The present invention relates to the field of radiation curable coating compositions for coating a substrate in order to provide it with a low gloss coating. The present invention also relates to a process for producing a low gloss coating from a radiation-curable coating composition.

"Low gloss" surfaces give products a much sought-after aesthetic effect, especially in the wood-furniture, flooring and wall covering industry, because they can create a very natural appearance that contribute to giving greater emphasis to the materiality of the article. At present, the creation of matte surfaces frequently involves the use of coating products the formulation of which contains matting agents made from organic and/or inorganic substances which, by positioning themselves on the coated surface and/or emerging on it, are able to act on the degree of reflection of light, giving the observer the visual sensation of a low gloss surface. However, the use of matting agents produces a worsening of the surface performance of the coating since, not being involved in the crosslinking and polymerization process, they lead to a significant reduction of resistance to chemical agents. Moreover, the incorporation of these matting agents in the formulation of the coating product significantly influences the rheology modifying the viscosity thereof to the point that it is impossible to use high concentrations of such matting agents without negatively altering the "application" characteristics of the coating product.

Further there is a tendency for the matting agent to migrate to the coating surface after application and consequently the matting agent might get lost upon mechanical deformation, caused by for example scratch, resulting in an increase of gloss.

The resistance to typical household chemicals, such as coffee, red wine and/or mustard, is also strongly reduced by the use of matting agents. Long-term action of these household chemicals leads at least to a reduction in quality of the coating and possibly even to its complete destruction.

The object of the present invention is to provide a method for obtaining a low gloss coating with an at least good visual appearance from a radiation-curable coating composition.

According to the invention there is provided a process for producing a coating from a radiation-curable coating composition, wherein the process comprises

(1) Irradiating the radiation-curable coating composition with UV light having a wavelength < 220 nm under inert gas, followed by (2) Irradiating with UV light having a wavelength > 300 nm or with E-beam, wherein the radiation-curable coating composition comprises

(A) One or more polymers selected from the group of ester functional polymers (A) with a weight average molecular weight of from 6000 to 500000 g/mol, and

(B) One or more radiation-curable diluents (B) with a molar mass less than 750 g/mol and with an acrylate functionality of 2 or 3, and wherein the amount of (A) is from 5 to 60 wt.% and the amount of (B) is from 40 to 95 wt.%, based on the total amount of (A) and (B), and the total amount of (A) and (B) is at least 50 wt.% by weight of the radiation-curable coating composition.

It has surprisingly been found that the method of the present invention makes it possible to obtain low gloss coatings with an at least good visual appearance, preferably with a very good or excellent visual appearance, from radiation-curable coating compositions as defined herein, without having to use matting agents.

WO-A-2013/092521 describes a process for the production of homogeneous matted coatings on flat surfaces based on a so-called 100% radiation-curable coating compositions. In this method, first, the 100% radiation-curable coating composition, that contains a low molecular weight, radiation-curable oligomer as binder and optionally one or more reactive thinners to reduce the viscosity, is coated on the surface of a flat substrate with a spiral blade. This wet paint layer is subsequently irradiated with UV light with a wavelength of from 200 to 420 nm and a radiation dose of 25 to 120 mJ/cm ² resulting in partial gelation of the coating composition. Then the so-obtained coating is irradiated with UV light from an Excimer lamp having a wavelength from 120 nm to 230 nm under inert gas, followed by finish curing using conventional UV emitters. WO-A-2013/092521 does not teach that low gloss coatings could be obtained from radiation-curable coating composition containing high molecular weight polymer as binder. According to Bauer et all (Progress in Organic Coatings vol 64, p474-481 , year 2009) production of a low gloss coating by irradiation at < 220nm is due to a wrinkling effect of the surface. In light of this, the current invention is especially surprising as according to US20130101837 the addition of polymers is a facile way to inhibit or even prevent wrinkling.

An additional advantage of the present invention is that with the present invention low gloss coatings with improved coffee, red wine and/or mustard resistance can be obtained compared to when the coating compositions contain matting agent. More in particular with the process of the invention a coating can be obtained with a gloss measured at 20° geometry of angle lower than 10 gloss units and preferably with a gloss measured at 60° geometry of angle lower than 40 gloss units (further referred to as low gloss), more preferably with a gloss measured at 60° geometry of angle lower than 30 gloss units, more preferably lower than 20 gloss units, even more preferably lower than 10 gloss units. The radiation-curable coating composition according to the invention allows to obtain a difference in gloss measured at 60° geometry of angle with and without the excimer radiation step of at least 30 gloss units, preferably of at least 40 gloss units, more preferably of at least 50 gloss units, more preferably of at least 60 gloss units. An additional advantage of the present invention is that handling of matting agents is not required, which is advantageous since matting agents have a large surface area and contain a large proportion of dust-forming small particles that may create exposure and explosion hazards. An additional advantage of not having to use matting agents for obtaining low gloss coatings is that coating compositions with less or no settling and thus improved storage stability can be achieved.

The coating composition used in the process of the invention is radiation-curable. By radiation-curable is meant that radiation is required to initiate crosslinking of the composition. The coating composition used in the process of the invention contains ethylenically unsaturated (C=C) bond functionality which under the influence of irradiation, preferably in combination with the presence of a (photo)initiator can undergo crosslinking by free radical polymerisation.

As used herein, the acrylate functionality of a compound is the number of acrylate functional groups per molecule of the compound.

An acrylate functional group has the following formula:

CH ₂ =CH-C(O)O-

For all upper and/or lower boundaries of any range given herein, the boundary value is included in the range given, unless specifically indicated otherwise. Thus, when saying from x to y, means including x and y and also all intermediate values.

Ester functional polymers (A)

With esters functional polymers is meant polymers with multiple ester groups (-C(O)O-), optionally substituted with O,S or N, i.e. (-OC(O)O-) ( -SC(O)O-), or (-N-C(O)O-). Preferred ester functional polymers are polymers with multiple -C(O)O- groups. This includes the group of polymers with -C(O)O- groups in the polymer backbone and acrylics i.e.

-C(O)O- groups pendent to the polymer backbone. Examples are cellulose acetate butyrate, (meth)acrylate (co)polymers, vinyl acetate (co)polymers and the like. Said one or more ester functional polymers (A) have a weight average molecular weight of at least 6000 g/mol, preferably of at least 7000 g/mol, more preferably of at least 8000 g/mol, even more preferably of at least 10000 g/mol. As used herein, the weight average molecular weight is determined by Size Exclusion Chromatography (SEC) as described further herein.

Said one or more ester functional polymers (A) have a weight average molecular weight of at most 500000 g/mol, preferably of at most 400000 g/mol and more preferably of at most 300000 g/mol.

It has furthermore surprisingly been found that low gloss coatings could even be obtained from radiation-curable coating composition containing, as binder, high molecular weight, ester functional polymers with a high average weight per radiation-curable, ethylenically unsaturation (WPU), as determined using ¹ H NMR as described further herein, i.e. having a low amount of radiation-curable, ethylenically unsaturation on average weight. WO-A- 2013/092521 teaches to apply radiation-curable coating composition, that contains a low molecular weight, radiation-curable oligomer as binder and furthermore according to US20130101837 the addition of polymers is a facile way to inhibit or even prevent wrinkling.

Suitable ester functional polymers (A) for inclusion in the radiation-curable coating compositions used in the process of the invention include ester functional polymers with no radiation-curable, ethylenically unsaturation and ester functional polymers with radiation- curable, ethylenically unsaturation. The preferred ester functional polymers (A) for inclusion in the radiation-curable coating compositions used in the process of the invention include ester functional polymers with an average weight per radiation-curable, ethylenically unsaturation (WPU), as determined using ¹ H NMR as described herein, of preferably higher than 1000 g/mol, more preferably higher than 1200 g/mol, even more preferably higher than 1400 g/mol.

The average weight per radiation-curable, ethylenically unsaturation (WPU) is determined via ¹ H-NMR spectroscopy according to the method described below. More specifically, the WPU of a polyester is calculated according to the following equation:

Wpyr is the weight of pyrazine (internal standard), Wresin is the weight of the ester functional polymer, Wpyr and Wresin are expressed in the same units,

MWpyr is the molecular weight of the pyrazine (= 80 Da) (internal standard).

Apyr is the peak area for methine protons attached to the aromatic ring of pyrazine, and Npyr is the number of the methine protons of pyrazine that is equal to 4.

Ac=c is the peak area for methine protons (,..-CH=...) of the carbon-carbon double bond moiety (,.. >C=C<...) present

Nc=c is the number of methine protons (,..-CH=...) attached to the carbon-carbon double bond moiety (,.. >C=C<...) present

The peak areas of the methine protons of pyrazine and methine protons are determined as follows: a sample of 75 mg of ester functional polymer is diluted at 25 °C in 1 ml deuterated chloroform containing a known amount (mg) of pyrazine as internal standard for performing ¹ H-NMR spectroscopy. Subsequently, the ¹ H-NMR spectrum of the ester functional polymer sample is recorded at 25 °C on a 400 MHz BRLIKER NMR-spectrometer. Afterwards, the chemical shifts (ppm) of the methine protons of pyrazine and the methine protons of Ac=c are identified. Subsequently, with the help of suitable commercially available software for analyzing ¹ H-NMR spectra such as the ACD/Spectrus Processor software provided by ACD/Labs, the peak areas of the methine protons of pyrazine and of Ac=c are determined and these values are used in above mentioned equation to calculate the WPU.

Most preferred ester functional polymers (A) for inclusion in the radiation-curable coating compositions used in the process of the invention include ester functional polymers that do not contain radiation-curable, ethylenically unsaturations.

In a preferred embodiment, said one or more ester functional polymers (A) are (co-)polymers obtained by free radical polymerization of a monomer composition comprising (i) one or more ester functional, ethylenically unsaturated monomers preferably selected from the group consisting of acrylates, methacrylates, itaconates, and any mixture thereof, more preferably selected from the group consisting of acrylates, methacrylates, and any mixture thereof, optionally (ii) (meth)acrylic acid, and optionally (iii) arylalkylene monomers selected from the group consisting of styrene, a-methyl styrene, vinyl toluene, t-butyl styrene, dimethyl styrene and any mixture thereof, especially styrene. Preferably the (meth)acrylates are hydrocarbo (meth)acrylate(s) and conveniently the hydrocarbo moiety may be C1-20 hydrocarbyl, more conveniently C1-12 alkyl, most conveniently C1-8 alkyl. Suitable (meth)acrylate(s) may be selected from: methyl (meth)acrylate, ethyl (meth)acrylate, isooctyl (meth)acrylate, 4-methyl-2-pentyl (meth) acrylate, 2-methylbutyl (meth) acrylate, isoamyl (meth)acrylate, sec-butyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-octyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate and/or mixtures thereof. The ester functional, ethylenically unsaturated monomers preferably contains one or more C1-8 alkyl (meth)acrylates, more preferably the ester functional, ethylenically unsaturated monomers is one or more C1-8 alkyl (meth)acrylates. Preferred examples are methyl (meth)acrylate, ethyl (meth)acrylate, iso-butyl (meth)acrylate, sec-butyl (meth)acrylate and n-butyl (meth)acrylate. More preferred examples are methyl methacrylate, ethyl acrylate, iso-butyl (meth)acrylate, sec-butyl (meth)acrylate and n-butyl (meth)acrylate. The amount of ester functional, ethylenically unsaturated monomers (i) is preferably in the range from 80 to 100 wt.%, more preferably from 90 to 100 wt.% and most preferably from 95 to 100 wt.%. In an embodiment of the invention, it is preferred that the one or more ester functional polymers are free of arylalkylenes.

Said one or more ester functional polymer (A) preferably have a glass transition temperature T _g lower than 150°C, preferably lower than 125°C, more preferably lower than 100°C and preferably higher than -25 °C, more preferably higher than 0 °C, more preferably higher than 25 °C, whereby the glass transition temperature is measured using Differential Scanning Calorimetry according to ISO Standard 1357 as described further herein.

Said one or more ester functional polymer (A) preferably have an acid value, determined titrimetrically by the ISO 2114-2000, of at least 0 mg KOH/g of the ester functional polymer

(A), and preferably lower than 100 mg KOH/g of the ester functional polymer (A), more preferably lower than 90 mg KOH/g of the ester functional polymer (A), even more preferably lower than 80 mg KOH/g of the ester functional polymer (A).

Said one or more ester functional polymer (A) preferably have an OH value, determined titrimetrically by the ISO 4629-2-2016, of at least 0 mg KOH/g of the ester functional polymer (A), and preferably lower than 100 mg KOH/g of the ester functional polymer (A), more preferably lower than 75 mg KOH/g of the ester functional polymer (A), even more preferably lower than 50 mg KOH/g of the ester functional polymer (A).

Radiation-curable diluent (B)

The radiation-curable coating composition comprises one or more radiation-curable diluents

(B) with a molar mass less than 750 g/mol and with an acrylate functionality of 2 or 3. In an embodiment, the radiation-curable coating composition comprises one or more radiation- curable diluent (B) with a molar mass less than 750 g/mol and with an acrylate functionality of 2. In another embodiment, the radiation-curable coating composition comprises one or more radiation-curable diluent (B) with a molar mass less than 750 g/mol and with an acrylate functionality of 3. In still another embodiment, the radiation-curable coating composition comprises one or more radiation-curable diluent (B) with a molar mass less than 750 g/mol and with an acrylate functionality of 2 and one or more radiation-curable diluent (B) with a molar mass less than 750 g/mol and with an acrylate functionality of 3.

The molar mass of the radiation-curable diluents (B) is calculated from their corresponding molecular formulas indicating the numbers of each type of atom in the radiation-curable diluent. Thus, the molar mass of (B) is the calculated molar mass obtained by adding the atomic masses of all atoms present in the structural formula of the compound.

Said one or more acrylate diluents (B) have a molar mass less than 750 g/mol, preferably less than 650 g/mol, more preferably a molar mass of at most 500 g/mol, more preferably of at most 450 g/mol. Said one or more acrylate diluents (B) preferably have a molar mass of at least 125 g/mol, preferably of at least 150 g/mol, more preferably of at least 175 g/mol and even more preferably of at least 200 g/mol.

Preferred examples of said one or more acrylate diluents (B) with an acrylate functionality of 2 are trimethylolpropane diacrylate, 1 ,6-hexane diol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, and any mixture thereof. If appropriate, they may further comprise (additional) alkoxy groups, preferably propoxy groups, whereby the maximum number of alkoxy groups is such that the molar mass remains lower than 750 g/mol. More preferred examples of said one or more acrylate diluents (B) with an acrylate functionality of

2 are dipropyleneglycol diacrylate (DPGDA) (with the corresponding molecular formula C12H18O5 and its corresponding molar mass of 242 g/mol); dipropyleneglycol diacrylate comprising additional alkoxy groups, preferably propoxy groups; and any mixture thereof.

Preferred examples of said one or more acrylate diluents (B) with an acrylate functionalilty of

3 are trimethylolpropane triacrylate, di(trimethylolpropane) triacrylate, pentaerythritol triacrylate, glyceryl propoxy triacrylate, and any mixture thereof. If appropriate, they may further comprise (additional) alkoxy groups, preferably propoxy groups, whereby the maximum number of alkoxy groups is such that the molar mass remains lower than 750 g/mol. More preferred examples of said one or more acrylate diluents (B) with an acrylate functionalilty of 3 are di(trimethylolpropane) tri-acrylate (di-TMP3A) with the corresponding molecular formula C21H32O8 and its corresponding molar mass of 412 g/mol; di(trimethylolpropane) tri-acrylate comprising alkoxy groups, preferably propoxy groups; glyceryl propoxy triacrylate (GPTA) with the corresponding molecular formula C21H32O9 and its corresponding molar mass of 428 g/mol; glyceryl propoxy triacrylate comprising additional alkoxy groups, preferably propoxy groups; pentaerythritol tri-acrylate (PET3A) with the corresponding molecular formula CuH O? and its corresponding molar mass of 298 g/mol; pentaerythritol tri-acrylate comprising alkoxy groups, preferably propoxy groups; trimethylolpropane triacrylate (TMPTA) with the corresponding molecular formula C15H20O6 and its corresponding molar mass of 296 g/mol; trimethylolpropane triacrylate comprising alkoxy groups, preferably propoxy groups; and any mixture thereof.

The radiation-curable diluents (B) with an acrylate functionality of 2 or 3 preferably comprises alkoxy groups, preferably propoxy groups (-CsHeO-).

The radiation-curable coating composition used in the process of the present invention may also comprise acrylate diluents with a molar mass as defined for the (B) compounds present in the radiation-curable coating composition (i.e. lower than 750 g/mol, preferably of at most 650 g/mol, more preferably of at most 500 g/mol, more preferably of at most 450 g/mol and preferably of at least 125 g/mol, more preferably of at least 150 g/mol, more preferably of at least 175 g/mol, even more preferably of at least 200 g/mol) but with a different acrylate functionality than defined for (B), for example with an acrylate functionality of 1, 4, or 5. Such acrylate diluents are preferably present in the radiation-curable coating composition in such an amount that the average acrylate functionality of the acrylate diluents with a molar mass as defined for (B) is in the range of preferably from 2 to 3. As used herein, the average acrylate functionality of the acrylate diluents with a molar mass as defined for (B) = f = y ^w k f

V ^w k in which Wk is the amount of acrylate diluents in g present in the radiation curable coating composition with a molar mass Mk as defined for (B) and with an acrylate functionality f _k which can be as defined for (B) or lower or higher than as defined for (B).

We illustrate the average acrylate functionality calculation with a theoretical example:

For a formulation consisting of 60 grams of ester functional polymer, 30 grams of DPGDA (having molar mass 242 g/mol and acrylate functionality of 2), 10 grams of Di-TMPTA (having molar mass 466 g/mol and acrylate functionality of 4), and 2.5 grams of photoinitiator: the summation over components k includes only DPGDA and Di-TMPTA and the calculated average functionality of acrylate diluents of this theoretical formulation is f = Preferably, the radiation-curable coating composition used in the process of the present comprises monofunctional diluent in an amount less than 7 wt.%, more preferably at less than 5 wt.%, more preferably less than 3 wt.%, more preferably less than 1 wt.%, most preferably less than 0.5 wt.%, relative to the weight of the entire radiation-curable coating composition.

The amount of (A) is from 5 to 60 wt.% and the amount of (B) is from 40 to 95 wt.%, preferably the amount of (A) is from 7 to 55 wt.% and the amount of (B) is from 45 to 93 wt.%, more preferably the amount of (A) is from 10 to 50 wt.% and the amount of (B) is from 50 to 90 wt.%, whereby the amounts of (A) and (B) are given relative to the total amount of (A) and (B).

The summed amount of (A) and (B) is at least 50 wt.%, preferably at least 55 wt.%, more preferably at least 60 wt.%, even more preferably at least 65 wt.%, more preferably at least 70 wt.%, most preferably at least 75 wt.%, based on the entire weight of the radiation- curable coating composition.

The radiation-curable coating composition may further comprise one or more acrylate functional oligomers with a number average molecular weight M _n as determined using Triple Detection Size Exclusion Chromatography with tetra hydrofuran THF as eluent of from 1100 to 5000 g/mol, preferably of at least 1200 g/mol, preferably of at least 1300 g/mol and preferably of at most 4000 g/mol, more preferably of at most 3000 g/mol. Said one or more acrylate functional oligomers are preferably selected from the group consisting of polyether acrylates, polyester acrylates, polyether urethane acrylates, polyester urethane acrylates, epoxy acrylates and any mixture thereof.

The radiation-curable coating composition used in the process of the present invention is preferably substantially free of water and non-polymerizable volatile compounds. As used herein, substantially free of water and non-polymerizable volatile compounds means that the composition contains less than 20 wt.%, preferably less than 10 wt.% more preferably less than 5 wt.%, more preferably less than 3 wt.%, more preferably less than 1 wt.% of water and non-polymerizable volatile compounds by weight of the radiation-curable coating composition of the present invention. A non-polymerizable volatile compound is a compound having an initial boiling point less than or equal to 250° C measured at a standard atmospheric pressure of 101.3 kPa. The coating composition usually further contains an additive compound; that is, a collection of one or more than one individual additives having one or more than one specified structure or type. Suitable additives are for example light stabilizers, such as UV absorbers and reversible free-radical scavengers (HALS), photosensitizers, antioxidants, degassing agents, wetting agents, emulsifiers, slip additives, waxes, polymerization inhibitors, adhesion promoters, flow control agents, film-forming agents, rheological aids such as thickeners, flame retardants, corrosion inhibitors, waxes, driers and biocides. One or more of the aforementioned additives can be employed in the coating composition used in the process of the present invention in any suitable amount and may be chosen singly or in combination of one or more of the types enumerated herein. In a preferred embodiment, the additive compound is present in an amount, relative to the entire weight of the radiation-curable coating composition, of from about 0 wt.% to 40 wt.%, or from 0 wt.% to 30 wt.%, or from 0 wt.% to 20 wt.%, or from 0 wt.% to 10 wt.%, or from 0 wt.% to 5 wt.%; or from 0.01 wt.% to 40 wt.%; or from 0.01 wt.% to 30 wt.%, or from 0.01 wt.% to 20 wt.%, or from 0.01 wt.% to 10 wt.%, or from 0.01 wt.% to 5 wt.%, or from 0.1 wt.% to 2 wt.%. An additional advantage of the present invention is that the coating composition can also be pigmented, while this does not significantly complicate the application of the coating composition on the substrate. The coating composition then contains at least one pigment. The coating composition can also contain external matting agents which have an additional matting effect, although this is not preferred. Suitable external matting agents are for example inorganic silica or organic waxes. The maximum amount of external matting agents is preferably at most 1.5 wt.%, more preferably at most 1 wt.% and most preferably at most 0.5 wt.%, relative to the entire weight of the coating composition.

The process of the present invention comprises

(1) Irradiating a radiation-curable coating composition with UV light having a wavelength < 220 nm under inert gas, preferably with a wavelength > 120 nm is applied, more preferably > 150 nm, particularly preferably 172 nm or 195 nm, causing micro-folding followed by

(2) Irradiating with UV light having a wavelength > 300 nm or with E-beam.

Suitable radiation sources for step (1) are excimer UV lamps, which emit UV light with a wavelength < 220 nm and preferably with a wavelength > 120 nm, more preferably > 150 nm, particularly preferably 172 nm or 195 nm. The radiation dose used in step (1) is usually in the range from 0.1 to 150 mJ/cm ² , preferably in the range of from 1 to 100 mJ/cm ² , more preferably from 1 to 20 mJ/cm ² , more preferably from 2 to 15 mJ/cm ² . Step (1) must be performed in an inert gas atmosphere. An inert gas atmosphere is understood to mean an essentially oxygen-free atmosphere, i.e. an atmosphere which contains less than 0.5 percent by volume of oxygen, preferably less than 0.1 percent by volume of oxygen and especially preferably less than 0.05 percent by volume of oxygen. As a rule, an inert gas atmosphere is achieved by flushing the area which is exposed to the UV radiation with a stream of inert gas. The inert gas atmosphere prevents undesired ozone formation on the one hand and prevents the polymerization of the lacquer layer from being inhibited on the other hand. Examples of inert gases are nitrogen, helium, neon or argon. Nitrogen is particularly preferably used. This nitrogen should only contain very small amounts of foreign gases such as oxygen, preferably with a purity grade of < 300 ppm oxygen.

In step (2) of the process of the present invention, the coating layer obtained in step (1) is irradiated with UV light having a wavelength > (higher than or equal to) 300 nm or with E- beam to achieve that the radiation-curable compounds of the coating composition largely or preferably completely polymerizes, so that the coating layer is preferably fully cured. In case E-beam irradiation (150 to 300 kV) is applied in step (2), usually a dose of 10 to 100 kGy, preferably 20 to 50 kGy, is applied. In step (2) UV irradiation is preferred, preferably with a wavelength of from 300 to 420 nm and preferably with a radiation dose of from 100 to 4000 mJ/cm ² , more preferably from 150 to 2500 mJ/cm ² . High- and medium-pressure mercury vapour lamps can in particular be used as UV radiation sources, wherein the mercury vapour can be doped with further elements such as gallium or iron. Step (2) can optionally also be performed in an inert gas atmosphere. In case UV irradiation is applied in step (2), the radiation-curable coating composition comprises a photo-initiator. If the radiation curable coating composition of the invention comprise one or more photo-initiators, they are included in an amount sufficient to obtain the desired cure response. Typically, the one or more photo-initiators are included in amounts in a range of from 0.1 to 10% by weight of the coating composition. Preferably, the one or more photo-initiators are present in an amount, relative to the entire weight of the coating composition, of from 0.25 wt.% to 10 wt.%, more preferably from 0.5 wt.% to 8 wt.% and even more preferably from 0.5 wt.% to 5 wt.%. A photoinitiator is a compound that chemically changes due to the action of light or the synergy between the action of light and the electronic excitation of a sensitizing dye to produce at least one of a radical, an acid, and a base. Well-known types of photoinitiators include cationic photoinitiators and free-radical photoinitiators. According to an embodiment of the present invention, the photoinitiator is a free-radical photoinitiator.

In an embodiment, the photoinitiator compound includes, consists of, or consists essentially of one or more acylphosphine oxide photoinitiators. Acylphosphine oxide photoinitiators are known, and are disclosed in, for example, U.S. Pat. Nos. 4324744, 4737593, 5942290, 5534559, 6020529, 6486228, and 6486226. Preferred types of acylphosphine oxide photoinitiators for use in the photoinitiator compound include bisacylphosphine oxides (BAPO) or monoacylphosphine oxides (MAPO). More specifically, examples include 2,4,6- trimethylbenzoylethoxyphenylphosphine oxide (CAS# 84434-11-7) or 2,4,6- trimethylbenzoyldiphenylphosphine oxide (CAS# 127090-72-6).

In a preferred embodiment, the photoinitiator compound may also optionally comprise, consist of, or consist essentially of a-hydroxy ketone photoinitiators. For instance, suitable a-hydroxy ketone photoinitiators are a-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2- methyl-1 -phenylpropanone, 2-hydroxy-2-methyl-1-(4-isopropylphenyl)propanone, 2-hydroxy- 2-methyl-1-(4-dodecylphenyl)propanone, 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)- benzyl]-phenyl}-2-methyl-propan-1 -one and 2-hydroxy-2-methyl-1 -[(2- hydroxyethoxy)phenyl]propanone.

In another embodiment, the photoinitiator compound includes, consists of, or consists essentially of: a-aminoketones, such as 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)- 1 -propanone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-but anone, 2-(4- methylbenzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1 -butanone or 2-benzyl-2- (dimethylamino)-1-[3,4-dimethoxyphenyl]-1-butanone; benzophenones, such as benzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 2- methylbenzophenone, 2-methoxycarbonylbenzophenone, 4,4’-bis(chloromethyl)- benzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone, 4,4’-bis(dimethylamino)- benzophenone, 4,4’-bis(diethylamino)benzophenone, methyl2-benzoylbenzoate, 3,3’- dimethyl-4-methoxybenzophenone, 4-(4-methylphenylthio)benzophenone, 2,4,6-trimethyl-4’- phenyl-benzophenone or 3-methyl-4’-phenyl-benzophenone; ketal compounds, for example 2,2-dimethoxy-1,2-diphenyl-ethanone; and monomeric or dimeric phenylglyoxylic acid esters, such as methylphenylglyoxylic acid ester, 5,5’-oxo-di(ethyleneoxydicarbonylphenyl) or 1,2-(benzoylcarboxy)ethane.

Yet further suitable photoinitiators for use in the photoinitiator compound include oxime esters, such as those disclosed in U.S. Pat. No.6, 596, 445. Still another class of suitable photoinitiators for use in the photoinitiator compound include, for example, phenyl glyoxalates, for example those disclosed in U.S. Pat. No. 6,048,660.

In another embodiment, the photoinitiator compound may comprise, consist of, or consist essentially of one or more alkyl-, aryl-, or acyl- substituted compounds not mentioned above herein.

According to another embodiment, the composition may contain a photoinitiator that is an alkyl-, aryl-, or acyl- substituted compound. In an embodiment the alkyl-, aryl-, or acylsubstituted photoinitiator possesses or is centered around an atom in the Carbon (Group 14) group. In such instance, upon excitation (via absorption of radiation) the Group 14 atom present in the photoinitiator compound forms a radical. Such compound may therefore produce a radical possessing or centered upon an atom selected from the group consisting of silicon, germanium, tin, and lead. In an embodiment, the alkyl-, aryl-, or acyl-substituted photoinitiator is an acylgermanium compound. Such photoinitiators are described in, US9708442.. Known specific acylgermanium photoinitiators include benzoyl trimethyl germane (BTG), tetracylgermanium, or bis acyl germanoyl (commercially available as Ivocerin® from Ivoclar Vivadent AG, 9494 Schaan/Liechtenstein).

Photoinitiators may be employed singularly or in combination of one or more as a blend. Suitable photoinitiator blends are for example disclosed in U.S. Pat. No. 6,020,528 and U.S. Pat. App. No. 60/498,848. According to an embodiment, the photoinitiator compound includes a photoinitiator blend of, for example, bis(2,4,6-trimethylbenzoyl) phenyl phosphine oxide (CAS# 162881-26-7) and 2, 4, 6, -trimethylbenzoylethoxyphenylphosphine oxide (CAS# 84434-11-7) in ratios by weight of about 1:11, 1:10, 1 :9, 1 :8 or 1 :7.

Another especially suitable photoinitiator blend is a mixture of bis(2,4,6- trimethylbenzoyl)phenyl phosphine oxide, 2, 4, 6, -trimethylbenzoylethoxyphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1 -propanone (CAS# 7473-98-5) in weight ratios of for instance about 3:1:15 or 3:1 :16 or 4:1 :15 or 4:1:16. Another suitable photoinitiator blend is a mixture of bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide and 2-hydroxy-2-methyl-1- phenyl-1 -propanone in weight ratios of for instance about 1 :3, 1:4 or 1 :5.

One or more of the aforementioned photoinitiators can be employed for use in the photoinitiator compound in compositions according to the present invention in any suitable amount and may be chosen singly or in combination of one or more of the types enumerated herein. In a preferred embodiment, the photoinitiator compound comprises, consists of, or consists essentially of free-radical photoinitiators, preferably of the a-cleavage type.

The process of the present invention optionally includes an additional radiation curing step prior to the excimer radiation step, i.e. prior to the step of irradiating by UV light with a wavelength < 220 nm under inert gas. In this additional radiation curing step irradiation is preferably effected with UV light having a wavelength of from 300 nm to 450 nm with a radiation dose which results in partial curing of the coating composition. Accordingly, the process of the invention for producing a coating from a radiation-curable coating composition comprises the following steps:

(la) Providing an uncured layer of a radiation-curable coating composition as defined herein above on a surface of a substrate,

(lb) Optionally irradiating the uncured layer from step (1) with UV light having a wavelength of from 300 to 450 nm, preferably from 300 to 420 nm with a radiation dose which results in partial curing of the layer, preferably with a radiation dose from 20 to 200 mJ/cm ² , more preferably with a radiation dose from 30 to 100 mJ/cm ² , (1) Irradiating the uncured layer from step (1a) or the partially cured layer from step (1b) with UV light having a wavelength of < (lower than or equal to) 220 nm under inert gas, and

(2) Irradiating the coating layer from step (1) with UV light having a wavelength > (higher than or equal to) 300 nm or with E-beam.

In step (1a) the radiation-curable coating composition is applied to a substrate by methods known to the person skilled in the art, such as for example knife coating, brushing, roller coating. The coating composition is applied to the substrate in a coating thickness (before curing) of preferably from 3 to 150 micron, more preferably from 3 to 120 micron, more preferably from 3 to 100 micron, more preferably from 3 to 50 micron, even more preferably from 3 to 30 micron and even more preferably from 5 to 30 micron. In a preferred embodiment of the invention, the curing of the radiation-curable coating composition is effected in only 2 irradiation steps (i.e. step (1) and (2)). In this preferred embodiment, the radiation-curable coating composition may be applied to the substrate in a coating thickness (before curing) of at most 150 micron, more in particular of at most 120 micron, more in particular of at most 100 micron and more in particular of at most 50 micron.

In optional step (1b) some of the reactive ethylenically unsaturated double bonds of the curable compounds polymerize in the uncured coating layer, so that the coating layer partially cures but is not yet fully cured. This process is also known as pre-curing. The irradiating in step (1b) preferably takes place under atmospheric conditions, in other words not under inert gas conditions and/or not in an oxygen-reduced atmosphere. UV-A-emitting radiation sources (e.g. fluorescent tubes, LED lamps), high- or medium-pressure mercury vapour lamps, wherein the mercury vapour can be modified by doping with other elements such as gallium or iron, pulsed lamps (known as UV flash lamps) or halogen lamps are suitable as radiation sources for UV light in the specified wavelength range in step (1b). In a preferred embodiment of the invention, the process is performed without step (1b).

Suitable substrates for the process according to the invention are for example mineral substrates such as fiber cement board, wood, wood containing materials, paper including cardboard, textile, leather, metal, thermoplastic polymer, thermosets, ceramic, glass.

Suitable thermoplastic polymers are for example polyvinylchloride PVC, polymethylmethacrylate PMMA, acrylonitrile-butadiene-styrene ABS, polycarbonate, polypropylene PP, polyethylene PE, polyamide PA, polyethylene terephthalate PET and polystyrene PS. Suitable thermosets are for example linoleum, epoxy, melamine, novolac, polyesters and urea-formaldehyde. The substrate is optionally pre-treated and/or optionally pre-coated. For example, thermoplastic plastic films can be treated with corona discharges before application or precoated with a primer. Mineral building materials are also usually provided with a primer before the coating composition is applied.

The coating obtained in the process of the invention can advantageously be used in a floor or wall covering or in automotive interior or on furniture.

With the process of the invention, low gloss coatings can advantageously be obtained with a dry thickness of at least 3 micron, or of at least 4 micron, or of at least 5 micron, and of at most 150 micron, or of at most 100 micron, or of at most 75 micron, or of at most 50 micron.

The present invention further relates to the radiation-curable coating composition as described herein above. The present invention further relates to a coated substrate that is obtained by coating a substrate with the process as described herein above.

The present invention is now illustrated by reference to the following examples. Unless otherwise specified, all parts, percentages and ratios are on a weight basis.

Method to calculate the dry film thickness

The dry film thickness is calculated by multiplying the wet film thickness times the solids content of the formulation used.

DFT = WFT* solids content/100

Where

DFT: dry film thickness in pm

WFT: wet film thickness in pm

Solids content (wt.%): total weight of all solid compounds present in formulation divided by (total weight of the formulation *100).

Weight average molecular weight M _w

The weight average molecular weight M _w is determined by Size Exclusion Chromatography (SEC) using a method which is a modification of ISO/FDIS 13885-1 and DIN 55672: Weigh-in approximately 32 mg sample (re-calculated to 100% solids) into a 10ml culture tube with screw cap and PTFE inlay. Add approximately 8 ml Tetrahydrofuran (THF), 99.8%, stabilised with Bis Hydroxy Toluene (250 mg per liter) and mix regularly until completely dissolved. Accordingly, 1 pL is injected on a SEC apparatus consisting of eluent reservoir, degasser, pump delivering a pulse free reproducible and constant flow (Flow rate 1.0 mL/min +/- 0.1%), injection system with no memory effects (Reproducibility 1% or better, carry over less than 0.1%), column(s) (1 x PLgel 5pm Guard 50x7.5mm + 3 x PLgel 5pm Mixed-C 300x7.5mm), differential refractometer (cell volume < 1 Opl) and data station with GPC software. Molecular weight is calculated from the resulting chromatogram using polystyrene Mp 160-10,000,000 Daltons (polymer standard service (PSS) DIN certified) standards. Glass transition temperature, T _g

The glass transition temperature is determined using Differential Scanning Calorimetry according to ISO Standard 1357. Thermal characteristics of the samples were investigated under a nitrogen atmosphere using a Q2000 DSC from TA Instruments. The DSC sample is prepared by sealing approximately 5 mg sample in a standard aluminum pan. Indium was used for the enthalpy and temperature calibration of the instrument and an empty pan was used as the reference. The thermal transitions of the samples were investigated with the temperature program described in the Table below. The first heating to 160°C erased the thermal history of the samples and reported thermal characteristics were obtained from the second heating curve. DSC temperature program

Materials

Preparation of formulations used in Examples 1-19 and Comparative Experiments 1-9

A vessel was charged with the diluents listed in the table below. Under mechanical stirring, after heating to around 65°C the ester functional polymers were slowly added to the diluent. After complete addition the mixture was stirred until a clear solution was obtained. Next the photoinitiator was dissolved into the formulation. Application of formulations

The formulations obtained were applied on a Leneta card (2C Leneta Inc) using a 12pm wire rod applicator (#2 K bar, RK Printcoat Instruments Ltd) unless otherwise stated.

Curing of the formulations

Excimer/UV cure:

Immediately (within 20 seconds) after application the formulations were cured on a UVio curing rig with a conveyor belt speed of 15 m/min equipped with 2 lamps. The first Lamp was a Excirad 172 lamp (IOT GmbH, xenon based excimer lamp generating 172nm light) under which the cure was performed with a radiation dose of 6.9mJ/cm ² (determined with an ExciTrack172, IOT GmbH) in a nitrogen atmosphere (02 level < 50 ppm detected with IOT inline detector). The next cure step was performed by the second lamp being a Light Hammer 10 Mark II equipped with a H-bulb operating @ 75% power (Heraeus Holding, Hg doped UV lamp generating UV light with wave lengths >300 nm, 327 mJ/cm ² total dose as determined with a Power Puck II (EIT Inc)).

Conventional UV cure inert (Conv UV cure inert):

Immediately (within 20 seconds) after drying the formulations were cured on a UVio curing rig with a conveyor belt speed of 15 m/min. The cure step was performed by a Light Hammer 10 Mark III equipped with a H-bulb operating @ 75% power (Heraeus Holding, Hg doped UV lamp generating UV light with wave lengths >300 nm, 327 mJ/cm ² total dose as determined with a Power Puck II (EIT Inc)).

Testing of the cured formulations

The gloss, the coffee, red wine and mustard resistances, and the visual appearance of the cured coatings were determined as described above Gloss

The gloss is determined according to ISO2813 in the direction of the drawdown and is expressed in gloss units (GU).

Stain resistances

The coffee, red wine and mustard resistances were determined colorimetric using an eXact Standard Handheld Spectrophotometer from X-rite and are reported in Tables 5 and 6. For coffee, the spot exposure time was 1 hr resp. 6 hr and was rated after 24hrs. For red wine and mustard, the spot exposure time was 6 hr and was rated after 24hrs The a- and fa- values were measured according to ISO 7724. The coffee and mustard resistances were determined by Ab value where Ab-value = bfafter resp 6 and 1 hr coffee exposure or 6 hr mustard exposure and rated after 24 hours) - before exposure). A higher Ab value indicates larger colour change due to staining, therefore worse stain resistance performance. The red wine resistance was determined colorimetric using Aa value where Aa-value ^— Sfafter 6 hr red wine exposure and rated after 24 hours) ^— 3(before exposure). A higher Aa value indicates larger colour change due to staining, therefore worse stain resistance performance. The a* axis is relative to the green-red opponent colours, with negative values toward green and positive values toward red. The b*axis represents the blue-yellow opponents, with negative numbers toward blue and positive toward yellow.

Visual appearance

The visual appearance was rated from 0 to 5, where

0=very bad or insufficient cure, unable to measure gloss 1=very poor, no cohesive film , unable to measure gloss 2= poor, many defects, gloss measurements unreliable 3=good, defects visible, low gloss

4=very good, some minor defects visible, low gloss

5= excellent, low gloss

As used herein, a coating with an at least good visual appearance is a coating with a visual appearance with a rating of at least 3, preferably of at least 4.

In the following examples and comparative experiments, the formulations were cured with the Excimer/UV cure process, unless indicated differently. In some comparative experiments, the formulations were cured with the Conventional UV cure inert process (Conv UV cure inert), as indicated in the Tables below.

Table 1

Table 1 demonstrates that Eximer/UV cure is required for low gloss

Table 2

Table 2 demonstrates that the radiation-curable diluent (RD) should have an acrylate functionality of 2 or 3 and that methacrylate functional radiation-curable diluents do not work. Na = not applicable. Table 3

Table 3 shows that M _w of the ester functional polymer should be > 5000 g/mol. Table 4

Table 5 Mixtures of diluents

Table 5 demonstrates that mixtures of radiation-curable diluents can be used with an average functionality of between 2 and 3

Table 6: Effect of layer thickness on gloss values for formulation of Ex. 1 (25% B-725 in DPGDA)

Table 7: Effect of layer thickness on gloss values for formulation of Ex. 6 (25% B-875 in DPGDA)

Table 6 and 7 show that with the process of the invention, low gloss coatings can be obtained for various layer thicknesses.

Table 8: Stain resistances of formulations of Examples 1, 6 and 7 when cured with Excimer and conventional cure, both under inert atmosphere.

The stain resistances are very good resulting in very low delta b en delta a values.