Active radiation curable coating compositions containing bio-based monomers

Abstract

The present invention relates to an active radiation-curable coating composition comprising: 10 to 90 wt. % of a poly(trimethylene ether) (meth)acrylate compound A having up to two (meth)acrylate groups, which compound A is obtainable by a condensation reaction of a bio-based 1,3 poly(trimethylene ether) glycol having a number average molecular weight Mn of 350 to 600 g / mol, more preferably 400 to 550 g / mol, with a (meth)acrylate compound selected from the group consisting of (meth)acrylic acid, (meth)acryloyl chloride, and / or alkyl esters thereof; and 10 to 89.99 wt. % of an ethylenically unsaturated oligomeric compound B, different from compound A, having a viscosity at 25°C greater than 5 Pa·s.

Description

[Technical Field]

[0001] The present invention relates to an active radiation-curable coating composition containing poly(trimethylene ether) (meth)acrylate and an ethylenically unsaturated oligomeric compound having high viscosity, which coating composition exhibits high-performance coating properties after curing. The present invention further relates to a method for forming a coating on a substrate with such a coating composition; and to the use of poly(trimethylene ether) (meth)acrylate as a diluent monomer in such an active radiation-curable coating composition. [Background technology]

[0002] Active radiation-curable compositions have been used for many years for numerous types of coating applications and typically contain (meth)acrylate compounds. Many coating compositions contain viscous (meth)acrylate oligomers that can provide specific properties to the deposited material after curing. Typical types of properties include flexibility, toughness, solvent / stain resistance, and glass transition properties, which are controlled by the viscous (meth)acrylate oligomers present in the formulation. While high-viscosity resins can be used in some applications, low-viscosity resins may be more practical in other applications. It is well known in the art that diluent monomers, which are low-viscosity (meth)acrylate compounds, are often added to these oligomers to adjust viscosity. It is important to control the balance so that the properties provided by the oligomer can be maintained as much as possible without being diminished by adding too much diluent monomer. In fact, too much monomer content can result in a coating that is, for example, more brittle after curing. The type of monomer selected also affects the properties of the final coating.

[0003] In general, there is an increasing demand in the market for more sustainable coatings, and therefore more sustainable active radiation-curable compositions. One way to increase the sustainability of resins is by increasing the biobased carbon content. Patent application WO2012 024402 describes biobased radiation-curable coating compositions having poly(trimethylene ether)urethane (meth)acrylates made by reacting isocyanates with biobased poly(trimethylene ether)diols. It is noted that these compounds have very high viscosities, and many monomers are used to reduce the viscosity. Summary of the Invention [Problem to be solved by the invention]

[0004] It is an object of the present invention to provide active radiation curable compositions with increased sustainability. A further object is to provide diluent monomers suitable for active radiation curable compositions with bio-based carbon content while maintaining or improving the coating properties of the formulation in which the monomer is used. A further object is to provide molecules that help increase the bio-based carbon content of the coating composition. [Means for solving the problem]

[0005] In a first aspect, the present invention provides an active radiation curable coating composition comprising the following compound: a. 10 to 90 wt. % of a poly(trimethylene ether) (meth)acrylate compound A having up to two (meth)acrylate groups, which can be obtained by a condensation reaction between a bio-based 1,3 poly(trimethylene ether) glycol having a number average molecular weight Mn of 350 to 600 g / mol, more preferably 400 to 550 g / mol, and a (meth)acrylate compound selected from the group consisting of (meth)acrylic acid, (meth)acryloyl chloride, and / or alkyl esters thereof, based on the total weight of the coating composition; b. 10% to 89.99% by weight of an ethylenically unsaturated oligomeric compound B different from compound A and having a viscosity greater than 5 Pa·s at 25°C, based on the total weight of the coating composition; c. optionally, a low molecular weight ethylenically unsaturated monomeric compound C; d. Optionally, a further compound D which is a polymer without reactive ethylenically unsaturated groups. The present invention relates to a composition comprising:

[0006] According to another aspect, the present invention relates to the use of a poly(trimethylene ether) (meth)acrylate compound A having up to two (meth)acrylate groups as a diluent monomer in an active radiation-curable coating composition.

[0007] In yet another aspect of the present invention, there is provided a method of forming a coating comprising the steps of applying a layer of an active radiation curable coating composition according to the first aspect to at least a portion of a substrate and subjecting the coated substrate to curing conditions.

[0008] In yet another aspect, the present invention relates to the use of the active radiation curable composition according to the first aspect in additive manufacturing, laminating adhesives, waterproofing membranes or inks.

[0009] In another aspect, the present invention relates to a substrate in contact with a coating composition according to the first aspect. [Brief explanation of the drawings]

[0010] [Figure 1] Mw distribution of PPDODA determined by standard gel permeation chromatography (GPC). Figure 1 shows the Mw distribution diagram for the poly(trimethylene ether) diacrylate of Example 1, where the X-axis shows Log Mw in g / mol and the Y-axis shows dW / dLogMw (normal distribution of slice molecular weights or molecular weight-normalized area of ​​the slices). DETAILED DESCRIPTION OF THE INVENTION

[0011] A first aspect is an active radiation curable coating composition comprising the following compound: 10 to 90% by weight, based on the total weight of the coating composition, of a poly(trimethylene ether) (meth)acrylate compound A having up to two (meth)acrylate groups, obtainable by condensation reaction of a bio-based 1,3 poly(trimethylene ether) glycol having a number average molecular weight Mn of 350 to 600 g / mol, more preferably 400 to 550 g / mol, with a (meth)acrylate compound selected from the group consisting of (meth)acrylic acid, (meth)acryloyl chloride, and / or alkyl esters thereof; · 10 to 89.99 wt. % of an ethylenically unsaturated oligomeric compound B different from compound A and having a viscosity at 25°C greater than 5 Pa·s, relative to the total weight of the coating composition; optionally, a low molecular weight ethylenically unsaturated monomeric compound C; Optionally, a further compound D which is a polymer having no reactive ethylenically unsaturated groups. The present invention relates to a composition comprising:

[0012] It has been unexpectedly found that the active radiation-curable coating composition according to the first aspect provides a coating with high toughness and elongation / modulus after curing. The composition is suitable for coating substrates such as wood, has excellent stain resistance, scratch abrasion, and impact resistance, and does not yellow after curing. Furthermore, the radiation-curable coating composition according to the first aspect provides a coating with high reactivity and excellent adhesion when cured. Furthermore, pigment wetting during application of a pigmented topcoat is improved when compared to coating formulations made with conventional monomers.

[0013] Surprisingly, it has also been found that poly(trimethylene ether) (meth)acrylate compound A, having up to two (meth)acrylate groups, can be used as a diluent monomer and provide performance equal to or even better than commercially known di-(meth)acrylate monomers such as TPGDA or DPGDA. Furthermore, this compound has been found to be a good alternative compared to other well-known bio-based monomers, such as propoxylated glycerol triacrylate (also known as OTA). Furthermore, poly(trimethylene ether) (meth)acrylate compound A is capable of softening harder oligomers so that coatings are less brittle when used at the same concentration compared to other types of known monomers.

[0014] As used herein, "bio-based compounds" or "biogenic compounds" or "compounds with carbon content from natural or renewable sources" or "compounds with biogenic carbon content" or "compounds with biocarbon content" can be used interchangeably and all refer to compounds sourced from or made from natural renewable sources, such as biomass or plant-based sources.

[0015] Currently, there are at least two different techniques for measuring the C content of a sample: (i) by liquid scintillation counter, or (ii) by mass spectrometry, where the sample is transferred into CO, then reduced to graphite and analyzed in a mass spectrometer to separate C atoms from C atoms and determine their ratio. All of these methods for measuring the C content of a substance are clearly described in American standards ASTM D6866 or ASTM D7026, as well as in European standards EN 16785 or EN 16640.

[0016] Bio-based carbon content values ​​according to the present invention are measured using the accelerated mass spectrometry protocol described in standard ASTM D6866-22.

[0017] According to the present invention, when a compound / composition is said to have, for example, a biocarbon content of at least 20%, it means that at least 20% of the carbon is from bio-based sources in view of the total carbon content of that compound / composition.

[0018] In one embodiment, the biocarbon content of compound A, compound B, and, if present, compound C and / or compound D, is greater than 5% by weight of the total carbon content, preferably greater than 10%, more preferably greater than 30%, and even more preferably greater than 50%, as measured using the accelerated mass spectrometry protocol described in standard ASTM D6866-22.

[0019] As used herein, "ethylenically unsaturated compound" refers to a compound having a polymerizable ethylenically unsaturated group. A polymerizable ethylenically unsaturated group means that the carbon-carbon double bond can undergo radical polymerization under the influence of an initiator and / or irradiation, and ultimately in the presence of a photoinitiator. The polymerizable ethylenically unsaturated group generally consists of a (meth)acrylic group. In the present invention, the term "(meth)acrylate group" or "(meth)acryloyl group" is understood to encompass both acrylate and methacrylate groups present on the compound, either individually or as a mixture thereof.

[0020] As used herein, "active radiation-curable composition" refers to a composition that can be polymerized using ethylenically unsaturated groups. Such compositions can be cured, at least in part, by electromagnetic radiation, particularly UV light, such as near-infrared, visible, UV, or X-ray radiation, or by particle radiation, such as electron beam radiation. UV light radiation refers to irradiation via ultraviolet light sources, including high- or low-pressure mercury lamps, cold cathode fluorescent lamps, xenon lamps, black lights, ultraviolet lasers, and flashlights, as well as LED light sources. Typically, UV light sources have wavelengths between 240 and 405 nm. Radiation using LED light sources refers to irradiation via light-emitting diode sources, where semiconductor light sources are used. Wavelengths of 365, 385, 395, or 405 nm are typically used. "Active radiation-curable composition" also includes compositions that can be "thermally" cured via polymerization initiated by free-radical generators, including peroxides and azo-type initiators. Peroxide initiators include diacyl peroxides, hydroperoxides, ketone peroxides, peroxyesters, peroxyketals, dialkyl peroxides, alkyl peresters, and percarbonates, and the like, used alone or in combination with redox systems. Examples of these peroxides include methyl ethyl ketone peroxide (MEKP), methyl isobutyl ketone peroxide (MIBK), benzoyl peroxide (BPO), and cumene hydroperoxide (CHP). Combinations of two or more peroxides may be used to cure the resin. Azo-type initiators include azobisisobutyronitrile (AIBN) and related compounds.

[0021] Poly(trimethylene ether) (meth)acrylate Compound A The poly(trimethylene ether) (meth)acrylate compound A having up to two (meth)acrylate groups can be obtained by a condensation reaction of a bio-based 1,3 poly(trimethylene ether) glycol with a (meth)acrylate compound selected from the group consisting of (meth)acrylic acid, (meth)acryloyl chloride, and / or its alkyl esters; the bio-based 1,3 poly(trimethylene ether) glycol has a number average molecular weight Mn of 350 to 600 g / mol, more preferably 400 to 550 g / mol.

[0022] The poly(trimethylene ether) (meth)acrylate compound A can be obtained by the condensation reaction of bio-based 1,3 poly(trimethylene ether) glycol with a (meth)acrylate compound selected from the group consisting of (meth)acrylic acid, (meth)acryloyl chloride, and / or its alkyl esters, preferably H2C=C(R)CO2-R 1 -COOH or H2C=C(R)CO2-R 1 -Cl, where R is H or CH3, and R 1 is a divalent group having a divalent linear alkyl group having 1 to 20 carbon atoms, preferably 1 to 5 carbon atoms, a divalent branched alkyl group having 3 to 20 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms.

[0023] 1,3 poly(trimethylene ether) can be biochemically obtained from renewable sources. This can be through a fermentation process using renewable biological sources, such as corn feed. Examples of commercially available biobased 1,3 poly(trimethylene ether) glycols are available from WeylChem® and are described, for example, in patent application WO2010 074805.

[0024] The 1,3 poly(trimethylene ether) glycols used to prepare compound A have a number average molecular weight Mn of 350 to 600 g / mol, more preferably 400 to 550 g / mol. The 1,3 poly(trimethylene ether) glycols used have a weight average molecular weight Mw of between 450 and 900 g / mol, preferably 500 to 650 g / mol. Preferably, the poly(trimethylene ether) glycol has trimethylene ether repeat units in the range of 1 to 25, preferably in the range of 1 to 20.

[0025] Surprisingly, it has been found that compound A having a broad molecular weight distribution, such as that illustrated in Figure 1, can provide a diluent monomer, has a low viscosity, and can provide coatings of good quality even when used in large amounts.

[0026] The biocarbon content of compound A is preferably at least 50%, more preferably above 60%, for example about 66%, of the total carbon content of compound A.

[0027] In one embodiment, compound A has a viscosity at 25° C. between 10 and 100 mPa·s, preferably between 20 and 50 mPa·s, for example 30 mPa·s.

[0028] The condensation reaction or esterification is preferably carried out by reacting 1,3 poly(trimethylene ether) glycol with a stoichiometric excess of (meth)acrylate groups present on a (meth)acrylate compound selected from the group consisting of (meth)acrylic acid, (meth)acryloyl chloride, and / or alkyl esters thereof. The reactants are generally used in a proportion corresponding to an equivalent ratio of (meth)acrylate groups to alcohol groups of the 1,3 poly(trimethylene ether) glycol of between 2.0:1.0 and 2.2:1.0.

[0029] Preferably, the poly(trimethylene ether) (meth)acrylate compound A obtainable by the condensation reaction contains at least 90% by weight, more preferably at least 95% by weight, or at least 99% by weight, of poly(trimethylene ether) di-(meth)acrylate, taking into account the total poly(trimethylene ether) (meth)acrylate compound A.

[0030] To prepare poly(trimethylene ether) (meth)acrylate compounds A having up to two (meth)acrylate groups, 1,3 poly(trimethylene ether) glycol can be contacted with a (meth)acrylate compound, preferably in the presence of a gas, at a temperature of about 25° C. to about 250° C. The process can be carried out at atmospheric pressure or under vacuum. During the reaction, water is formed and can be removed in an inert gas stream or under vacuum to drive the reaction to completion.

[0031] To facilitate the reaction of poly(trimethylene ether) glycol with a (meth)acrylate compound, an esterification catalyst is typically used, preferably a mineral acid catalyst. Examples of acid catalysts include, but are not limited to, sulfuric acid, aryl or alkyl sulfonic acids, triflic acid, hydroiodic acid, and heterogeneous catalysts such as zeolites, heteropolyacids, amberlyst, dialkyltin dilaurates, titanium alkoxides, and ion exchange resins. Preferred esterification acid catalysts are selected from the group consisting of sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, triflic acid, dialkyltin dilaurates, titanium alkoxides, and hydroiodic acid. Particularly preferred acid catalysts are sulfuric acid, triflic acid, and ion exchange resins. The amount of catalyst used is about 0.01% to about 10% by weight of the reaction mixture, preferably 0.1% to about 5% by weight, and more preferably about 0.2% to about 2% by weight of the reaction mixture. To prevent the free radical polymerization of the (meth)acrylic acid ester of poly(trimethylene ether) glycol, an inhibitor is used, preferably 4-methoxyphenol. Examples of inhibitors include, but are not limited to, alkylphenols, alkoxyphenols, hydroxybenzyl alcohol, and hydroquinone. The amount of inhibitor can be about 0.001 to 5% by weight of the product. A preferred range is about 0.01 to 2.0% by weight. The esterification reaction can be carried out in the presence or absence of a solvent. Examples of solvents include, but are not limited to, acetonitrile, cyclohexane, hexane, methylcyclohexane, heptane, octane, tetrahydrofuran, toluene, and xylene. Preferred solvents are acetonitrile or toluene. The amount of solvent used can be about 0% to about 100% by weight of the reaction mixture, preferably 20% to about 100% by weight, and more preferably about 50% to about 100% by weight of the reaction mixture.

[0032] In one embodiment, compound A is added in an amount such that the viscosity of the active radiation-curable composition is between 5 and 50,000 mPa·s, preferably between 10 and 10,000 mPa·s, and more preferably between 20 and 5,000 mPa·s at the application temperature. The application temperature is the temperature at which the active radiation-curable coating composition has when the composition is contacted with the substrate. In most cases, the application temperature is room temperature, although the active radiation-curable coating composition may also be contacted with the substrate at a higher temperature.

[0033] Apart from Compound A, it is also possible to add a low molecular weight ethylenically unsaturated monomer Compound C to reduce viscosity. In addition to Compound A, it is also possible to add a solvent, such as a bio-based solvent, to reduce viscosity; the latter is not preferred. The bio-based carbon content is higher when more Compound A or only Compound A is added to the composition.

[0034] In yet another embodiment, substantially no additional low molecular weight ethylenically unsaturated monomeric compound C is added.

[0035] In yet another embodiment, the poly(trimethylene ether) (meth)acrylate compound A has a number average molecular weight Mn between 400 and 650 g / mol, more preferably between 450 and 600 g / mol.

[0036] In a preferred embodiment, the poly(trimethylene ether) (meth)acrylate compound A has in the range of 1 to 25, more preferably 1 to 20, trimethylene ether repeat units.

[0037] According to another embodiment, the poly(trimethylene ether) (meth)acrylate compound A having a maximum of two (meth)acrylate groups has a weight average molecular weight Mw between 600 and 850 g / mol.

[0038] Compound A is used in an amount of 10% to 90% by weight, preferably 15% to 70% by weight, even more preferably 30 to 50% by weight, relative to the total weight of the coating composition.

[0039] Ethylenically unsaturated oligomer compound B The ethylenically unsaturated oligomeric compound B, unlike compound A, has a viscosity at 25° C. of greater than 5 Pa·s, preferably greater than 7 Pa·s, for example greater than 10 Pa·s.

[0040] The ethylenically unsaturated oligomeric compound B is preferably an oligomer having at least one (meth)acrylate group, including those selected from the group consisting of polyester (meth)acrylates, polyether (meth)acrylates, epoxy (meth)acrylates, amino (meth)acrylates, polycarbonate (meth)acrylates, (poly)urethane (meth)acrylates, (meth)acrylated (meth)acrylic resins, or mixtures thereof.

[0041] Polyester (meth)acrylate oligomers are well known. These (meth)acrylated polyesters can be obtained by reacting a hydroxyl group-containing polyester backbone with (meth)acrylic acid, or by reacting a carboxyl group-containing polyester backbone with a hydroxyalkyl (meth)acrylate, such as 2-hydroxyethyl acrylate, 2- or 3-hydroxypropyl acrylate, or with glycidyl (meth)acrylate. The polyester backbone can be obtained by conventional methods by polycondensation of at least one polyhydroxy alcohol, such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexanediol, trimethylolpropane, bisphenol A, or pentaerythritol, and / or its ethoxylates and / or propoxylates, with at least one polycarboxylic acid or anhydride, such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, or trimellitic acid. By using unsaturated compounds in polyester synthesis, such as fumaric acid, maleic acid, and itaconic acid, polyesters can be obtained that retain both (meth)acrylic and ethylenic unsaturation in the polymer chain. Furthermore, polylactones and / or polylactides can be used as the polyester backbone. For example, poly(ε-caprolactone), polylactide, and / or poly(lactide, caprolactone) can be obtained by ring-opening polymerization of c-caprolactone and / or lactide, optionally in the presence of one or more polyhydroxy alcohols. Examples of suitable polyester (meth)acrylates include EBECRYL® 854, EBECRYL® 5849, EBECRYL® 450, EBECRYL® 452, EBECRYL® 657, EBECRYL® 810, EBECRYL® 852, EBECRYL® 853, EBECRYL® 870, and / or EBECRYL® 892 manufactured by Allnex. An example of an oil-modified polyester (meth)acrylate that may be used is RAYLOK® 1621 and / or RAYLOK® 1622.

[0042] Polyether (meth)acrylate oligomers can be prepared by esterification of hydroxy-functional polyethers with (meth)acrylic acid. Hydroxy-functional polyethers can be obtained by ring-opening homopolymerization or copolymerization of cyclic ethers, such as tetrahydrofuran, ethylene oxide, and / or propylene oxide, or can be prepared by reacting polyhydroxy alcohols with ethylene and / or propylene oxide. Other types of polyether acrylate oligomers are, for example, dipentaerythritol hexaacrylate (DPHA) and its ethoxylated and / or propoxylated derivatives.

[0043] Polycarbonate (meth)acrylate oligomers are also known. They can be prepared by esterification of hydroxy-functional polycarbonates with (meth)acrylic acid.

[0044] (Poly)urethane (meth)acrylate oligomers can be prepared by reacting di- and / or polyisocyanates, such as hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, with hydroxy-functional (meth)acrylates. Hydroxyl-functional (meth)acrylates such as those mentioned above can be used exclusively, but mono- or polyhydroxy alcohols can also be added for chain extension, such as those already mentioned for the synthesis of hydroxyl-containing polyesters, polyethers, or polycarbonates.

[0045] Examples of suitable urethane (meth)acrylates include EBECRYL® 264, EBECRYL® 265, EBECRYL® 4820, and / or EBECRYL® 4680, all available from Allnex. Examples of suitable aromatic urethane (meth)acrylates are EBECRYL® 210 and / or EBECRYL® 220, all available from Allnex.

[0046] The term "epoxy (meth)acrylate oligomer" refers to a (meth)acrylic acid ester of an epoxide, preferably a polyepoxide, i.e., a compound having at least one, preferably at least two, epoxide functional groups. Epoxy (meth)acrylate oligomers are generally obtained by the esterification reaction of (meth)acrylic acid with an epoxide. The epoxide is generally selected from epoxidized olefins, glycidyl esters of saturated or unsaturated carboxylic acids, glycidyl ethers of aromatic or aliphatic alcohols or polyols, and cycloaliphatic polyepoxides. Preferred epoxides are diglycidyl ethers of aromatic and aliphatic diols and cycloaliphatic diepoxides, such as diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, diglycidyl ether of poly(ethylene oxide-co-propylene oxide), diglycidyl ether of polypropylene oxide, diglycidyl ether of hexanediol, and diglycidyl ether of butanediol. Diglycidyl ether of bisphenol-A is particularly preferred. Epoxidized natural oils or epoxidized phenol-formaldehyde copolymers can also be used. Examples of natural oils include soybean oil, linseed oil, perilla oil, fish oil, dehydrated castor oil, tung oil, coconut oil, corn oil, cottonseed oil, olive oil, palm oil, palm kernel oil, peanut oil, sunflower oil, safflower oil, and castor oil. Examples of suitable epoxy (meth)acrylates include EBECRYL® 600, EBECRYL® 648, EBECRYL® 645, EBECRYL® 860, EBECRYL® 6040, EBECRYL® 3700, and / or EBECRYL® 3203, all available from Allnex.

[0047] (Meth)acrylated (meth)acrylic oligomers can be obtained by first preparing a (meth)acrylic copolymer by copolymerizing a (meth)acrylate monomer, such as butyl acrylate, with a monomer having a carboxylic acid side group, anhydride, hydroxyl, glycidyl, or isocyanate group, and then reacting this copolymer with a monomer having at least one (meth)acrylate functional group and at least one carboxylic acid, anhydride, hydroxyl, glycidyl, or isocyanate-reactive group. For example, a glycidyl group-containing copolymer can be first prepared by copolymerizing a functionalized monomer, such as glycidyl (meth)acrylate, with another (meth)acrylate monomer, and the glycidyl group-containing polymer is typically reacted with (meth)acrylic acid in the second step. When the functionalized monomer is (meth)acrylic acid, the carboxyl group-containing polymer is typically reacted with glycidyl (meth)acrylate in the second step. An example of a suitable (meth)acrylated (meth)acrylic is EBECRYL® 1200.

[0048] Amino(meth)acrylates can also be added to the compositions of the present invention by themselves. Amino(meth)acrylates can be obtained by the addition reaction of (meth)acrylates with amines. Examples of suitable amino(meth)acrylates include EBECRYL® 7100, EBECRYL® 80, EBECRYL® 81, EBECRYL® 83, EBECRYL® 85, EBECRYL® 880, EBECRYL® LEO 10551, EBECRYL® LEO 10552, and EBECRYL® LEO 10553, all available from Allnex.

[0049] Particularly preferred are ethylenically unsaturated oligomeric compounds B whose backbone is derived from bio-based compounds, such as fatty acid-derived compounds or alcohols obtained by further fermentation and / or reaction of plant-based materials.

[0050] The ethylenically unsaturated oligomeric compound B is typically a poly(meth)acrylate having 2 to 18 (meth)acryloyl groups per molecule. More typically, compound B has 2 to 6, most typically 2 to 4 (meth)acryloyl groups. Acryloyl groups are preferred herein.

[0051] The ethylenically unsaturated oligomeric compound B may be selected to enhance the flexibility, strength, and / or modulus, among other attributes, of the cured polymer prepared using the polymerizable composition of the present invention.

[0052] The ethylenically unsaturated oligomeric compound B may have a number average molecular weight greater than or equal to 500 g / mol, in particular between 800 and 15,000 g / mol, more in particular between 1,000 and 5,000 g / mol.

[0053] Compound B is present in an amount of from 10% to 89.99% by weight, preferably from 30% to 84.99% by weight, and even more preferably from 50% to 69.99% by weight, relative to the total weight of the coating composition.

[0054] Low molecular weight ethylenically unsaturated monomer compound C The low molecular weight ethylenically unsaturated monomer compound C can be any conventional diluent monomer that is an active radiation curable compound. Typically, these compounds have low viscosity and are added to reduce the viscosity of the curable composition of the present invention and to adjust the flexibility, strength, solubility, and / or modulus, among other properties, of the finished product obtained by curing the composition.

[0055] Preferably, the viscosity of the low molecular weight ethylenically unsaturated monomer compound C is in the range of 5 mPa·s to 2 Pa·s at a temperature of 25° C., most preferably <500 mPa·s. Preferably, the low molecular weight ethylenically unsaturated monomer compound C has a number average molecular weight (Mn) in the average range of 100 to 1000 Daltons, more preferably 200 to 800 Daltons, most preferably 200 to 500 Daltons. Typically, the weight average molecular weight (MW) is at most 1000 Daltons.

[0056] The low molecular weight ethylenically unsaturated monomer compound C can be monofunctional, i.e., have one ethylenically unsaturated functional group, or polyfunctional, i.e., have at least two ethylenically unsaturated functional groups, such as a (meth)acrylate functional monomer. The ethylenically unsaturated monomer may, for example, comprise at least one compound selected from the group consisting of cyclic, linear, and branched mono(meth)acrylate-functionalized and mono-(meth)acrylamide-functionalized monomers.

[0057] Vinyl compounds can also be used. Suitable vinyl compounds include, for example, styrene, [alpha]-methylstyrene, vinyltoluene, bromostyrene, tert-butylstyrene, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl stearate, vinyl 2-ethylhexanoate, methyl vinyl ketone, ethyl vinyl ketone, vinyl ethers of C1-C20 alcohols, 2,3-dihydrofuran, vinyl (meth)acrylate, allyl vinyl ether, and divinyl ethers of C1-C20 diols.

[0058] Suitable (meth)acrylated compounds include butyl (meth)acrylate, methyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-hexyl (meth)acrylate, isobornyl (meth)acrylate, iso-octyl (meth)acrylate, n-lauryl (meth)acrylate, octyl / decyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenolate, ethoxylated mono(meth)acrylate, 2-(-2-ethoxyethoxy)-ethyl-(meth)acrylate, 2-butoxyethyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate (HDD(M)A), di- or tripropylene glycol di(meth)acrylate (DPGD(M)A, TPGD(M)A), ethoxylated and / or propoxylated neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate (PETI(M)A), and their ethoxylated and / or propoxylated derivatives. ethoxylated and / or propoxylated derivatives thereof, trimethylolpropane tri(meth)acrylate (TMPT(M)A) and their ethoxylated and / or propoxylated derivatives, di-trimethylolpropane tri(meth)acrylate (diTMPT(M)A), glycol tri(meth)acrylate, dianhydrohexitol di(meth)acrylate (isosorbide di(meth)acrylate, etc.) and their ethoxylated and / or propoxylated derivatives, bisphenol A di(meth)acrylate and their ethoxylated and / or propoxylated derivatives These include derivatives, phenyl glycidyl ether (meth)acrylate, and their ethoxylated and / or propoxylated derivatives, the (meth)acrylates being obtained from the esterification of aliphatic glycidyl ethers, particularly those in which the alkyl chain has from 6 to 24 carbon atoms, more preferably from 8 to 18 carbon atoms, and / or glycidyl esters of saturated and unsaturated carboxylic acids, particularly those in which the alkyl chain has from 6 to 24 carbon atoms, more preferably from 8 to 18 carbon atoms, with (meth)acrylic acid.

[0059] Di- and / or tri(meth)acrylated monomers, such as 1,6-hexanediol di(meth)acrylate (HDD(M)A), di- or tripropylene glycol di(meth)acrylate (DPGD(M)A, TPGD(M)A), trimethylolpropane tri(meth)acrylate (TMPT(M)A), and their ethoxylated and / or propoxylated derivatives, pentaerythritol tri(meth)acrylate (PETI(M )A) and its ethoxylated and / or propoxylated derivatives, glycerol tri(meth)acrylate and its ethoxylated and / or propoxylated derivatives, dianhydrohexitol di(meth)acrylate (such as isosorbide di(meth)acrylate) and its ethoxylated and / or propoxylated derivatives, bisphenol A di(meth)acrylate and its ethoxylated and / or propoxylated derivatives are preferred. In an embodiment of the present invention, at least one di- and / or tri(meth)acrylated monomer is present in the radiation-curable matte composition (II) of the present invention. It is preferred to keep the amount of monofunctional (meth)acrylates, in particular monofunctional alkyl (meth)acrylates, more particularly C8-C20 monofunctional alkyl (meth)acrylates (such as lauryl acrylate), well below a level of 10 wt. % (percent by weight), preferably below 8 wt. %, more preferably below 5 wt. %, based on the total weight of the matte composition (II) of the present invention. In an embodiment of the present invention, no monofunctional (meth)acrylates are present. In another preferred embodiment of the present invention, stenomeric (meth)acrylate monomers are substantially absent, in this case, not added at all.

[0060] The active radiation curable coating composition may comprise from 35 to 50% by weight of low molecular weight ethylenically unsaturated monomer compound C, based on the total weight of the radiation curable coating composition.

[0061] In one embodiment, the active radiation curable composition preferably has a Tg (glass transition temperature) after curing of at least 20° C., more preferably above 25° C., even more preferably at least 30° C. Typically, the Tg is below 160° C., for example below 140° C. As used herein, Tg is measured according to standard method ASTM D4065-01, as described below.

[0062] In another embodiment, the active radiation curable composition may have a Young's modulus after curing of at least 500 MPa, such as greater than 700 MPa, or greater than 1000 MPa.

[0063] Other ingredients The active radiation curable composition of the present invention may optionally contain a polymeric compound D that does not have ethylenically unsaturated groups. Examples of such polymers are saturated polyesters, halogenated or non-halogenated hydrocarbons (such as styrene-based hydrocarbon resins), styrene-allyl alcohols, acrylics (such as acrylic (co)polymers), (poly)urethane resins, polyethylene vinyl acetate resins, polyvinyl chloride resins, chlorinated polyolefin resins, and / or ketone resins. Other types of polymers may be bio-based polymers, such as polymers and copolymers of lactic acid, cellulose esters (such as cellulose acetate, cellulose propionate, cellulose butyrate, and combinations thereof), polyhydroxyalkanoates (e.g., polyhydroxybutyrate and copolymers), lignin derivatives, hemicellulose derivatives, etc.

[0064] The active radiation curable coating composition of the present invention may further comprise between 0.01 and 15 wt. % of a photoinitiator, based on the weight of the composition.

[0065] Any photoinitiator or mixture thereof capable of generating free radicals when exposed to radiation may be used. Preferred photoinitiators include IRGACURE® 184; acylphosphine oxides such as IRGACURE® 819; benziketals such as IRGACURE® 651 available from BASF; benzophenones such as ADDITOL® BP available from Allnex, IRGACURE® 1173, and IRGACURE® BP available from BASF, or Speedcure photoinitiators from Lambson Ltd.

[0066] Curing of the composition can also be carried out without the use of a photoinitiator.

[0067] The composition typically contains an inhibitor. Examples of suitable inhibitors include, but are not limited to, phenolic inhibitors such as hydroquinone (HQ), methylhydroquinone (THQ), tert-butylhydroquinone (TBHQ), parabenzoquinone (BQ), 4-tert-butylcatechol, di-tert-butylhydroquinone (DTBHQ), hydroquinone monomethyl ether (MEHQ), 2,6-di-tert-butyl-4-methylphenol (BHT), and the like. They may also contain phosphines such as triphenylphosphine (TPP), and other materials such as tris-nonylphenylphosphite (TNPP), phenothiazine (PTZ), and triphenylantimony (TPS). When present, the inhibitor is preferably present in an amount of up to 0.5% by weight of the composition, particularly 0.0001 to 0.2% by weight, preferably 0.01 to 0.1% by weight.

[0068] Light stabilizers can be classified as UV absorbers (UVA), deactivators (quenchers), hydroperoxide decomposers, and radical scavengers known as hindered amine light stabilizers (HALS).

[0069] In some embodiments, the composition may further comprise a UV absorber and / or a hindered amine light stabilizer. UVA protects the polymer by absorbing destructive UV radiation, while HALS materials protect by reacting with the free radicals that are produced after high-energy UV photons break the chemical bonds in the polymer.

[0070] Examples of UVAs are benzotriazoles such as Tinuvin® 328, Tinuvin® 1130, Tinuvin® 900, Tinuvin® 99-2, and Tinuvin® 384-2; triazines such as Tinuvin® 400, Tinuvin® 405, Tinuvin® 460, Tinuvin® 477, and Tinuvin® 479; and benzophenones such as Tinuvin® 531.

[0071] Examples of HALS are Tinuvin® 123, Tinuvin® 144, and Tinuvin® 292, 2,2,6,6-tetramethylpiperidine, and 2,6-di-tert-butylpiperidine.

[0072] When present, light stabilizers may be used in an amount of 0.1 to 5.0, preferably 0.5 to 2.5, percent by weight of the composition.

[0073] The composition may also contain further additives such as fiber wetting agents, for example functionalized silanes; and (acidic) adhesion promoters.

[0074] The active radiation curable coating compositions of the present invention may contain coalescing organic solvents, pigments, dyes, heat stabilizers, defoamers, leveling agents, anti-agents, fillers, settling inhibitors, UV absorbers, antioxidants, and the like, introduced at any stage of the preparation process or thereafter, as well as other conventional ingredients.

[0075] In another aspect, the present invention relates to the use of the above-mentioned poly(trimethylene ether) (meth)acrylate compound A having up to two (meth)acrylate groups as a diluent monomer in an active radiation-curable coating composition.

[0076] In one embodiment of this aspect, the poly(trimethylene ether) (meth)acrylate compound A having up to two (meth)acrylate groups is added to the active radiation curable coating composition in an amount of 10 to 90 wt. %, preferably 15 to 70 wt. %, and even more preferably 30 to 50 wt. %, based on the total weight of the coating composition.

[0077] In another embodiment of this aspect, the poly(trimethylene ether) (meth)acrylate compound A having up to two (meth)acrylate groups is added in an amount such that the viscosity of the active radiation curable composition at the application temperature is between 5 and 50,000 mPa·s, preferably between 10 and 10,000 mPa·s, more preferably between 20 and 5,000 mPa·s.

[0078] In a third aspect, the present invention relates to a method of forming a coating comprising the steps of applying a layer of the above-described active radiation curable coating composition to at least a portion of a substrate and subjecting the coated substrate to curing conditions.

[0079] The method of applying the layer of active radiation curable coating composition can be done, for example, via spraying, for example, via spraying of wood and plastic substrates.

[0080] In one embodiment according to this aspect, the curing conditions are selected from peroxide curing, LED curing, UV curing, and / or electron beam curing.

[0081] In another embodiment, the substrate is selected from the group consisting of wood, plastic, leather, metal, composite, ceramic, paper, and mineral substrates such as glass.

[0082] In a fourth aspect, the present invention relates to the use of the active radiation curable composition in additive manufacturing, laminating adhesives, waterproofing membranes, or inks such as flexographic printing inks.

[0083] In yet another aspect, the present invention relates to a substrate in contact with the above-described coating composition.

[0084] material: Velvetol® H250: Polypropanediol with a number average molecular weight Mn between 200 and 300 and a hydroxyl number between 370 and 550 mg KOH / g (Weylchem®) Ebecryl® 6000: Diacrylate ester of bisphenol A epoxy resin with a viscosity of >10,000 mPa·s at 25°C - available from Allnex® Ebecryl® 5849: EBECRYL® 5849 is a high-performance, medium-viscosity bio-based aliphatic diacrylate. Viscosity at 25°C: 7000-12000 mPa·s TPGDA: Tripropylene glycol diacrylate - available from Allnex® DPGDA: Dipropylene glycol diacrylate - available from Allnex® OTA 480: OTA-480 is a triacrylated reactive diluent based on a glycerol derivative - available from Allnex® Additol® MBF: Methyl benzoyl formate - available from Allnex® Ebecryl® 7100: An acrylate-functional oligomeric amine resin available from Allnex® Ebecryl® 8811 is a difunctional aliphatic urethane acrylate available from Allnex® BHT: butylated hydroxytoluene pBTC: para-butylcatechol Ebecryl® LED 03: Low viscosity amine-modified polyether acrylate oligomer - available from Allnex® ADDITOL® TPO (TPO-L) is a radical photoinitiator - available from Allnex®

[0085] method The number-average molecular weight Mn and weight-average molecular weight Mw were determined by conventional gel permeation chromatography (GPC) using polystyrene standards. The polystyrene standards used were EasyCal (molecular weight range: 200–400,000 g / mol) manufactured by Polymer Laboratories. Samples were dissolved in tetrahydrofuran (THF) containing 0.5% toluene as a flow marker (1.0 wt%). Analysis was performed using a liquid chromatograph (Agilent 1260) equipped with three PLGel mixed-D LS polystyrene-divinylbenzene GPC columns (300 × 7.5 mm × 5 μm). Sample components were separated by the GPC columns based on their molecular size in solution and detected by a refractive index detector. Data were collected and processed using Agilent GPC / SEC software. It is important to note that the samples were filtered on a 0.45 μm regenerated cellulose Whatman filter (Spartan™ 30 / 0.45RC) before being injected into the GPC system.

[0086] Viscosity was measured using a rotational rheometer in cone-plate configuration at a shear rate of 20 s -1 and is measured according to DIN EN ISO 3219.

[0087] Preparation of coatings To determine the glass transition and tensile properties, the liquid UV-curable compositions were applied to glass substrates pre-cleaned with acetone and isopropanol using a bar coater. The coating layer was applied at 5 m min -1 The curing was carried out using two UV lamp belt conveyors in series, each operating at a speed of 80 W / cm². -1Ga-doped medium pressure mercury vapor (Hg) lamp followed by 80Wcm -1 Curing was performed with a medium pressure Hg lamp. After curing, the coating was recovered from the glass substrate as a free-standing film.

[0088] Glass transition properties The glass transition temperature (Tg) marks the boundary between a glassy, ​​rigid state and a softer, relaxed state of a polymer or polymer network, which may be rubbery or even fluid.

[0089] A suitable method for determining the glass transition temperature of a solid polymer or cured polymer network is dynamic mechanical thermal analysis (DMTA), such as that described in standard method ASTM D4065-01 (Standard Test Method for Assignment of Glass Transition Temperature by Dynamic Mechanical Analysis).

[0090] DMTA measurements were performed using a DMA Q800 (TA Instruments) instrument in tension mode. The sample dimensions between the clamps were typically 11 mm x 8.0 mm x 0.04 mm. Cyclic strain deformation was applied at a frequency of 1 Hz with an amplitude of 30 μm. Viscoelastic properties were measured following a temperature profile with a heating rate of 3°C per minute from -50°C to 200°C. Tg was determined as the temperature at the maximum of the loss factor curve (i.e., T(tanδ)). max )) is determined as

[0091] Tensile Properties Young's modulus, or tensile modulus, is a mechanical property that provides an indication of the degree of stiffness of a solid material. It defines the relationship between the tensile stress (force per unit area) and tensile strain (relative deformation) of a material for small uniaxial deformations. Young's modulus (E Y) is the ratio between tensile stress and tensile strain and is reported in units of pressure. Ultimate tensile elongation (UTE) or elongation at break (in %) indicates a material's resistance to fracture. Tensile properties are reported at a temperature of 23°C in accordance with one of the following standard methods for determining tensile properties: ASTM D638 (Standard Test Methods for Tensile Properties of Plastics), ASTM D882 (Standard Test Methods for Tensile Properties of Thin Plastic Sheets), or ISO 527-1 (Plastics - Determination of Tensile Properties).

[0092] Reactivity For successful application, UV-curable compositions should exhibit high reactivity after exposure to UV light. To evaluate reactivity characteristics, liquid UV-curable compositions were deposited onto white, non-absorbent paper at thicknesses of 20–25 μm. UV curing was performed in a similar manner to that described above for glass substrates. The transport speed was varied to determine the maximum transport speed required to obtain a fully cured film. The level of cure was assessed by applying some fine graphite powder to the coating surface and rubbing it with a finger and then with cotton. As long as dark marks remain present after removing excess graphite powder, the film is not sufficiently cured and the transport speed must be reduced and UV exposure increased. The coating was subjected to 100 double rubs using cotton dipped in acetone. A fully cured film was visually unaffected after this test. The UV dose (fixed power of the UV lamp (W·cm)) required to pass both tests was calculated. -1 ) at conveying speed (m min -1 ) is referred to as the reactivity of the coating.

[0093] Adhesion A 20-22 μm film is deposited on the primer and fully cured as described for the reactive method. A square pattern is cut into the coating with a cutter. A piece of adhesive tape (Tesa 4104) is pressed onto the surface to degas the inner layer. The tape is then peeled off. Based on the number of squares removed by the tape, an adhesion value is assigned: 0B (100% of the squares removed), 1B (65-35% of the squares removed), 2B (35-15% of the squares removed), 3B (15-5% of the squares removed), 4B (less than 5% of the squares removed), 5B (0%).

[0094] Scratch resistance Hamberger-Hobel (Coin Test): The full coating system is applied to polished beech wood, cured and placed on a Hamberger Hobel testing machine. The device is equipped with a rotatable screw so that the pressure of the coin on the coating can be varied. The load is increased in steps until a scratch of several centimeters is created on the coating surface. The higher the load value, the better the scratch resistance. The scratch resistance is expressed in Newtons.

[0095] Abrasion Test Grit feeder: This method is based on standard test method ASTM F510-93 and uses a Taber Abrader 5150 equipped with a leather-covered wheel (S-39); the sand used in the test is Alodur ESK 240 EN 14354 type manufactured by Treibacher. The full coating system is applied to sanded beech wood and allowed to harden. All equipment and substrates are conditioned in an air-conditioned room (21±1°C, 50±5% relative humidity) for at least 24 hours before testing. The coated substrate is abraded in steps of 500 cycles until a spot where the coating has been completely removed appears (initial point). The initial point is reached when blue spots form on the specimen after application of methylene blue solution. After determining the initial point, abrasion is performed for another 500 cycles. Methylene blue solution is again applied for visual comparison. Wear is measured by mass loss (in mg, accuracy of ±0.1 mg) after each 500 cycle step.

[0096] Persoz pendulum hardness (ASTM D4366) The Persoz pendulum hardness test measures the time for the amplitude of the Persoz pendulum to decrease from 12° to 4°. A 60 micron thick film is applied to a glass plate and cured with an electron beam at 250 kilovolts to 3 kGy.

[0097] Yellowing after curing UV-cured coatings tend to yellow after curing, especially on white or lightly colored substrates. Considering the problem of yellowing, the Δb value is obtained as the yellowing index and investigated at reactive cure speed after 2 hours and 2 days.

[0098] Pigment wetting Pigment wetting is the first step in dispersing a pigment in a formulation. Sufficient wetting is important and involves surrounding the pigment particles in liquid instead of air to reduce surface tension before proceeding to steps such as milling. Wetting performance is measured via the viscoelastic properties of the pigment-resin mixture.

[0099] Stain resistance Stain resistance is defined as the ability to resist several common stains and is an important performance characteristic of interior and exterior coatings. It is measured by exposing the coating to droplets of stain for a specified number of hours and temperature. The coating integrity is evaluated after exposure (rating: 5 - no visible staining / / 4 - very light staining / / 3 - moderate staining / / 2 - heavy staining / / 1 - very heavy staining / / 0 - coating damage). Curing is performed under the coating's optimal performance conditions: thickness: 20 μm, curing: EB curing at 250 kV - 30 kGy. A white Leneta paper substrate is typically used.

[0100] Coatings on wood Wood coatings typically consist of various layers, each with special characteristics. A typical system contains a primer, a sealer, and is finished with a topcoat. For optimal performance of the entire coating system, good interlayer adhesion is highly desirable.

[0101] Base coat A basecoat is typically the first layer of paint or other coating material, serving as a base onto which a top or finish coat is applied. If a primer coat is required, the basecoat is applied over it. Basecoats are usually formulated with pigments, fillers, and plasticizers to cover minor surface imperfections and enhance the color and overall visual appearance of the topcoat. A 20-micron coating is applied onto Leneta paper and cured under EB 250 kV to 30 kGy. Basecoat performance is measured by Persoz hardness and stain resistance.

[0102] Clear coat A clearcoat (often called a finish or topcoat) is essentially a transparent protective layer applied on top of a cured basecoat. This layer provides the substrate with final protection against scratches, solvents, and dirt. A 20 micron coating is applied on top of the basecoat and cured with a Ga+Hg lamp combination using 4% by weight of the photoinitiator MBF. Clearcoat performance is measured by adhesion and stain resistance on the basecoat.

[0103] Sealer Sealer coatings can be tinted and provide a protective layer to the wood, preventing the wood grain from showing. It is common practice to apply sealers to prevent wood bleeding. Sealer coatings can be applied multiple times after sanding to obtain a smooth surface. Sealer coatings are cured with 4% by weight of TPO-L photoinitiator and Ga lamps, sometimes in combination with LEDs.

[0104] Synthesis of poly(trimethylene ether) di-(meth)acrylate (PPDODA) (Compound A) One molar equivalent of Velvetol® H250, 150 g of toluene, 0.3 g of methoxyphenol, and 2 molar equivalents of acrylic acid were placed in a 250 ml three-neck round-bottom flask and refluxed for 3 hours. After 3 hours, a distillation head was attached to the flask, and the solvent was distilled off from the reaction mixture at 85°C. The temperature was slowly increased to 115°C, and the reaction was continued at 115°C for 90 minutes. The reaction mixture was cooled to room temperature and then diluted with 100 ml of deionized (DI) water. The aqueous mixture was thoroughly mixed and transferred to a separatory funnel for purification. The organic product was collected and dried at 35°C using a rotary evaporator. The acrylic ester product was stabilized with 200 ppm of 2,6-bis(1,1-dimethylethyl)-4-methylphenol (BHT), and the product was analyzed using proton NMR.

[0105] The resulting product has the following properties: Viscosity (cone plate, 25℃, 20s -1 ): 30 mPa·s Mn: 500g / mol Mw: 810g / mol

[0106] (Example 1) Dilution power of PPDODA in Ebecryl 6000 compared to conventional diacrylate monomers The viscosity at 25°C of various ratios of PPDODA to Ebecryl 6000 (EB 6000) was measured and compared with the standard monomer (Table 1). [Table 1]

[0107] Using EB6000 in this example, it can be concluded that PDDODA, like DPGDA, has strong dilution power.

[0108] (Example 2) Tensile properties of UV-cured films based on EB6000 / PPDODA compared to traditional di-acrylate monomers Free films of 120 μm were prepared from a mixture of Eb 6000 and PPDODA and compared with standard monomers. The mixture contained 5 wt.% of a photoinitiator (Additol CPK from Allnex). Curing was performed using two UV lamps in series, each 80 W / cm², operating at a speed of 5 m / min. -1 Ga-doped medium pressure mercury vapor (HG) lamp followed by 80Wcm -1 This was done using a belt conveyor equipped with a medium pressure Hg lamp. [Table 2]

[0109] With a similar Young's modulus, PPDODA provides coatings with higher ultimate tensile elongation and tensile strength when compared to conventional monomer diluted compositions.

[0110] (Example 3) Tensile properties of UV-cured films based on EB 5849 / PPDODA compared to traditional di-acrylate monomers Free films of 120 μm were prepared from a mixture of Eb 5849 and PPDODA and compared with standard monomers. The mixture contained 5 wt% of a photoinitiator (Additol CPK). Curing was performed using two UV lamps in series, operating at a speed of 5 m / min and each 80 W / cm². -1 Ga-doped medium pressure mercury vapor (Hg) lamp followed by 80Wcm -1 This was done using a belt conveyor equipped with a medium pressure Hg lamp. [Table 3]

[0111] Compared to classical monomers, PDDODA is shown to provide higher elongation and toughness (strength at break) with comparable Young's modulus.

[0112] (Example 4) Use of PPDODA as a diluent in coating formulations for wood coatings base coat A basecoat was prepared using EB 5849 with diluent and applied as described above. [Table 4]

[0113] Table 4 shows that the diluent monomer PPDODA provides high stain resistance and very good Persoz hardness.

[0114] clear coat Clearcoats were prepared using Eb 6000 or Eb 5849 with a diluent and applied as described above. [Table 5]

[0115] Table 5 shows that the coating diluted with PPDODA has very high adhesion and very good stain resistance.

[0116] colored top coat In comparison to OTA480, a PPDODA-based pigmented sealer was prepared and applied as described above. [Table 6]

[0117] Table 6 shows that compared to OTA480, PPDODA provides equal dilution power, better adhesion (due to softened coating) and flexibility (mechanical properties). Smudge resistance and pigment wetting remain equal to the OTA-based topcoat formulation.

[0118] (Example 5) PPDODA can also be used as a diluent monomer for LED curing Using a typical formulation for LED curing, PPDODA and TPGDA were compared. In LED, radical inhibitors and special additives (e.g., LED 03) play an important role in obtaining sufficient surface cure. Therefore, adjustments to the inhibitor content are required.

[0119] Reactivity is assessed by the "thumb twist" method, which gives an indication of surface cure: the fewer the number of passes under the lamp at 5 m / min to get a good thumb twist result, the better the reactivity. [Table 7]

[0120] Table 7 shows that the coating formulation diluted with PPDODA has significantly higher reactivity compared to the coating formulation diluted with TPGDA, even when cured with LED.

Claims

1. 1. An active radiation curable coating composition comprising the following compound: from 10 to 90% by weight, based on the total weight of the coating composition, of a poly(trimethylene ether) (meth)acrylate compound A having up to two (meth)acrylate groups, obtainable by condensation reaction of a bio-based 1,3 poly(trimethylene ether) glycol having a number average molecular weight Mn of 350 to 600 g / mol, more preferably 400 to 550 g / mol, with a (meth)acrylate compound selected from the group consisting of (meth)acrylic acid, (meth)acryloyl chloride, and / or alkyl esters thereof; from 10% to 89.99% by weight, relative to the total weight of the coating composition, of an ethylenically unsaturated oligomeric compound B different from compound A and having a viscosity at 25°C greater than 5 Pa·s; optionally a low molecular weight ethylenically unsaturated monomeric compound C, Optionally, a further compound D which is a polymer without reactive ethylenically unsaturated groups. A composition comprising:

2. 2. The active radiation curable composition of claim 1, wherein the poly(trimethylene ether) (meth)acrylate compound A is added in an amount such that the viscosity of the active radiation curable composition is between 5 and 50,000 mPa s at the application temperature.

3. 3. The active radiation curable composition according to claim 1, wherein substantially no further low molecular weight ethylenically unsaturated monomeric compound C is added.

4. 4. The active radiation curable composition according to claim 1, wherein the poly(trimethylene ether) (meth)acrylate compound A has a number average molecular weight Mn between 400 and 650 g / mol, more preferably between 450 and 600 g / mol.

5. 5. The active radiation curable composition according to claim 1, wherein the poly(trimethylene ether) (meth)acrylate compound A has a weight average molecular weight Mw between 600 and 850 g / mol.

6. 6. The active radiation curable composition according to claim 1, wherein the poly(trimethylene ether) (meth)acrylate compound A has from 1 to 25 trimethylene ether repeating units.

7. 7. The active radiation curable composition according to any one of claims 1 to 6, wherein the ethylenically unsaturated oligomeric compound B is at least one (meth)acrylate-functionalized oligomer selected from the group consisting of (meth)acrylate esters of aliphatic monoalcohols, (meth)acrylate esters of alkoxylated aliphatic monoalcohols, (meth)acrylate esters of aliphatic polyols, (meth)acrylate esters of alkoxylated aliphatic polyols, (meth)acrylate esters of aromatic alcohols, (meth)acrylate esters of alkoxylated aromatic alcohols, epoxy (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates, and amine- and sulfide-modified derivatives thereof, and combinations thereof.

8. 8. The active radiation curable composition according to any one of claims 1 to 7, wherein the biocarbon content of compound A, oligomeric compound B and, if present, compound C and / or compound D is more than 5% by weight of the total carbon content, preferably more than 30%, more preferably more than 50%, even more preferably more than 60%, said biocarbon content being measured using the accelerated mass spectrometry protocol described in standard ASTM D6866-22.

9. 9. The active radiation curable composition of claim 1, further comprising between 0.01 and 15 wt. % of a photoinitiator, based on the weight of the composition.

10. 10. The active radiation curable composition according to any one of claims 1 to 9, wherein said radiation curable composition has a Tg of at least 20°C after curing, said Tg being measured according to standard method ASTM D4065-01.

11. 11. Use of the poly(trimethylene ether) (meth)acrylate compound A having up to two (meth)acrylate groups according to any one of claims 1 to 10 as a diluent monomer in an active radiation-curable coating composition.

12. 12. The use according to claim 11, wherein the poly(trimethylene ether) (meth)acrylate compound A is added to the active radiation curable coating composition in an amount of 10 to 90% by weight, based on the total weight of the coating composition.

13. 13. Use according to any one of claims 11 or 12, wherein the poly(trimethylene ether) (meth)acrylate compound A is added in an amount such that the viscosity of the active radiation curable composition is between 5 and 50,000 mPa s at application temperature.

14. 10. A method of forming a coating, comprising the steps of applying a layer of the active radiation curable coating composition of any one of claims 1 to 9 to at least a portion of a substrate and subjecting the coated substrate to curing conditions.

15. 14. The method of claim 13, wherein the curing conditions are selected from peroxide curing, LED curing, UV curing, and / or electron beam curing.

16. 15. The method of claim 13 or 14, wherein the substrate is selected from the group consisting of wood, plastic, leather, metal, ceramic, paper, or mineral substrates such as glass.

17. 11. Use of the active radiation curable composition according to any one of claims 1 to 10 in additive manufacturing, laminating adhesives, waterproofing membranes, composites or inks.

18. A substrate in contact with the coating composition of any one of claims 1 to 9.

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