T, 11, 12, 12.6, 12.9, 12.10, 12.12, 12.13, 12.14, 12.16, 12.18, 12.36, 12.T, and mixtures thereof.

[0090] Advantageously, the polyamides used in the invention are (or comprise polyamide blocks of) the following polyamides: PA 6, PA 10, PA 11, PA 12, PA 5.4, PA 5.9, PA 5.10, PA 5.12, PA 5.13, PA 5.14, PA 5.16, PA 5.18, PA 5.36, PA 6.4, PA 6.9, PA 6.10, PA 6.12, PA 6.13, PA 6.14, PA 6.16, PA 6.18, PA 6.36, PA 10.4, PA 10.9, PA 10.10, PA 10.12, PA 10.13, PA 10.14, PA 10.16, PA 10.18, PA 10.36, PA 10.T, PA PA 12.4, PA 12.9, PA 12.10, PA 12.12, PA 12.13, PA 12.14, PA 12.16, PA 12.18, PA 12.36, PA 12.T, PA 6.6 / 6, PA 6.6 / 6.10 / 11 / 12, PA 10.10 / 11, PA 10.10 / 12, PA 10.10 / 14, PA 10.12 / 11, PA 10.12 / 12, PA 10.12 / 14, or mixtures or copolymers thereof. In the PA X designation, X represents the number of carbon atoms derived from amino acid residues or lactam residues. Designations such as PA X / Y and PA X / Y / Z refer to copolyamides where X, Y, Z, etc. represent homopolyamide units as described above.

[0091] Preferably, the polyamide according to the invention is selected from PA 11, PA 12, PA 6, PA 6.X1, PA 10, PA 10.X2, PA 10.X3 / Y1, or a combination thereof. Preferably, from the above list, X1 is selected from 10, 12, 14 or 18. Preferably, from the above list, X2 is selected from 10, 12 or 14. Preferably, from the above list, X3 is selected from 10 or 12. Preferably, from the above list, Y1 is selected from 11, 12 or 14.

[0092] Advantageously, the polyamide of the powder is(are) one or more homopolyamides.

[0093] More preferably, the polyamide is selected from the group consisting of polyamide 12, polyamide 11, polyamide 10, polyamide 6, polyamide 6.10, polyamide 6.12, polyamide 6.6, polyamide 10.10, polyamide 10.12, and combinations thereof. Particularly preferably, the polyamide is polyamide 12.

[0094] Alternatively, the polyamide may be a copolyamide, such as copolymer of caprolactam and lauryllactam (PA 6 / 12), copolymer of caprolactam, adipic acid and hexamethylenediamine (PA 6 / 6.6), copolymer of caprolactam, lauryllactam, adipic acid and hexamethylenediamine (PA 6 / 12 / 6.6), copolymer of caprolactam, lauryllactam, 11-aminoundecanoic acid, azelaic acid and hexamethylenediamine (PA 6 / 6.9 / 11 / 12), copolymer of caprolactam, lauryllactam, 11-aminoundecanoic acid, adipic acid and hexamethylenediamine (PA 6 / 6.6 / 11 / 12), copolymer of lauryllactam, azelaic acid and hexamethylenediamine (PA 6.9 / 12), and copolymer of 11-aminoundecanoic acid, terephthalic acid and 1,10-decamethylenediamine (PA 11 / 10.T).

[0095] The polyamide according to the invention may be a mixture of polyamides, for example a mixture of aliphatic and semi-aromatic polyamides, or a mixture of aliphatic and cycloaliphatic polyamides. When the polyamide is a mixture of polyamides, the polyamide particles may consist of a mixture of particles of each polyamide, or each particle may comprise a mixture of polyamides.

[0096] Advantageously, the polyamide particles have a volume median diameter Dv50 of 20 μm or less, preferably 1 to 20 μm, and more preferentially 5 to 20 μm. More specifically, the polyamide particles may have a volume median diameter Dv50 of 1 to 5 μm, or 5 to 10 μm, or 10 to 15 μm, or 15 to 20 μm. Dv50 corresponds to the particle size at the 50th percentile (by volume) of the cumulative particle size distribution. It can be determined according to ISO Standard 9276, Parts 1 to 6.

[0097] The polyamide powder according to the present invention can be prepared by grinding a polyamide in a solid form, for example, in the form of pellets. The polyamide, particularly if it comprises a mixture of two or more polyamides, is preferably melted and optionally mixed, for example, in a mixer. It is then ground after solidification. The grinding can be achieved by any means, more specifically, by hammer grinding, knife grinding, disk grinding, air jet grinding, and cryogenic grinding. The powder preparation process can also include a step of selecting powder particles having the desired particle size.

[0098] The curable composition preferably comprises polyamide particles in an amount of 0.01% to 2% by weight, more preferably 0.01% to 1.5% by weight, more preferentially 0.05% to 1.5% by weight, and even more preferentially 0.1% to 1.5% by weight, relative to the total weight of the composition. In particular, the polyamide particles may be present in an amount less than the amount of matting agents typically used to obtain a matting effect. In some embodiments, the curable composition can comprise from 0.01 wt % to 0.05 wt %, or from 0.05 wt % to 0.1 wt %, or from 0.1 wt % to 0.2 wt %, or from 0.2 wt % to 0.3 wt %, or from 0.3 wt % to 0.5 wt %, or from 0.5 wt % to 0.8 wt %, or from 0.8 wt % to 1 wt %, or from 1 wt % to 1.2 wt %, or from 1.2 wt % to 1.5 wt %, or from 1.5 wt % to 1.7 wt %, or from 1.7 wt % to 2 wt % polyamide particles, based on the total weight of the composition.

[0099] Photoinitiator The curable composition according to the present invention may contain at least one photoinitiator. In this case, the composition, more particularly the compound(s) curable by actinic radiation, is preferably curable by radiant energy (visible and / or ultraviolet radiation). A photoinitiator may be considered to be any type of substance that, upon exposure to radiation (e.g., actinic radiation), forms a species that initiates the reaction and curing of organic polymeric materials present in the curable composition. Photoinitiators suitable for the present invention include free radical photoinitiators, cationic photoinitiators, and combinations thereof.

[0100] Polymerization initiators that act via a free radical pathway are substances that form free radicals when irradiated. The use of free radical photoinitiators is preferred. Non-limiting examples of free radical photoinitiators suitable for use in the curable compositions of the present invention include benzoin, benzoin ether, acetophenone, benzil, benzil ketal, anthraquinone, phosphine oxide, α-hydroxyketone, phenylglyoxylate, α-aminoketone, benzophenone, thioxanthone, xanthone, acridine derivatives, phenazene derivatives, quinoxaline derivatives, triazine derivatives, and mixtures thereof.

[0101] When a photoinitiator is present in the curable composition, it is preferably present in an amount up to 15 wt%, more specifically 0.05 wt% to 15 wt%, based on the total weight of the curable composition. For example, the curable composition may advantageously comprise 0.1 wt% to 10 wt% photoinitiator, based on the total weight of the curable composition. In some embodiments, the curable composition comprises 0.05 wt% to 0.5 wt%, or 0.5 wt% to 5 wt%, or 5 wt% to 10 wt%, or 10 wt% to 15 wt% photoinitiator, based on the total weight of the composition.

[0102] Non-reactive solvents The curable composition preferably does not contain or essentially does not contain non-reactive solvents. As used herein, the term "non-reactive solvent" refers to a solvent that cannot be cured by actinic radiation, in contrast to the compound(s) that can be cured by actinic radiation present in the composition. However, a non-reactive solvent may react with one or more components of the composition through other mechanisms.

[0103] For example, the curable composition may comprise less than 5 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or 0 wt% of non-reactive solvent, based on the total weight of the composition.

[0104] In some embodiments, the curable composition may contain a certain amount of one or more non-reactive solvents. For example, non-reactive solvents may be used to help solubilize one or more components of the composition and / or to reduce the viscosity of the composition. The type of non-reactive solvent that can be used is not limited, so long as it does not interfere with the ability of the composition to be cured by exposure to actinic radiation. Suitable non-reactive solvents include, for example, ketones (e.g., acetone), esters, ethers, alcohols (including halogenated alcohols such as fluoroalcohols, aromatic hydrocarbons, etc.), and combinations thereof. The actinic radiation-curable composition may contain at least 0.5 wt %, or at least 1 wt %, or at least 2 wt %, or at least 5 wt % of one or more non-reactive solvents, based on the total weight of the composition. Alternatively, or in addition, the curable composition may comprise up to 90 wt%, or up to 80 wt%, or up to 70 wt%, or up to 60 wt%, or up to 50 wt%, or up to 40 wt%, or up to 30 wt%, or up to 25 wt%, or up to 20 wt%, of one or more non-reactive solvents, based on the total weight of the composition. For example, the curable composition may comprise from 1 wt% to 50 wt%, or from 1 wt% to 25 wt% of non-reactive solvents.

[0105] The non-reactive solvent may be a volatile non-reactive solvent or a non-volatile non-reactive solvent. As used herein, the term "volatile solvent" refers to a solvent having a boiling point of 100°C or less at atmospheric pressure, and the term "non-volatile solvent" refers to a solvent having a boiling point of more than 100°C at atmospheric pressure. A combination of volatile and non-volatile solvents may also be used.

[0106] In the context of the present invention, it is also possible to use one or more non-reactive solvents when formulating a composition, particularly to help solubilize certain components, and then, after the components of the composition (including one or more non-reactive solvents) have been combined, removal of at least a portion (up to all of the non-reactive solvent) of the non-reactive solvent can be carried out to provide a final curable composition for use in a method according to the present invention. For example, the components of the composition can be combined and then subjected to mixing and / or heating to obtain a product or homogeneous solution, and then at least a portion of the non-reactive solvent can be removed by suitable means, such as distillation or stripping under vacuum.

[0107] Other additives The curable composition according to the present invention may contain one or more other additives. Such additives may be selected from, for example, chain transfer agents, light-blocking agents (light screeners), wetting agents (surface tension modifiers), matting agents, colorants, dyes, pigments, adhesion promoters, fillers, rheology agents / modifiers, flow control or leveling agents, thixotropic agents, plasticizers, light absorbers, light stabilizers, dispersants, antioxidants, antistatic agents, lubricants, opacifiers, antifoaming agents, polymerization inhibitors, and combinations thereof. Generally speaking, the curable composition may contain any additive conventionally used in the field of coatings.

[0108] The curable composition preferably contains no more than 2% by weight, more preferably no more than 1% by weight, more preferably no more than 0.5% by weight, more preferably no more than 0.2% by weight of a matting agent, and more preferably no matting agent. In the sense of the present invention, a "matting agent" is any particle, more particularly a polymeric or inorganic particle, used to create roughness on the surface of a coating, such as, for example, particles of silica, quartz, inorganic oxides, carbonates, nitrides, polyorganosiloxanes, elastomers, or silsesquioxanes or urea-methanal condensates, but excluding particles of the above-mentioned polyamides (which are therefore not included in the term "matting agent" in the context of the present invention).

[0109] The curable composition of the present invention may contain one or more light-blocking agents (also called absorbers). The one or more light-blocking agents may be any known substance, including, for example, non-reactive pigments and non-reactive dyes. The light-blocking agent may be, for example, an agent that blocks visible light or an agent that blocks ultraviolet light. Examples of suitable light-blocking agents include titanium dioxide, carbon black, and organic ultraviolet absorbers, such as hydroxybenzophenone, hydroxyphenylbenzotriazole, oxalanilide, benzophenone, thioxanthone, hydroxyphenyltriazine, Sudan I, bromothymol blue, 2,2'-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole) (especially sold under the trademark Benetex® OB Plus), and benzotriazole-type ultraviolet absorbers. The curable composition may contain the light-blocking agent in an amount of 0.001% to 10% by weight, based on the weight of the curable composition.

[0110] Preparation of the curable composition The curable compositions of the present invention can be prepared by any suitable method. For example, the various components can be combined and mixed in one or more steps. The components, preferably after mixing and / or stirring, can optionally be heated to obtain a particularly homogeneous composition. Other homogenization methods can also be employed. Additionally, as described above, one or more non-reactive solvents can be used. In some embodiments, the polyamide particles are added, preferably slowly, to the other components of the composition at a temperature of 20°C to 90°C while mixing.

[0111] Coating Method The curable compositions described above are used to form coatings on surfaces.

[0112] The coating method according to the present invention comprises applying a curable composition as a layer to a surface.

[0113] The surface can be any type of surface. The surface can be, for example, the surface of a high surface energy substrate, such as a metal substrate, or a low surface energy substrate, such as a plastic substrate. The substrate having a surface can include or consist of one or more metals, paper, cardboard, glass, one or more thermoplastic polymers, such as polyolefins, polycarbonates, acrylonitrile butadiene styrene (ABS) polymers and mixtures thereof, composite materials, wood, leather, or combinations thereof.

[0114] The curable composition can be applied to the surface by any known conventional method. More specifically, the composition can be applied, for example, by spraying, knife coating, roll coating, applicator bar, curtain coating, drum coating, dip coating, or a combination thereof. Application can be carried out at room temperature (i.e., 15 to 30°C) or at higher temperatures, particularly 30 to 60°C. In particular, if the curable composition is not liquid at room temperature or has too high a viscosity, it can be heated to a temperature that allows liquefaction or a reduction in viscosity before application to facilitate application. More specifically, the composition can be heated, for example, to about 50°C for spray applications that require the composition to have a very low viscosity.

[0115] The layer advantageously has a thickness of 100 μm or less (e.g. 1 to 100 μm), preferably 50 μm or less (e.g. 1 to 50 μm), more preferably 20 μm or less (e.g. 1 to 20 μm, preferably 3 to 20 μm, more preferably 10 to 20 μm). In particular, the layer of the curable composition may have a thickness of 1 to 3 μm, or 3 to 5 μm, or 5 to 10 μm, or 10 to 15 μm, or 15 to 20 μm, or 20 to 25 μm, or 25 to 30 μm, or 30 to 40 μm, or 40 to 50 μm, or 50 to 60 μm, or 60 to 70 μm, or 70 to 80 μm, or 80 to 90 μm, or 90 to 100 μm.

[0116] The layer of curable composition is subjected to a step of irradiation with a first radiation. This first radiation is preferably monochromatic or quasi-monochromatic radiation. This first radiation is very advantageously UV radiation, and may also be VUV ("vacuum ultraviolet") radiation. This first radiation is preferably emitted by a UV lamp, more preferably by an excimer lamp. An excimer lamp (or laser) is a gas discharge lamp that emits monochromatic or quasi-monochromatic radiation. Typically, these lamps have a synthetic quartz lamp body filled with xenon (for example, for radiation at 172 nm) or krypton with a chlorine donor (for example, for radiation at 222 nm).

[0117] The irradiation is preferably carried out under an inert gas, more preferably under dinitrogen and / or carbon dioxide, even more preferably under dinitrogen. The residual oxygen content is preferably 1000 ppm or less, more preferably 500 ppm or less.

[0118] More preferably, the first radiation has a wavelength of 100 to 280 nm, preferably 150 to 250 nm, more preferably 150 to 200 nm, more preferably 168 to 180 nm, more preferentially 172 to 175 nm, and even more preferentially 172 nm. For example, the first radiation may have a wavelength of 100 to 125 nm, or 125 to 150 nm, or 150 to 175 nm, or 175 to 200 nm, or 200 to 225 nm, or 225 to 250 nm, or 250 to 280 nm.

[0119] The wavelengths mentioned above allow for surface hardening of the layer of the composition, meaning that the layer is hardened over a small thickness below its surface (typically over a thickness of about 1 μm or less, particularly over a thickness of about 0.5 μm), for example by free radical polymerization and / or cationic polymerization. Hardening only at the surface of the layer leads to the formation of wrinkles on the surface of the layer.

[0120] This produces a partially cured, or more specifically, surface-cured, composition, which generally means that additional curing (or more specifically, curing deeper within the layer of curable composition) is possible.

[0121] The composition is subjected to a step of irradiation with a second radiation, which can be UV radiation or visible light, and / or electron beam radiation.

[0122] According to a first variant, the second radiation is UV radiation or visible light. It may be polychromatic or monochromatic. The second radiation comprises at least one wavelength different from that of the first radiation, more particularly at least one wavelength longer than that of the first radiation. Highly preferably, it has a wavelength spectrum ranging from 100 to 900 nm. Even more preferably, the second radiation has a wavelength spectrum ranging from 180 to 500 nm. Alternatively or additionally, the second radiation may comprise UVA and / or UVB and / or UVC radiation, or may be UVA and / or UVB and / or UVC radiation.

[0123] The second radiation preferably comprises at least one wavelength longer than 280 nm, preferably in the range [longer than 280 nm] to 900 nm, more preferably in the range 285 to 900 nm, and more preferentially in the range 300 to 500 nm (in these embodiments, the second radiation may also optionally comprise wavelengths outside the aforementioned ranges). In particular, the second radiation may comprise at least one wavelength from [longer than 280 nm] to 300 nm, or from 300 to 320 nm, or from 320 to 350 nm, or from 350 to 380 nm, or from 380 to 400 nm, or from 400 to 420 nm, or from 420 to 450 nm, or from 450 to 480 nm, or from 480 to 500 nm, or from 500 to 550 nm, or from 550 to 600 nm, or from 600 to 700 nm, or from 700 to 800 nm, or from 800 to 900 nm.

[0124] This radiation can be emitted by a mercury lamp, more specifically a medium- or high-pressure mercury lamp (mercury vapor optionally doped with elements such as gallium and / or iron), or a metal halide lamp, an electroluminescent diode (or LED, short for "light-emitting diode"), more specifically an LED that emits ultraviolet light, or a pulsed laser lamp (also called a flash lamp). The second radiation is preferably emitted by an undoped mercury lamp, by a doped mercury lamp, or by an LED lamp, the latter preferably having a wavelength of 350 nm to 405 nm.

[0125] The radiation dose applied during irradiation is advantageously between 80 and 4000 mJ / cm 2 , preferably 80 to 2000 mJ / cm 2 , and more preferably 80 to 600 mJ / cm 2 , e.g., 80 to 300 mJ / cm 2 , or 300 to 600 mJ / cm 2 , or 600 to 1000 mJ / cm 2 , or 1000 to 2000 mJ / cm 2 , or 2000 to 3000 mJ / cm 2 , or 3000-4000mJ / cm 2 is.

[0126] According to a second variant, the second radiation is an electron beam. The electron beam preferably has an energy of 70 to 300 keV, preferably 150 to 300 keV, for example 70 to 150 keV, or 150 to 200 keV, or 200 to 250 keV, or 250 to 300 keV. The irradiation dose is advantageously 10 to 100 kGy, preferably 20 to 50 kGy, for example 10 to 20 kGy, or 20 to 30 kGy, or 30 to 40 kGy, or 40 to 50 kGy, or 50 to 70 kGy, or 70 to 100 kGy. Any suitable electron beam emitter can be used, in particular a scanner-type or curtain-type emitter.

[0127] The step of irradiating with the second radiation can optionally be carried out in the absence of oxygen, for example, in an inert gas atmosphere or in an oxygen-deficient atmosphere. In some embodiments, the irradiation can be carried out by covering the composition with a radiation-transparent medium (e.g., a plastic film). In particular, when the second radiation is an electron beam, the irradiation is preferably carried out under an inert gas.

[0128] The irradiation, whether carried out according to the first and / or second variant, allows the layer to continue to harden, for example by free radical and / or cationic polymerization. In particular, it allows the hardening of the part of the layer located under the part hardened during exposure to the first radiation. This layer is preferably hardened throughout its entire thickness. A hardened composition is then obtained. In the sense of the present invention, a "hardened composition" means that the degree of crosslinking of the composition after the step of irradiating with the second radiation is greater than the degree of crosslinking of the partially hardened composition.

[0129] The coating, once cured, preferably has a thickness of 100 μm or less (e.g., 1 to 100 μm), preferably 50 μm or less (e.g., 1 to 50 μm), more preferably 10 to 20 μm. In particular, the cured layer may have a thickness of 1 to 5 μm, or 5 to 10 μm, or 10 to 15 μm, or 15 to 20 μm, or 20 to 25 μm, or 25 to 30 μm, or 30 to 40 μm, or 40 to 50 μm, or 50 to 60 μm, or 60 to 70 μm, or 70 to 80 μm, or 80 to 90 μm, or 90 to 100 μm.

[0130] The method according to the invention may comprise one or more other steps of curing the composition, more particularly by irradiation with actinic radiation. These additional steps may be carried out at any point in the method, in particular before irradiation with the first radiation, between irradiation with the first radiation and irradiation with the second radiation, and / or after irradiation with the second radiation. The radiation used in each of these additional steps may independently be any known type of radiation.

[0131] In particular, the method according to the present invention can include an irradiation step (herein referred to as a "pre-crosslinking step") prior to the irradiation with the first radiation, which pre-crosslinking step is preferably carried out using UV radiation, more particularly UVA radiation. Pre-crosslinking is advantageously carried out using radiation with a wavelength of 200 to 420 nm, more preferably 280 to 420 nm. In some embodiments, the wavelength of the pre-crosslinking radiation can be 200 to 280 nm, or 280 to 320 nm, or 320 to 380 nm, or 380 to 420 nm. The radiation dose applied is preferably 25 to 120 mJ / cm. 2 , more preferably 30 to 100 mJ / cm 2 This radiation can be emitted by any suitable light source, in particular an LED lamp, a low-, medium- or high-pressure mercury lamp (optionally doped with other elements such as gallium or iron), a pulse (or flash) lamp, or a halogen lamp.

[0132] The radiation sources for the first and second radiation, and possibly other radiation (e.g., pre-crosslinking radiation), may be independently fixed or mobile. When the radiation source is fixed, the object whose surface is covered with the composition to be irradiated is preferably moved past the irradiation source, for example, by a device such as a conveyor belt. When the irradiation source is mobile, the object containing the composition to be irradiated is preferably kept fixed during the irradiation step by the irradiation source.

[0133] The above method can be repeated one or more times, and thus another layer of curable composition can be applied to the layer of cured composition and then subjected to curing by exposure to actinic radiation, more specifically according to the method as described above.

[0134] The coating advantageously has a specular gloss at 85° of less than or equal to 10 GU, preferably less than or equal to 8 GU. Specular gloss at 85° can be measured according to ISO standard 2813:2014.

[0135] According to another aspect, the present invention relates to a coating layer obtained or obtainable from a curable composition as described above, more particularly obtained or obtainable by a method as described above.

[0136] According to another aspect, the present invention relates to an object comprising a surface covered with a coating layer obtained or obtainable from a curable composition as described above. The present invention also relates to an object comprising a surface covered with a coating layer obtained or obtainable by a method as described above.

[0137] The object may be, for example, a furniture panel, clothing (especially made of artificial leather), or a floor.

[0138] In another aspect, the present invention relates to the use of an excimer lamp for at least partially curing (or crosslinking) a curable composition comprising at least one compound curable by actinic radiation and particles of at least one polyamide. The excimer lamp advantageously has a wavelength of 150 to 250 nm, preferably 150 to 200 nm, more preferably 168 to 180 nm, and even more preferentially 172 to 175 nm. The curable composition is preferably in the form of a layer. The above explanations, which specifically relate to the curable composition, the polyamide, the layer of the curable composition, and the excimer lamp, and their uses, are equally applicable to this aspect of the invention. [Example]

[0139] The following examples illustrate the invention without limiting it.

[0140] Preparation of the curable composition The following curable compositions were prepared containing the components in the amounts (expressed as weight percentages) specified in the table below.

[0141] [Table 1] TIFF2025533968000002.tif136170

[0142] Composition A is a comparative curable composition, and compositions 1, 2 and 3 are curable compositions according to the invention.

[0143] The compositions were prepared as follows. - Preparation of polyamide 12 powder pre-dispersion (Premix B) Five grams of polyamide 12 powder was introduced into a mixture of 47.5 grams of acrylate-functionalized epoxy oligomer (CN2003EU, Sartomer) and 47.5 grams of 1,6-hexanediol diacrylate (SR238, Sartomer) using a turbine-equipped disperser while stirring at 1,000 revolutions per minute. The polyamide 12 powder was introduced in small portions over approximately 15 minutes to ensure proper dispersion of the powder. Once the introduction was complete, the mixture was left for another 15 minutes with stirring. Preparing a premix of the PA12 powder in the CN2003EU product allowed for effective dispersion of the polyamide 12 powder during the preparation of the final composition. -Preparation of the composition: - Composition A (comparison): Using the same disperser, 195.10 g of acrylate-functionalized epoxy oligomer (Sartomer CN2003EU) was diluted with stirring in 195.10 g of 1,6-hexanediol diacrylate (Sartomer SR238). Subsequently, the following were introduced in this order with stirring: 2.00 g of phosphine oxide photoinitiator (Lambson Speedcure® TPO-L) and 7.80 g of hydroxyacetophenone photoinitiator (Lambson Speedcure® 84). The mixture was left stirring for another 15 minutes. - Composition 1: Using the same disperser, 35.10 g of acrylate-functionalized epoxy oligomer (Sartomer CN2003EU) was diluted with stirring in 35.10 g of 1,6-hexanediol diacrylate (Sartomer SR238). Subsequently, the following were introduced in this order with stirring: 28.10 g of Premix B, then 0.40 g of phosphine oxide photoinitiator (Lambson Speedcure® TPO-L) and 1.40 g of hydroxyacetophenone photoinitiator (Lambson Speedcure® 84). The mixture was left stirring for another 15 minutes. - Composition 2: Using the same disperser, 35.10 g of acrylate-functionalized epoxy oligomer (Sartomer CN2003EU) was diluted with stirring in 35.10 g of 1,6-hexanediol diacrylate (Sartomer SR238). Subsequently, the following were introduced in this order with stirring: 14.05 g of Premix B, then 0.40 g of phosphine oxide photoinitiator (Lambson Speedcure® TPO-L) and 1.40 g of hydroxyacetophenone photoinitiator (Lambson Speedcure® 84). The mixture was left stirring for another 15 minutes. - Composition 3: Using the same disperser, 35.10 g of acrylate-functionalized epoxy oligomer (Sartomer CN2003EU) was diluted with stirring in 35.10 g of 1,6-hexanediol diacrylate (Sartomer SR238). Subsequently, the following were introduced in this order with stirring: 7.025 g of Premix B, then 0.40 g of phosphine oxide photoinitiator (Lambson Speedcure® TPO-L) and 1.40 g of hydroxyacetophenone photoinitiator (Lambson Speedcure® 84). The mixture was left stirring for another 15 minutes.

[0144] Preparation of coatings Each of the above curable compositions was used to form a coating having a thickness of 12 μm on a polyethylene terephthalate (PET) film.

[0145] To achieve this, the curable compositions were applied to a rigid PET support plate using a 12 μm applicator bar. These compositions were crosslinked according to the following protocol: films coated with the curable compositions were arranged on a conveyor belt and passed sequentially under a UV LED lamp (to pre-crosslink), an excimer lamp, and finally another UV lamp. The operating parameters were as follows: - Belt speed: 10m / s - Crosslinking with a Xeradex® excimer lamp adjusted to a power of 5 W / cm, wavelength of 172 nm, and power of 50%. - Maximum output 200W / cm, output 70% (illuminance 750mW / cm 2 UV crosslinking with an ISTI-400-U-3-80 mercury lamp regulated to 1000 nm (equivalent to 1000 nm) and emitting UVA, UVB, and UVC rays.

[0146] Tests performed: The following tests were carried out on the coatings obtained above. - Coating appearance: The coating was observed by optical microscope and scanning electron microscope. - The number of defects was counted within an 8 cm x 8 cm square on the image obtained by optical microscopy. - Specular gloss at 85°: measured using a glossmeter according to ISO standard 2813:2014. - Buffing resistance: Buffing resistance is estimated as the increase in gloss measured according to ISO standard 2813:2014 after the coating has been rubbed (150 double strokes) with a standardized white wool felt weighted with 3.5 kg according to ISO standard 11640:2018. The smaller the increase in gloss of the rubbed coating, the better the buffing resistance. - Chemical resistance: Chemical resistance is evaluated by rubbing (back and forth) a cotton ball (1.5cm x 1.5cm x 0.5cm) saturated with methyl ethyl ketone and a weight of 1 kg on the surface of the coating. The back and forth movement is carried out and counted until the coating breaks down or peels off from the substrate. The more cycles until this occurs, the better the chemical resistance. - Stain resistance: This property is determined by the change in color (ΔE) of the coating after exposure to black iron oxide dust. The initial color of the coating is measured in accordance with ISO standard 18314 using a Malvern Insitec spectrophotometer at their coordinates L * , a * , b * A 33% solution of black iron oxide in water is applied to the surface of the coating with a soft brush. The solution is left in contact with the coating for 3 hours at 23°C, followed by 1 hour at 60°C and finally drying for 20 hours at 23°C. Excess staining solution is removed with a soft brush and the color of the coating is then measured according to ISO standard 18314 on its coordinate L. * , a * , b * The color difference is measured by the formula ΔE calculated according to TIFF2025533968000003.tif10170 * where ΔL, Δa, and Δb are the coordinates L between the contaminated and uncontaminated coatings according to ISO 18314. * , a * , b * ΔE * The lower the value, the better the stain resistance of the coating.

[0147] result The results are shown in the table below. [Table 2] TIFF2025533968000004.tif41170

[0148] Scanning electron micrographs of the coating formed from Composition A and the coating formed from Composition 3 are shown in Figures 1 and 2, respectively.

[0149] It was found that the coating obtained from the curable composition containing polyamide particles had a uniform appearance, substantially free of any defects, whereas the coating obtained from composition A (which did not contain polyamide particles) showed numerous defects, which were fan-shaped oriented wrinkles.

[0150] Furthermore, coatings obtained from curable compositions according to the present invention are more matte (i.e., have lower gloss), and exhibit better buffing resistance, better chemical resistance, and better stain resistance than coatings obtained from Comparative Composition A.

[0151] Two comparative examples (4 and 5) were prepared in the same manner as composition 1, except that 1.4% silica was added instead of 1.4% polyamide 12 powder. [Table 3] TIFF2025533968000005.tif136170

[0152] [Table 4] TIFF2025533968000006.tif22170

[0153] It was found that the coating obtained from the composition containing silica particles exhibited numerous defects which were fan-shaped oriented wrinkles and therefore had poor resistance to staining due to the presence of attachment points (defects).

Claims

1. A method for coating a surface, comprising the following steps: - A step of applying a layer of curable composition to the surface; - A step of irradiating a curable composition with a first radiation having a wavelength of 100 to 280 nm to obtain a partially cured composition; and - A step of irradiating a partially cured composition with a second radiation and / or an electron beam having at least one wavelength longer than the wavelength of a first radiation to obtain a cured composition. Including; Here, the curable composition comprises at least one compound curable by chemical radiation and at least one polyamide particle. method.

2. The method according to claim 1, wherein the curable composition comprises 0.01% to 2% by weight of at least one polyamide particles, preferably 0.01% to 1.5% by weight of at least one polyamide particles, based on the total weight of the composition.

3. The method according to claim 1, wherein at least one polyamide particle has a median volume diameter Dv50 of 20 μm or less, preferably 1 to 20 μm.

4. The method according to claim 1, wherein the polyamide is selected from the group consisting of polyamide 12, polyamide 11, polyamide 10, polyamide 6, polyamide 6.10, polyamide 6.12, polyamide 6.6, polyamide 10.10, polyamide 10.12, and combinations thereof.

5. The method according to claim 1, wherein at least one chemically ray-curable compound is an ethylenically unsaturated compound, preferably comprising at least one group selected from acrylate, methacrylate, cyanoacrylate, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconate, allyl, propenyl, vinyl, methylidenemalonate, and combinations thereof; more preferably comprising at least one functional group selected from acrylate, methacrylate, and vinyl; and even more preferably comprising at least one functional group selected from acrylate and methacrylate.

6. The method according to claim 1, wherein the curable composition comprises at least one photoinitiator, the at least one photoinitiator preferably selected from the group consisting of benzoin, benzoin ether, acetophenone, benzyl, benzyl ketal, anthraquinone, phosphine oxide, α-hydroxyketone, phenylglyoxylate, α-aminoketone, benzophenone, thioxanthone, xanthone, acridine derivative, phenazene derivative, quinoxaline derivative, triazine derivative, and combinations thereof.

7. The method according to claim 1, wherein the first radiation has a wavelength of 150 to 250 nm, preferably 150 to 200 nm, more preferably 168 to 180 nm, and more preferably 172 to 175 nm.

8. The method according to claim 1, wherein the curable composition is irradiated with a first radiation using an excimer lamp.

9. The method according to claim 1, wherein the second radiation has a wavelength spectrum in the range of 100 to 900 nm, preferably in the range of 180 to 500 nm.

10. The method according to claim 1, wherein the second radiation includes at least one wavelength in the range of 285 to 900 nm, preferably in the range of 300 to 500 nm.

11. The method according to claim 1, wherein the second radiation is emitted by an undoped mercury lamp, a doped mercury lamp, or an LED lamp, preferably at a wavelength in the range of 350 to 405 nm.

12. The method according to claim 1, wherein the layer of curable composition applied to the surface has a thickness of 100 μm or less, preferably 50 μm or less, and more preferably 20 μm or less.

13. A coating layer obtained by the method described in claim 1.

14. An object comprising a surface covered with the coating layer described in claim 13.

15. A composition comprising at least one compound curable by chemical rays, and at least one polyamide particle in an amount of 0.01% to 2% by weight, preferably 0.01% to 1.5% by weight, relative to the total weight of the composition.

16. A coating layer based on the composition described in claim 15.

17. Use of an excimer lamp to at least partially cure the composition according to claim 15.

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