Water-based radiation hardening components

Abstract

a) reacting at least one ethylenically unsaturated compound (A) with a compound of the general formula (I): DO-(R 1 O) n -X(I) (wherein D is a moiety containing an ethylenically unsaturated group (E), and R 1 is a linear or branched C2-C6 alkylene group, X is an ionic moiety, and n is in the range of 4 to 50), thereby obtaining a premix; and b) adding water to the premix until phase inversion occurs.

Description

[Technical Field]

[0001] The present invention relates to an aqueous radiation-curable composition and a coating composition comprising said aqueous radiation-curable composition. [Background technology]

[0002] Plastic coatings are an important and high-growth segment of the coatings industry, targeting challenging requirements for advanced surface finishing techniques that encompass aesthetics as well as additional protective and functional features. Coatings in so-called 3C applications, including computers, communications, and consumer electronics, are particularly challenging to formulate, as they utilize a variety of low surface energy substrates, including, for example, polycarbonates and additional synthetic polymers or fibers, but are notoriously difficult to bond to substrates.

[0003] As stricter VOC emission regulations are implemented worldwide, the demand for low-VOC coating solutions is rapidly increasing. In this context, waterborne radiation-curable coating compositions are becoming increasingly popular as an alternative to solvent-based resins. However, waterborne radiation-curable coating compositions known in the art are known to be limited in their use in difficult plastic applications, particularly due to poor adhesion performance.

[0004] Partial solutions are described, for example, in U.S. Patent Application Publication No. 2020 / 0181451 (Su et al.). There remains a need for low-VOC radiation-curable compositions that at least partially overcome the above-mentioned drawbacks without disputing the technical advantages associated with solutions known in the art. Summary of the Invention

[0005] According to one aspect, the present disclosure provides a method for manufacturing a semiconductor device comprising: a) mixing at least one ethylenically unsaturated compound (A) with at least one reactive ionic external emulsifier (B) having the general formula (I): DO-(R 1O) n -X (I) (In the formula, D is a moiety containing an ethylenically unsaturated group (E), R 1 is a linear or branched C2-C6 alkylene group, X is an ionic moiety; and mixing the resulting mixture with a reactive ionic external emulsifier (B) represented by the formula (I), where n is in the range of 4 to 50, thereby obtaining a premixture. b) relates to aqueous radiation-curable compositions obtained by adding water to the premix until phase inversion occurs.

[0006] According to another aspect, the present disclosure relates to a coating composition comprising the above-described aqueous radiation-curable composition.

[0007] In yet another aspect of the present disclosure, there is provided a method for producing an aqueous radiation curable composition, comprising: a) mixing at least one ethylenically unsaturated compound (A) as described above with at least one reactive ionic external emulsifier (B) as described above, thereby obtaining a premix; b) adding water to the pre-mixture until phase inversion occurs.

[0008] According to yet another aspect, the present disclosure relates to the use of the above-described water-based radiation curable or coating compositions in computer, communication and consumer electronics applications, dual cure applications, coating applications, composite applications, three-dimensional (3D) applications, printing applications, adhesive applications, paper impregnation applications, or thick pigmented systems. DETAILED DESCRIPTION OF THE INVENTION

[0009] According to a first aspect, the present disclosure provides a method for manufacturing a semiconductor device, comprising: a) mixing at least one ethylenically unsaturated compound (A) with at least one reactive ionic external emulsifier (B) having the general formula (I): DO-(R1 O) n -X (I) (In the formula, D is a moiety containing an ethylenically unsaturated group (E), R 1 is a linear or branched C2-C6 alkylene group, X is an ionic moiety; and mixing the resulting mixture with a reactive ionic external emulsifier (B) represented by the formula (I), where n is in the range of 4 to 50, thereby obtaining a premixture. b) relates to aqueous radiation-curable compositions obtained by adding water to the premix until phase inversion occurs.

[0010] In the context of the present disclosure, it has surprisingly been found that the above-described aqueous radiation-curable compositions possess excellent colloidal stability even under severe aging conditions, as well as advantageous formulation flexibility.

[0011] Quite surprisingly, it has been found that the above-described aqueous radiation curable compositions are particularly suitable for forming coatings with excellent properties and performance attributes with respect to adhesion to difficult-to-bond plastic substrates (especially polycarbonate, acrylonitrile butadiene styrene, and combinations thereof), hot water resistance, hydrolysis resistance, visual aesthetics in complex formulations (e.g., metallic or matte formulations), abrasion resistance, and low VOC characteristics.

[0012] Without wishing to be bound by theory, these superior properties and attributes are believed to be due in particular to the use of a specific combination of (a) at least one ethylenically unsaturated compound (A) and (b) at least one reactive ionic external emulsifier (B) as defined above, the aqueous radiation curable composition being specifically obtained by premixing compound (A) and compound (B) and adding water to the resulting premix until phase inversion occurs.

[0013] More specifically, this unique combination of ingredients, along with the premixing aspect detailed above, is believed to contribute to providing aqueous radiation-curable compositions with advantageous properties, particularly relatively high solids content, relatively small particle size, and excellent viscosity characteristics, resulting in coatings with the excellent properties and performance attributes detailed above. Furthermore, the reactive ionic external emulsifier (B) is believed to contribute significantly to providing aqueous radiation-curable compositions with the advantageous properties detailed above, particularly due to the presence of the ethylenically unsaturated group (E) and the ionic moiety (X) in its structure, as well as the specific advantageous balance of hydrophilicity (via its polyalkylene oxide segment (RO)) and hydrophobicity (via its moiety (D)). The presence of the ethylenically unsaturated group (E) in the structure of the reactive ionic external emulsifier (B) is also believed to prevent (or at least substantially reduce) the presence of free emulsifier after polymerization. The presence of such free or mobile emulsifiers after curing is known to adversely affect various characteristics of the resulting coating, particularly its visual aspects, due to unwanted migration of these free emulsifiers through the coating layer to its outer surface.

[0014] As such, the aqueous radiation curable compositions of the present disclosure are well suited for forming coatings for use in 3C applications.

[0015] In the context of the present disclosure, the expression "reactive ionic external emulsifier" is intended to refer to an emulsifier that has the ability to copolymerize with monomers through radically polymerizable groups present in the molecule, further comprises an ionic moiety, and is added externally to stabilize the emulsion.

[0016] The aqueous radiation-curable composition of the present disclosure comprises, as a first component, at least one ethylenically unsaturated compound (A).

[0017] The ethylenically unsaturated compound (A) used herein is not particularly limited. Suitable ethylenically unsaturated compounds (A) used herein will be easily identified by those skilled in the art in light of the present disclosure.

[0018] As used herein, compound (A) contains at least one, typically at least two, polymerizable ethylenically unsaturated groups per molecule, also referred to herein as "ethylenically unsaturated functional group" or "ethylenically unsaturated group." Throughout this disclosure, "polymerizable ethylenically unsaturated group" refers to a carbon-carbon double bond capable of undergoing radical polymerization under the influence of irradiation. Examples of such groups are (meth)acryloyl, (meth)acrylamide, vinyl, vinyl ether, allyl, styrenyl, methylstyrenyl, maleyl, or fumaryl functional groups. As used herein, the polymerizable ethylenically unsaturated group is generally selected from (meth)acryloyl and / or allyl groups, preferably (meth)acryloyl groups, and more preferably acryloyl groups. In this disclosure, the term "(meth)acryloyl" should be understood to encompass both acryloyl and methacryloyl groups or derivatives thereof, as well as mixtures thereof.

[0019] The compound (A) used in the present disclosure can be a monomeric, oligomeric, and / or polymeric ethylenically unsaturated compound. Blends of monomeric, oligomeric, and / or polymeric ethylenically unsaturated compounds (A) can also be used.

[0020] Typically, the ethylenically unsaturated compound (A) is monomeric or oligomeric in nature. Advantageously, the compound (A) used herein is oligomeric. Typical monomeric compounds (A) have a weight average molecular weight (M) in the range of 50 to 300 g / mol, 100 to 250 g / mol, or even 100 to 200 g / mol, as measured by conventional gel permeation chromatography (GPC) techniques. wTypical oligomeric compounds (A) have a weight average molecular weight (Mw) in the range of 300 to 20,000 g / mol, 500 to 15,000 g / mol, 500 to 10,000 g / mol, or even 800 to 5,000 g / mol, as measured by conventional gel permeation chromatography (GPC) techniques.

[0021] In an advantageous embodiment, the ethylenically unsaturated compound (A) used herein is a water-insoluble compound. In the present disclosure, the term "water-insoluble compound" refers to an ethylenically unsaturated compound that is neither self-emulsifying nor self-dispersing, but forms an emulsion or dispersion in water or an aqueous solution in the presence of one or more reactive ionic external emulsifiers (B) as defined above. More particularly, according to this advantageous embodiment of the present disclosure, the compound (A) is a non-self-dispersing, non-self-emulsifying, non-water-dilutable compound. Typically, the compound (A) of the present invention is a non-self-dispersing compound. In the present disclosure, the term "self-dispersing compound" refers to a compound that, when mixed with water, forms a stable two-phase system of small particles dispersed in water without the aid of an additional emulsifier. In the present disclosure, the term "self-emulsifying compound" refers to a compound that, when mixed with water, forms a stable two-phase system of small droplets dispersed in water without the aid of an additional emulsifier. "Stable" herein refers to the substantial absence of coalescence (droplets) or aggregation (particles) that would result in phase separation, creaming, or sedimentation of a heterogeneous system after 2 days or more, typically 4 days or more, and preferably 10 days at 60°C. Typically, compound (A) as used herein is not a water-dilutable compound. "Water-dilutable compound," as used herein, refers to a compound that allows the formation of a homogeneous single-phase mixture when mixed with water over a concentration range of 5 to 75% by weight based on the total mass of water and compound, in the absence of an emulsifier.

[0022] Compound (A) is typically characterized by an amount of copolymerizable ethylenically unsaturated groups of at least 1 meq / g, at least 2 meq / g, at least 3 meq / g, at least 4 meq / g, at least 5 meq / g, at least 6 meq / g, at least 7 meq / g, at least 8 meq / g, or even at least 9 meq / g. Typically, this amount does not exceed 13 meq / g or even 12 meq / g. The amount of ethylenically unsaturated groups is typically measured by nuclear magnetic resonance spectroscopy (NMR) according to techniques well known in the art and is expressed in meq / g of solid material.

[0023] In exemplary embodiments, the ethylenically unsaturated compound (A) used herein contains at least 2, at least 4, at least 6, at least 8, or even at least 10 or more ethylenically unsaturated functional groups per molecule.

[0024] Advantageously, compound (A) combines the functionality and degree of unsaturation indicated above. In particular, preferred compounds (A) used herein are characterized by a functionality of at least 2, at least 4, at least 6, at least 8, or even at least 10 or more ethylenically unsaturated groups per molecule, and an amount of ethylenically unsaturated groups of at least 4 meq / g, at least 6 meq / g, at least 8 meq / g, or even at least 9 meq / g.

[0025] According to an exemplary embodiment, the ethylenically unsaturated compound (A) used in the present disclosure is a (meth)acrylated compound, particularly selected from the group consisting of urethane (meth)acrylate (A1), polyester (meth)acrylate (A2), polyepoxy (meth)acrylate (A3), polycarbonate (meth)acrylate (A4), polyether (meth)acrylate (A5), and polyacryl (meth)acrylate (A6).The exemplary ethylenically unsaturated compound (A) used herein is extensively detailed in U.S. Patent Application No. 2014 / 0377466 (Tielemans et al.), the contents of which are fully incorporated herein by reference.

[0026] According to an advantageous embodiment of the present disclosure, the ethylenically unsaturated compound (A) used herein is selected from the group consisting of urethane (meth)acrylates (A1), polyester (meth)acrylates (A2), epoxy (meth)acrylates (A3), and any combination or mixture thereof.

[0027] In a preferred embodiment, the ethylenically unsaturated compound (A) is selected from the group consisting of urethane (meth)acrylates (A1). It has been surprisingly found that urethane (meth)acrylates provide excellent compatibility with the reactive ionic external emulsifier (B), excellent stability of the aqueous radiation-curable composition (and the resulting aqueous emulsion), and consequently improved properties and performance attributes of the corresponding radiation-cured coating or article. Furthermore, the use of urethane (meth)acrylates (A1) as the ethylenically unsaturated compound (A) has been found to provide outstanding adhesion performance to difficult-to-bond plastic substrates (especially polycarbonate and acrylonitrile butadiene styrene, and any combination thereof), particularly those used in 3C applications.

[0028] In a beneficial embodiment of the aqueous radiation-curable composition of the present disclosure, the ethylenically unsaturated compound (A) used herein further comprises an ionic functional group. Advantageously, the ionic functional group used herein can be at least partially neutralized by an (organic or inorganic) neutralizing agent (C) to provide a salt therefrom.

[0029] Advantageously, the ionic functional groups used herein are anionic functional groups, in particular anionic bases derived from acidic functional groups, in particular acidic functional groups selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, and any combination or mixture thereof. Thus, preferred anionic bases used herein are selected from carboxylate, sulfonate, and phosphonate groups.

[0030] More advantageously, the ionic functional group used herein is a pendant hydrophilic group that can render the corresponding ethylenically unsaturated compound (A) at least partially self-dispersible, self-emulsifying, water-soluble, or water-reducible.

[0031] According to an advantageous embodiment, the ethylenically unsaturated compound (A) further comprising an acidic (anionic) functional group has an acid number of at least 5 mg KOH / g, at least 10 mg KOH / g, at least 20 mg KOH / g, at least 50 mg KOH / g, or even at least 100 mg KOH / g, when the acid number is determined according to the ASTM D974-64 standard test method.

[0032] In the context of the present disclosure, it has been found that ethylenically unsaturated compounds (A) further comprising ionic functional groups (especially anionic groups derived from acidic functional groups) not only provide excellent compatibility / affinity with the reactive ionic external emulsifier (B), but also favorably influence the overall stability of the aqueous radiation-curable composition (and the resulting water-based emulsion) by facilitating the attainment of relatively small particle sizes, thereby improving the properties of the corresponding radiation-cured coating or article. Without wishing to be bound by theory, it is believed that the presence of ionic functional groups in compound (A) provides additional "internal" stabilization of the aqueous radiation-curable composition, thereby contributing to providing an advantageous dual stabilization effect together with the "external" stabilization provided by the reactive ionic emulsifier (B).

[0033] Furthermore, it has been found that ethylenically unsaturated compounds (A), especially those derived from acrylic oligomers, can be advantageously used in dual (radiation and thermal) cure applications.

[0034] Ethylenically unsaturated compounds (A) further comprising ionic functional groups are well known in the art and are commercially available as they are, or may be obtained according to conventional techniques well known to those skilled in the art. Exemplary ethylenically unsaturated compounds (A) further comprising ionic functional groups used herein, including the method for obtaining the aforementioned compounds, including the neutralization step of the hydrophilic functional groups with a typical neutralizing agent, are described in detail, for example, in WO 2022 / 128462 (Tielemans), the contents of which are fully incorporated herein by reference. Typical neutralizing agents used herein include organic tertiary amines (e.g., triethylamine, etc.) and inorganic bases (e.g., sodium hydroxide, etc.).

[0035] In another beneficial aspect of the aqueous radiation-curable composition of the present disclosure, the ethylenically unsaturated compound (A) used herein is at least partially biobased, in particular having a biobased content of more than 10%, more than 20%, more than 40%, more than 50%, more than 60%, or even more than 80% by weight of the total carbon content of the ethylenically unsaturated compound (A), when the biobased content is determined according to the ASTM D6866 standard test method. Exemplary biobased ethylenically unsaturated compounds (A) used herein, and methods for obtaining them, are also broadly described in WO 2022 / 128462 (Tielemans), the contents of which are incorporated herein by reference in their entirety.

[0036] The aqueous radiation curable composition of the present disclosure comprises, as a second component, at least one reactive ionic external emulsifier (B), which is represented by the general formula (I): DO-(R 1 O) n -X (I) (In the formula, D is a moiety containing an ethylenically unsaturated group (E), R 1 is a linear or branched C2-C6 alkylene group, X is an ionic moiety; where n is in the range of 4 to 50).

[0037] The reactive ionic external emulsifier (B) used herein is not particularly limited as long as it satisfies the above general formula (I). Suitable reactive ionic external emulsifiers (B) used herein will be readily identified by those skilled in the art in light of the present disclosure.

[0038] In the context of the present disclosure, the alkylene oxide group (R 1 When the repeating number of the polyalkylene oxide segment (R O) is specifically maintained within the range of 4 to 50, the hydrophilicity (the polyalkylene oxide segment (R O) 1 It has been found that a particular advantageous balance of hydrophobicity (via moiety (O)) and hydrophobicity (via its moiety (D)) is achieved, which contributes significantly to providing an aqueous radiation-curable composition having the advantageous properties detailed above. Furthermore, the low content of emulsifier (B) that can be used minimizes the formation of water pockets, while at the same time maintaining the excellent colloidal stability of the aqueous radiation-curable composition and the excellent performance attributes of the resulting cured coating or article, such as (hot) water resistance, hydrolysis resistance, and visual appearance.

[0039] More specifically, when the integer n is less than 4, the reactive ionic external emulsifier (B) is inadequate in terms of hydrophilicity, which adversely affects the overall stability of the aqueous radiation-curable composition. Furthermore, the mechanical stability of the resulting cured coating or article has been found to be insufficient.

[0040] Furthermore, when the integer n is greater than 50, the reactive ionic external emulsifier (B) becomes too hydrophilic, resulting in increased formation of water pockets and reduced water release, again adversely affecting not only the overall stability of the aqueous radiation-curable composition but also various performance attributes of the resulting cured coating or article, such as (hot) water resistance, hydrolysis resistance, and visual appearance.

[0041] In advantageous embodiments of the reactive ionic external emulsifier (B), the integer n is 50 or less, 45 or less, 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or even 10 or less.

[0042] More advantageously, n is in the range of 4 to 45, 4 to 40, 4 to 35, 4 to 30, 5 to 30, 5 to 25, 5 to 20, 6 to 20, 6 to 15, 8 to 15, 8 to 12, or even 9 to 11.

[0043] In another advantageous embodiment, R1 is a linear or branched C2-C4 alkylene group, in particular a linear C2-C4 alkylene group, more in particular a linear C2-C3 alkylene group, and even more in particular a linear C2 alkylene group. Preferably, R1 is selected to be ethylene.

[0044] According to yet another advantageous embodiment of the reactive ionic external emulsifier (B), the ethylenically unsaturated group (E) contained in the portion (D) is selected from the group consisting of allyl, vinyl, propenyl, allyloxy, vinyloxy, propenyloxy, allyloxymethyl vinyloxymethyl, propenyloxymethyl, (meth)acryloyl, and any combination or mixture thereof. Preferably, the ethylenically unsaturated group (E) used herein is selected from the group consisting of allyl, vinyl, propenyl, and any combination or mixture thereof.

[0045] In another advantageous embodiment of the reactive ionic external emulsifier (B), the moiety (D) used herein is selected from the group of linear or branched alkyl groups, linear or branched aryl groups, linear or branched alkyl ether groups, linear or branched aryl ether groups, further substituted with an ethylenically unsaturated group (E).

[0046] According to a more advantageous embodiment, the moiety (D) used herein is of general formula (II): R 3 -O-CH2-CHR 2 - (II) (In the formula, R2 is -CH2-O-CH2-CH=CH2, R 3 is a straight or branched chain (C8-C 14 ) alkyl groups, especially straight chain (C 10 ~C 12 ) alkyl group) Or general formula (III): R 3 -CH2-CHR 2 - (III) (In the formula, R 2 is -CH2-O-CH2-CH=CH2, R 3 is a straight or branched chain (C8-C 14 ) alkyl groups, especially straight chain (C 10 ~C 12 ) alkyl group) Or general formula (IV): [ka] (In the formula, (E) is -CH=CR 4 -CH3, or -CH2-CR 4 =CH2, R 4 is H or a straight or branched chain (C1-C6) alkyl group, (R 5 )teeth, [ka] and m 1 and m 2 are independently 1 or 2).

[0047] In another advantageous embodiment of the reactive ionic external emulsifier (B), the ionic moiety (X) used herein is preferably an anionic moiety selected from the group consisting of sulfate groups, sulfonate groups, phosphate groups, phosphonate groups, phosphite groups, and any combination or mixture thereof. Preferably, the ionic moiety (X) used herein is selected from sulfate groups.

[0048] As will be readily apparent to those skilled in the art, the ionic moiety (X) will typically be associated with a suitable counterion. Exemplary counterions used herein are typically selected from the group consisting of sodium cations, ammonium cations, quaternary ammonium cations, and any mixtures thereof. Preferably, the counterions used herein are selected to be ammonium cations, as this provides the corresponding coating with significant (hot) water resistance.

[0049] In the context of the present disclosure, the use of ionic emulsifiers as detailed above has been found to be absolutely crucial to providing stable aqueous radiation-curable compositions according to the present disclosure. In contrast, the use of nonionic emulsifiers, including reactive nonionic emulsifiers, does not make it possible to obtain stable aqueous radiation-curable compositions.

[0050] According to another more advantageous embodiment, the reactive ionic external emulsifier (B) used herein is selected from the group consisting of (ethylenically unsaturated derivatives of) polyoxyethylene alkyl ether sulfate (ammonium) salts, and polyoxyethylene aryl ether sulfate (ammonium) salts, in particular polyoxyethylene styrenated phenyl ether sulfate (ammonium) salts.

[0051] According to an even more advantageous embodiment, the reactive ionic external emulsifier (B) used herein is selected from the group consisting of polyoxyethylene(allyloxymethyl) alkyl ether sulfate (ammonium) salts, polyoxyethylene(allyloxymethyl) alkoxy ether sulfate (ammonium) salts, polyoxyethylene(propenyl) aryl ether sulfate (ammonium) salts, in particular polyoxyethylene styrenated phenyl(propenyl) ether sulfate (ammonium) salts.

[0052] According to a particularly preferred embodiment, the reactive ionic external emulsifier (B) used in the aqueous radiation curable composition according to the present disclosure is [ka] and [ka] (In the formula, m 3 is either 1 or 2 R 3 and n is as defined above).

[0053] Further exemplary reactive ionic external emulsifiers (B) used herein have the following formula: [ka] (In the formula, R 3 and n is as defined above).

[0054] Suitable reactive ionic external emulsifiers (B) for use herein are commercially available under the trade names Hitenol® or Reasop®.

[0055] In one advantageous aspect, the aqueous radiation curable composition of the present disclosure is (substantially) free of (reactive and / or non-reactive) non-ionic (external) emulsifiers, in particular (substantially) free of reactive non-ionic (external) emulsifiers.

[0056] In another advantageous embodiment, the aqueous radiation curable composition of the present disclosure comprises only ionic (external) emulsifiers (reactive and non-reactive).

[0057] In yet another advantageous embodiment of the present disclosure, the aqueous radiation-curable composition comprises only the reactive ionic external emulsifier (B) represented by general formula (I). In other words, according to this particular embodiment, the (reactive) emulsifier comprised in the aqueous radiation-curable composition is exclusively the reactive ionic external emulsifier (B) represented by general formula (I).

[0058] The aqueous radiation curable composition of the present disclosure may further comprise, as an additional but optional component, a further compound (F).

[0059] The compound (F) used herein is not particularly limited. Suitable compounds (F) used herein will be easily identified by those skilled in the art in light of the present disclosure. The compound (F) will typically be selected depending on the additional properties that are the desired application and / or targeted application of the aqueous radiation-curable composition. The compound (F) may be oligomeric or polymeric in nature and may have various functional groups, such as, for example, acrylic, silicone, and halogen functional groups.

[0060] Compound (F) may be added at various steps in the formation of the aqueous emulsion. In a typical embodiment, this compound is mixed with at least one ethylenically unsaturated compound (A) and at least one reactive ionic external emulsifier (B), thereby obtaining a premixture. In an alternative embodiment, compound (F) may then be added to the premixture formed by mixing at least one ethylenically unsaturated compound (A) and at least one reactive ionic external emulsifier (B). Alternatively, compound (F) may be added after the aqueous emulsion has been formed following a suitable phase inversion.

[0061] In an advantageous embodiment, the compound (F) used herein is selected from the group of co-emulsifiers and additional surfactants. More advantageously, the compound (F) used herein has the ability to modify, in particular increase, the overall pH of the aqueous radiation-curable composition. Particularly advantageous compounds (F) used herein include acrylic and alkyd / acrylic resins, in particular acrylic resins.

[0062] As indicated above, the aqueous radiation-curable composition is obtained by adding water to a premix obtained by mixing at least one ethylenically unsaturated compound (A) with at least one reactive ionic external emulsifier (B). More specifically, water is added until phase inversion occurs.

[0063] The term "phase inversion" is well known in the field of emulsion chemistry, and achieving phase inversion in aqueous systems, thereby obtaining aqueous emulsions, is within the scope of those skilled in the art.Phase inversion emulsification is described in detail, for example, in the scientific publication "Phase inversion emulsification: Current understanding and applications" by A. Perazzo, V. Preziosi, and S. Guido, Advances in Colloid and Interface Science, 222 (2015), pp. 581-599, and in the reference book "Nanoemulsions: Formulation, Applications, and Characterization" (2018) by Perazzo, Antonio, and Valentina Preziosi, edited by Seid Mahdi Jafari and D. Julian McClements, Chapter 3 (Catastrophic Phase Inversion Techniques for Nanoemulsification).

[0064] In typical embodiments of the aqueous radiation-curable composition according to the present disclosure, water is added to the premix until phase inversion occurs, resulting in the formation of a water-based emulsion. Advantageously, water is added to the premix until catastrophic phase inversion occurs.

[0065] In an advantageous embodiment of the present disclosure, the phase inversion caused by adding water to a premix obtained by mixing at least one ethylenically unsaturated compound (A) with at least one reactive ionic external emulsifier (B) occurs without the use of forced emulsification techniques, i.e., without applying significant pressure to the mixture. In particular, the phase inversion occurs without the use of high shear or high pressure treatment, typically assisted by a high-pressure and / or high-shear homogenizer or emulsifier. In other words, the aqueous emulsion resulting from the phase inversion described in the present disclosure does not fall under the forced emulsification type.

[0066] In the context of the present disclosure, it has been found that the order of addition of water, compound (A), and emulsifier (B) is absolutely critical to providing a stable aqueous radiation-curable composition according to the present disclosure. Indeed, it has been surprisingly found that the formation of a premix containing compound (A) and emulsifier (B) before the actual addition of water is necessary to achieve a suitable phase inversion and a resulting stable aqueous radiation-curable composition. In contrast, if water is first mixed with emulsifier (B) and then compound (A) is added, a suitable phase inversion cannot be achieved, and therefore a stable aqueous radiation-curable composition (emulsion) cannot be obtained. Without wishing to be bound by theory, it is believed that the ambivalence range around the phase inversion, including the transition from water-in-oil to oil-in-water, is particularly suitable for achieving a reduction in droplet size toward a stable emulsion with a high droplet surface area.

[0067] According to an advantageous embodiment, at least one reactive anionic external emulsifier (B) is (pre-)diluted in water and then mixed with at least one ethylenically unsaturated compound (A), thereby forming a pre-mixture comprising compound (A) and (diluted) emulsifier (B). Typically, water is then added to this pre-mixture until phase inversion occurs. It has been found that pre-diluting the emulsifier in water before mixing with the at least one ethylenically unsaturated compound (A) advantageously influences not only the formation of phase inversion but also the overall stability of the resulting aqueous radiation-curable composition (emulsion).

[0068] In one advantageous embodiment, the aqueous radiation curable composition of the present disclosure has a particle (droplet) size of 800 nm or less, 600 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, 100 nm or less, or even 80 nm or less, as determined by DLS measurements according to the test methods described in the Experimental Section.

[0069] In another advantageous embodiment, the aqueous radiation curable composition has a particle (droplet) size in the range of 50 to 1000 nm, 60 to 800 nm, 65 to 600 nm, 65 to 400 nm, 65 to 350 nm, 70 to 300 nm, 70 to 250 nm, 70 to 200 nm, 70 to 150 nm, or even 70 to 100 nm, as determined by DLS measurements according to the test methods described in the experimental section.

[0070] In yet another advantageous embodiment, the aqueous radiation curable composition has a solids content of greater than 30 wt.%, greater than 35 wt.%, greater than 40 wt.%, greater than 45 wt.%, greater than 50 wt.%, greater than 55 wt.%, greater than 60 wt.%, or even greater than 65 wt.%, as determined gravimetrically according to the test methods described in the Experimental Section.

[0071] In yet another advantageous embodiment, the aqueous radiation curable composition has a solids content in the range of 35 to 65 wt. %, 40 to 55 wt. %, 45 to 55 wt. %, or even 50 to 55 wt. %, as determined gravimetrically according to the test methods described in the Experimental Section.

[0072] In another beneficial aspect, the aqueous radiation curable compositions described herein have a viscosity of greater than 10 mPa.s, greater than 50 mPa.s, greater than 100 mPa.s, greater than 200 mPa.s, greater than 400 mPa.s, greater than 600 mPa.s, greater than 800 mPa.s, greater than 1000 mPa.s, or even greater than 1500 mPa.s, as determined according to the test methods described in the Experimental Section.

[0073] In more advantageous embodiments, the aqueous radiation curable composition has a viscosity in the range of 5 to 1500 mPa.s, 5 to 1000 mPa.s, 10 to 800 mPa.s, 50 to 800 mPa.s, 50 to 600 mPa.s, 100 to 600 mPa.s, or even 100 to 400 mPa.s, as determined according to the test methods described in the Experimental Section.

[0074] The aqueous radiation-curable compositions of the present disclosure possess advantageous properties, particularly relatively high solids content, relatively small particle size, and relatively low viscosity, which not only beneficially affect the overall stability of the compositions but also contribute to providing corresponding coatings and articles with the superior properties and performance attributes detailed above.

[0075] Advantageously, the aqueous radiation curable compositions described herein are at least partially bio-based, in particular having a biocarbon content of more than 10%, more than 20%, more than 40%, more than 50%, more than 60%, or even more than 80% by weight of the total carbon content of the composition, where the bio-based content is determined according to the ASTM D6866 standard test method.

[0076] In typical embodiments, the aqueous radiation curable composition of the present disclosure comprises at least 0.5 wt %, at least 1 wt %, at least 2 wt %, at least 3 wt %, at least 4 wt %, or even at least 5 wt % of the reactive ionic external emulsifier (B), based on the total weight of compounds (A) and (B).

[0077] In another exemplary embodiment, the aqueous radiation curable composition of the present disclosure comprises 0.5 to 30 wt %, 0.5 to 25 wt %, 1 to 25 wt %, 2 to 25 wt %, 2 to 20 wt %, 3 to 20 wt %, 5 to 15 wt %, or even 5 to 10 wt % of the reactive ionic external emulsifier (B), based on the total weight of compounds (A) and (B).

[0078] In another exemplary embodiment, the aqueous radiation-curable composition of the present disclosure comprises 70 to 99.5 wt %, 75 to 99.5 wt %, 75 to 99 wt %, 75 to 98 wt %, 80 to 98 wt %, 80 to 97 wt %, 85 to 95 wt %, or even 90 to 95 wt % of the ethylenically unsaturated compound (A), based on the total weight of compounds (A) and (B).

[0079] As is customary in the art, the aqueous radiation-curable compositions of the present disclosure may further comprise a variety of additional ingredients, depending on the targeted application and properties of such compositions. In a typical embodiment, the aqueous radiation-curable composition further comprises at least one additive selected from the group consisting of photoinitiators, inhibitors, antioxidants, biocides, UV stabilizers, UV absorbers, nanoparticles, dispersants, slip aids, fillers, plasticizers, flow additives, antifoam additives, rheology modifiers, anti-settling agents, wetting agents, defoamers, flame retardants, leveling agents, slip agents, water scavengers, matting agents, waxes, pigments, dyes, cosolvents, resinous materials dispersed or solubilized in the composition, and any combination or mixture thereof.

[0080] In an advantageous embodiment, the aqueous radiation-curable composition may further comprise one or more external thermal crosslinkers that allow for dual curing (radiation and heat). Examples of suitable crosslinkers are (blocked) polyisocyanates, polyaziridines, polycarbodiimides, polyepoxides, polyalkoxysilanes, and metal salts such as ammonium zirconium carbonate. Polyisocyanates are particularly suitable, especially hydrophilic polyisocyanates commercially available from Covestro AG under the trade name BAYHYDUR.

[0081] The aqueous radiation-curable compositions of the present disclosure can be prepared in a variety of ways according to techniques well known to those skilled in the art. In a typical procedure, the compositions are prepared by blending compounds (A), (B), optionally (F), and optionally other ingredients under high shear, for example, using a Cowless propeller at 20 to 2000 rpm (depending on the Cowless diameter, vessel diameter, and volume being stirred) at a temperature between 20 and 80°C. Addition of water in such amounts over a period of 5 to 60 minutes at a temperature between 15 and 80°C results in an aqueous composition with a solids content corresponding to phase inversion, typically near 80%.

[0082] Typically, the aqueous radiation-curable compositions of the present disclosure can be referred to as aqueous emulsions, more typically oil-in-water emulsions. The aqueous radiation-curable compositions disclosed herein typically contain 25 to 95 wt. %, more typically 35 to 60 wt. % water, based on the total weight of the composition. Compositions according to the present disclosure typically contain less than 25 wt. %, less than 20 wt. %, less than 15 wt. %, less than 10 wt. %, less than 5 wt. %, or even less than 1 wt. % organic solvents and volatile organic compounds (VOCs), based on the total weight of the composition. Advantageously, the aqueous radiation-curable compositions according to the present disclosure are free of organic solvents and volatile organic compounds.

[0083] According to another aspect, the present disclosure relates to a coating composition comprising the aqueous radiation-curable composition described above. The aqueous radiation-curable composition disclosed herein is in fact particularly well suited for preparing coatings. All the specific preferred aspects described above in the context of the aqueous radiation-curable composition, particularly with regard to the ethylenically unsaturated compound (A) and the reactive ionic external emulsifier (B), are fully applicable to the coating composition.

[0084] Advantageously, coatings obtained from the described aqueous radiation curable compositions possess excellent properties and performance attributes with respect to adhesion to difficult-to-bond plastic substrates (especially polycarbonate and acrylonitrile butadiene styrene), hot water resistance, hydrolysis resistance, visual appearance and gloss in complex formulations (e.g., metallic or matte formulations), abrasion resistance, and low VOC characteristics.

[0085] In an advantageous embodiment, the coating composition is a hard coat composition.Therefore, the aqueous radiation-curable composition of the present disclosure is very suitable for forming coatings used in 3C applications, which are of particular interest in the context of the present disclosure.Product applications in this industry segment are practically limitless and can typically be related to consumer electronics (such as mobile phones, computers, televisions, compact discs, etc.), automotive plastics for interior applications (such as dashboards, trims, etc.) or exterior applications (such as headlights, mirrors, bumpers, wheel covers, etc.), and industrial plastics (such as films, labels, boxes, toys, sporting goods, garden furniture, etc.).

[0086] The aqueous radiation curable compositions according to the present disclosure are also suitable for use in overprint varnishes, inks, adhesives, and for coating three-dimensional articles.

[0087] Therefore, according to another aspect, the present disclosure relates to an ink (e.g., inkjet), overprint varnish, adhesive, or three-dimensional article comprising the above-described water-based radiation curable composition or coating composition.

[0088] Another aspect of the present disclosure relates to an article or substrate that is at least partially coated, printed, or treated with the waterborne radiation curable composition, coating composition, ink, overprint, varnish, or adhesive described above.

[0089] In yet another aspect of the present disclosure, there is provided a method for producing an aqueous radiation curable composition, comprising: a) mixing at least one ethylenically unsaturated compound (A) as described above with at least one reactive ionic external emulsifier (B) as described above, thereby obtaining a premix; b) adding water to the pre-mixture until phase inversion occurs.

[0090] In an advantageous embodiment of this method, the mixing step a) comprises mixing at least one ethylenically unsaturated compound (A) with at least one reactive ionic external emulsifier (B) and a further compound (F), the compound (F) being selected in particular from the group of co-emulsifiers and additional surfactants.

[0091] Further advantageously, the method for producing an aqueous radiation-curable composition further comprises a step of (pre-)diluting at least one reactive ionic external emulsifier (B) in water before carrying out the step of mixing with the at least one ethylenically unsaturated compound (A).

[0092] According to yet another aspect, the present disclosure provides a method for coating an object or substrate, comprising: a) providing an aqueous radiation curable composition or coating composition as described above; b) applying the composition to at least a portion of a surface of an object or substrate; and c) curing the composition by subjecting the coated surface to actinic radiation and / or thermal energy.

[0093] Typically, a water evaporation step is carried out before the curing step. Typically, at least 98%, preferably at least 99%, and preferably all of the water is evaporated. The active energy rays used for curing are preferably ultraviolet light, electron beam, X-ray, radioactive, or radio frequency. Ultraviolet light with a wavelength of 180 to 400 nm is particularly preferred from an economical standpoint. Curing by irradiation may be followed by, or alternatively replaced by, thermal curing in the presence of a suitable external (thermal) crosslinker.

[0094] In particular embodiments of the present invention, the article or substrate comprises plastic, more particularly is made from plastic. In another particular implementation, the article or substrate comprises wood.

[0095] The aqueous radiation-curable compositions or coating compositions described above are typically cured by ultraviolet radiation, generally in the presence of a photoinitiator. Alternatively, they can be cured by electron beam radiation, allowing the use of photoinitiator-free compositions. The compositions according to the present invention offer extremely rapid curing, characterized by higher reactivity, which allows for higher line speeds or less radiation energy curing, and improved productivity. Low-energy ultraviolet light sources (LED lamps) can also be used.

[0096] According to yet another aspect, the present disclosure relates to the use of the above-described water-based radiation curable or coating compositions in computer, communications, and consumer electronics applications, dual cure applications, (wood and flexible) coating applications, composite applications, three-dimensional (3D) applications, (inkjet) printing applications, adhesive applications, paper impregnation applications, or thick pigmentation systems. [Example]

[0097] The present disclosure is further illustrated by the following examples, which are for illustrative purposes only and are not intended to limit the scope of the appended claims.

[0098] Throughout this disclosure and the Examples section, the following test and measurement methods are used to characterize exemplary aqueous radiation curable compositions and coatings obtained therefrom.

[0099] Test Method: A) Particle size Dynamic light scattering (DLS) measurements are used to characterize the hydrodynamic size of particles in various aqueous compositions. Prior to DLS measurements, concentrated compositions are diluted with deionized distilled water to obtain a particle concentration of 0.05 w / w%. The diluted compositions are then filtered. DLS measurements are then performed at 23°C using a Beckman-Coulter Delsa Nano-c particle analyzer. The wavelength of incident monochromatic light used in DLS measurements is λ = 658 nm. Scattered light is detected at an angle of 165° in a near-backscattering configuration. The z-average particle size, along with the polydispersity index, is determined from second-order cumulant analysis of the electric field autocorrelation function. The single-particle diffusion coefficient is then estimated from the average decay constant. From this, the median particle size d50 can be derived using the Stokes' relationship.

[0100] B) Solid content The solids content (SC) of the various aqueous compositions is determined by a gravimetric method, which in the case of radiation curable emulsions involves drying at 120° C. for 2 hours.

[0101] C) Viscosity The viscosity of the various aqueous compositions is measured at 23° C. using a cone-plate rheometer MCR092 (Paar-Physica) according to test method DIN EN ISO 3219. A fixed shear rate of 25 s −1 is used.

[0102] D) Colloidal stability The colloidal stability of various aqueous compositions is assessed at 23°C by visually observing decantation and / or phase separation (expressed as a percentage of the total height) in samples weighing 20 g and placed in an oven at 60°C. Colloidal stability is reported herein as the number of days until settling exceeds 2% of the total height of the sample. In the context of this disclosure, good colloidal stability is achieved if no degradation of the product is observed over 10 days at 60°C.

[0103] E) Molecular weight and polydispersity The number-average molecular weight (Mn), weight-average molecular weight (Mw), and polydispersity (D) were determined by conventional gel permeation chromatography (GPC) using Polymer Laboratories EasyCal polystyrene standards (molecular weight range: 200–400,000 g / mol). Samples were dissolved in tetrahydrofuran (THF) containing 0.5% toluene as a flow marker (1.0% wt. / wt.). Analysis was performed by liquid chromatography (Merck-Hitachi L7100) 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 molecular size in solution and detected by a refractive index detector. Data were collected and processed using Polymer Laboratories Cirrus GPC software.

[0104] F) Glossiness Gloss evaluation is carried out on coatings formed on Leneta™ Plain White Chart. Gloss values ​​are given in gloss units at an angle of 60° [GU] and are determined in accordance with test method DIN EN ISO 2813.

[0105] G) Adhesiveness The adhesive performance of the coatings to the surface of the corresponding substrate (initial adhesion ADH) is evaluated using a crosshatch test according to test method ASTM D3359 B. In each case, five parallel cuts, 1 cm long and 1 mm apart, are first made in the coating using a knife. Next, five parallel cuts, 1 cm long and 1 mm apart, are made transversely. An adhesive tape (Scotch®) is then firmly pressed onto the cross-cut coating and quickly removed. Damage to the cross-cut surface area of ​​the coating due to loss of adhesion is expressed on a scale of 0B to 5B, with a score of 5 corresponding to the best adhesion.

[0106] H) Hot water resistance This resistance test is performed only on coatings that show good initial adhesion (ADH test = 5B). The coating is immersed in hot water (temperature 80 or 85°C) for 30 or 60 minutes. The adhesive performance of the crosshatch tape is re-evaluated on the coating, which has been dried according to the procedure described above. The hot water resistance test is passed if it achieves a score of at least 4B.

[0107] I) Hydrolysis resistance This resistance test is performed according to industry test standard VW TL 226 (Volkswagen AG) on only those coatings that exhibit excellent initial adhesion (ADH test = 5B). The coated substrates are placed in a humidity chamber at 60°C and 95% relative humidity for 96 hours. The coatings on the coated substrates are then evaluated for visual damage, gloss, and crosshatch adhesion after the humidity test. The hydrolysis resistance test is considered to have passed if the coating is not visually damaged and achieves the same level of gloss and adhesion before and after the test.

[0108] J) Scratch resistance Scratch resistance is determined using a Resistant Coating to Abrasion (RCA) abrader - Norman Tool Tester, according to test method ASTM F-2357. The RCA test is performed using standard paper as the abrasive. Abrasion is performed by pressing the standard paper with a specific load (175 g) onto the coated polycarbonate substrate. The back side of the standard paper is in contact with a rubber ring. The results are expressed as the number of cycles required until the coated substrate begins to show visual damage, cloudiness, or white areas. The higher the number of cycles, the better the abrasion resistance.

[0109] K) Hardness The measurement method relates to surface hardness. A coating 120 micrometers thick applied wet to a glass substrate is dried for 5 minutes at 40°C, then 5 minutes at 80°C, and finally cured three times under a UV lamp (Hg) at 80 W / cm at a rate corresponding to the reactivity. The coated sample is allowed to stabilize for 24 hours in an air-conditioned room (20°C, 50% humidity), and the pendulum hardness (Persoz) is determined in seconds at three points on the surface. The average value is calculated.

[0110] Raw materials: In this example, the following raw materials and starting products are used: Ebecryl® 1290 is a hexafunctional aliphatic urethane acrylate oligomer commercially available from Allnex Germany GmbH, hereafter referred to as E-1290. Ebecryl® 5129 is a hexafunctional aliphatic urethane acrylate oligomer commercially available from Allnex Germany GmbH, hereafter referred to as E-5129. IRR 1094 is a hexafunctional aliphatic urethane acrylate oligomer available from Allnex GmbH, Germany. Ebecryl® 1872 is a polyester acrylate resin commercially available from Allnex Germany GmbH, hereafter referred to as E-1872. Ebecryl® 838 is a polyester acrylate resin commercially available from Allnex Germany GmbH, hereafter referred to as E-838. Ebecryl® 3700 is an epoxy acrylate resin commercially available from Allnex Germany GmbH, hereafter referred to as E-3700. Ebecryl® 5848 is a partially renewable resource based epoxy acrylate resin commercially available from Allnex Germany GmbH, hereafter referred to as E-5848. RAS-1 is an ether sulfate type reactive anionic surfactant, which uses a polyoxyethylene alkyl ether ammonium sulfate containing 10 oxyethylene units and is commercially available from ADEKA Corporation of Japan under the trade name Reasop® SR series. RAS-2 is a reactive anionic surfactant using polyoxyethylene styrenated phenyl ether ammonium sulfate, commercially available under the trade name Hitenol® AR series from Daiichi Kogyo Seiyaku Co., Ltd. of Japan. RAS-3 is an ether sulfate type reactive anionic surfactant, which uses a polyoxyethylene alkyl ether ammonium sulfate containing 30 oxyethylene units and is commercially available from ADEKA Corporation of Japan under the trade name Reasop® SR series. RNAS-C is a comparative reactive nonionic surfactant that uses a polyoxyethylene alkyl ether containing 30 oxyethylene units and is commercially available from ADEKA Corporation of Japan under the trade name Reasop® ER series. Maxemul® 7101 is a non-ionic surfactant commercially available from Croda, UK, hereafter referred to as M-7101. Rhodafac® RS-610 / A25 is a phosphated non-reactive anionic surfactant based on ammonium phosphate, polyoxyethylene tridecyl ether, commercially available from Solvay, hereafter referred to as R-610. HDDA is 1,6-hexanediol diacrylate commercially available from Allnex GmbH, Germany. EOEOEA is ethoxyethoxyethyl acrylate commercially available from Rahn USA Corp. under the trade name Miramer M170. ZAY 6840 is an alkyd / acrylic resin obtained from Allnex GmbH, Germany. IPDI is isophorone diisocyanate, commercially available from Sigma-Aldrich. Additol® HDMAP (also known as Photoinitiator 1173) is a photoinitiator commercially available from Allnex Germany GmbH, hereafter referred to as A-HDMAP. Omnirad 500 is a photoinitiator commercially available from IGM Resins, hereafter referred to as OMN-500. Additol® XL250 is a wetting and dispersing agent commercially available from Allnex GmbH, Germany, hereinafter referred to as A-XL250. Tafigel® PUR40 is a non-ionic polyurethane butyl triglycol / water associative thickener commercially available from Munzing, hereafter referred to as T-PUR40. Tafigel® PUR80 is a non-ionic polyurethane butyl triglycol / water associative thickener commercially available from Munzing, hereafter referred to as T-PUR80. BYK® 349 is a polyether-modified siloxane defoamer commercially available from BYK. NIPSIL E1011 is a matting agent commercially available from Tosoh Corporation of Japan. Hereinafter referred to as N-E1011. Additol® XL 250 is an anionic wetting and dispersing phosphine agent commercially available from Allnex GmbH, Germany, hereafter referred to as A-XL250. Additol® TPO is a phosphine oxide photoinitiator commercially available from Allnex GmbH, Germany. SBC AQJ6911 is an aluminum paste commercially available from Changzhou Yale, China. Butyl cellosolve (BCS) is commercially available from Dow Chemicals. Propylene glycol monomethyl ether (PGME) is commercially available from Dow Chemicals. N,N-dimethylethanolamine (DMEA) is commercially available from BASF.

[0111] example: Example 1: General preparation of exemplary aqueous radiation-curable compositions (Examples 1-12) and comparative examples (Examples C1-C5) The ethylenically unsaturated compound (A), the reactive ionic external emulsifier (B), which may be pre-diluted in water, and any additional components (e.g., cosurfactant, etc.) are charged into a double-walled stainless steel container at 23°C. The first portion of water W1 is then added, and the resulting blend is gradually stirred at 1000 rpm with a 60 mm diameter Cowles propeller until the phase inversion point (corresponding to the maximum viscosity) is reached, thereby forming an aqueous emulsion. Stirring at 1000 rpm is continued for at least 1.5 hours to further reduce the particle size of the emulsion. The second portion of water W2 is then added to the mixture at 23°C at a constant flow rate using a peristaltic pump for approximately 5 minutes, during which the Cowles rotation speed is gradually reduced to 500 rpm and the temperature is lowered to 23°C to complete the emulsion. [Table 1] [Table 2]

[0112] Example 2: General preparation of exemplary aqueous radiation-curable compositions (Examples 13 and 14) First, an ethylenically unsaturated compound containing ionic (carboxylate) functionality (A) is prepared by charging epoxy acrylate resin E-5848 and succinic acid into a double-walled stainless steel vessel at 23°C. The reactor is then started and the reactor jacket is heated to 80°C with air sparging. The reaction is maintained for 4-7 hours, with the partial and total acid numbers measured over time. IPDI is then added to the reaction mixture at 80°C, and the reaction is continued for approximately another 2 hours. The reaction mixture is then cooled to 50-60°C, after which a reactive ionic external emulsifier (B), which may be pre-diluted in water, is added with moderate stirring until completely homogeneous. The neutralizer solution is then added at 50-60°C with moderate stirring until completely homogeneous. An emulsion is then formed by phase inversion. To this end, the stirring is interrupted and the first portion of water (typically one-third of the total water) is added, before switching to high-shear stirring. If necessary, add some additional water portions to reach the phase inversion point (corresponding to the highest viscosity). Maximum mixing energy is applied at that stage for 15 minutes, after which the remaining water is added to complete the emulsion. The temperature is then reduced to below 35°C and the biocide is added. [Table 3]

[0113] Example 3: Properties and Stability of Exemplary Waterborne Radiation-Curable Compositions (Examples 1-6) and Comparative Examples (Examples C1-C2) The properties and stability performance of the emulsions according to Examples 1-6 and the comparative examples C1-C2 were determined according to the test methods described above. The exemplary compositions of Examples 1-6 and the comparative examples C1-C2 are all based on a urethane acrylate used as the ethylenically unsaturated compound (A). The comparative composition of Example C1 contains a copolymerizable nonionic surfactant, while the comparative composition of Example C2 contains a conventional nonionic surfactant. The results are shown in Table 4 below. [Table 4]

[0114] Example 4: Properties and Stability of Exemplary Waterborne Radiation-Curable Compositions (Examples 7-12) and Comparative Examples (Examples C3-C5) The properties and stability performance of the emulsions according to Examples 7-12 and the comparative examples C3-C5 were determined according to the test methods described above. The exemplary compositions of Examples 7 and 12, as well as the comparative examples C3-C4, are all based on a urethane acrylate used as the ethylenically unsaturated compound (A). The comparative composition of Example C3 contains a reactive nonionic surfactant, while the comparative composition of Example C4 contains a conventional nonreactive anionic surfactant. The exemplary compositions of Examples 8-10 are all based on a polyester acrylate used as the ethylenically unsaturated compound (A). The exemplary composition of Example 11 and the comparative example C5 are based on an epoxy acrylate used as the ethylenically unsaturated compound (A). The comparative composition of Example C5 contains a copolymerizable nonionic surfactant. The results are shown in Table 5 below. [Table 5]

[0115] Example 5: Properties and Stability of an Exemplary Waterborne Radiation Curable Composition (Example 12) and a Comparative Example (Example C6) The properties and stability performance of the emulsion according to Example 12 and the comparative example of Example C6 were determined according to the test methods described above. The exemplary composition of Example 12 is described above. The comparative example of Example C6 has the exact same composition as Example 12, except that the premix containing the ethylenically unsaturated compound (A) and the reactive ionic external emulsifier (B) was not preformed before adding water. In contrast, the comparative example of Example C6 was formed by first mixing water with the reactive ionic external emulsifier (B) and then adding the ethylenically unsaturated compound (A) to the preformed aqueous mixture. The results are shown in Table 6 below. [Table 6]

[0116] Example 6: Properties and Stability Performance of Exemplary Waterborne Radiation Curable Compositions (Examples 13-14) The properties and stability performance of the emulsions according to Examples 13 and 14 were determined according to the test methods described above. The exemplary compositions of Examples 13 and 14 are prepared using an ethylenically unsaturated compound (A) that further contains an ionic (carboxylate) functional group. The results are shown in Table 7 below. [Table 7]

[0117] As can be seen from the results shown in Tables 4-7, the aqueous radiation-curable compositions according to the present disclosure (Examples 1-14) exhibit excellent colloidal stability, even under severe aging conditions, as well as other advantageous properties, particularly relatively small particle size and relatively high solids content. In contrast, the performance and properties obtained with comparative aqueous radiation-curable compositions not according to the present disclosure (Examples C1-C6) are even less advantageous. In particular, the comparative compositions typically exhibit poor colloidal stability or undesirable particle size.

[0118] The aqueous radiation-curable compositions of Examples 13 and 14 exhibit excellent sustainability properties, as their biocarbon content was calculated to be approximately 75% based on the total carbon content of the compositions. These compositions offer easy application, good drying, and film formation, resulting in a wet-on-touch coating before curing. After UV curing, the resulting coating has a Persoz hardness of 75 seconds and solvent resistance of greater than 100 acetone double rubs. The aqueous radiation-curable compositions of Examples 13 and 14 have been found to be particularly suitable as primer coatings for wood substrates, providing good adhesion and substrate wetting combined with attractive gloss and adhesion. They can also be used for paper impregnation.

[0119] Example 7: General preparation of exemplary coating compositions (Examples 16-17) and comparative coating compositions (Examples C7 and C9) Before preparing the exemplary and comparative coating compositions, the exemplary aqueous radiation-curable composition of Example 15 and the comparative aqueous radiation-curable composition of Example C8 must first be prepared. The exemplary composition of Example 15 and the comparative composition of Example C8 are prepared according to the general procedure described in Example 1 above, based on the formulations set forth in Table 8 below. [Table 8]

[0120] An exemplary clear coating composition according to Example 16 and a comparative clear coating according to Example C7 are further prepared based on the formulations set forth in Table 9 below. [Table 9]

[0121] The coating formulation is applied to a polycarbonate substrate using a bar coater, thereby obtaining a 50 micrometer wet coating layer. The applied formulation is dried at 50°C for 6 minutes and then heated to 80 watts / cm. 2 The coating is cured under UV light using a 1000 kJ Hg lamp at a curing speed of 5 m / min. The cured coating is then used for further testing.

[0122] An exemplary metal coating composition according to Example 17 and a comparative metal coating according to Example C9 are further prepared based on the formulations set forth in Table 10 below. [Table 10]

[0123] The metal coating formulation is applied to a plastic substrate (PC or ABS) using a spray coater. The applied formulation is dried at 60°C for 10 minutes, thereby obtaining a dry film thickness (DFT) of approximately 10 micrometers. Subsequently, a dry film thickness of 80 watts / cm 2The coating is cured under UV light using a 1000 kJ Hg lamp at a curing speed of 5 m / min. The cured coating is then used for further testing.

[0124] Example 8: Performance Attributes of an Exemplary Clear Coating (Example 16) and a Comparative Clear Coating (Example C7) Various performance attributes of the exemplary clear coating composition (Example 16) and the comparative clear coating (Example C7), particularly adhesion to polycarbonate substrates, hot water resistance, and hydrolysis resistance, were determined according to the test methods described above, and the results are shown in Table 11 below. [Table 11]

[0125] As can be seen from the results shown in Table 11, a clear coating according to the present disclosure (Example 16) exhibits excellent performance attributes with respect to adhesion to polycarbonate substrates, hot water resistance, and hydrolysis resistance, even under stringent conditions. In contrast, the performance and properties obtained with a comparative clear coating not according to the present disclosure (Example C7) are less favorable. In particular, the comparative clear coating typically exhibits poor hot water resistance and hydrolysis resistance.

[0126] Example 9: Performance Attributes of an Exemplary Metal Coating (Example 17) and a Comparative Metal Coating (Example C9) Various performance attributes of the exemplary metal coating (Example 17) and the comparative metal coating (Example C9), particularly adhesion to polycarbonate and ABS substrates, hot water resistance, scratch resistance, and gloss, were determined according to the test methods described above. The results are shown in Table 12 below. [Table 12]

[0127] As can be seen from the results shown in Table 12, the metallic coating according to the present disclosure (Example 17) possesses excellent performance attributes with respect to adhesion to polycarbonate and ABS substrates, hot water resistance, scratch resistance, and gloss. In contrast, the performance and properties obtained with the comparative metallic coating not according to the present disclosure (Example C9) are less favorable. In particular, the comparative metallic coating typically exhibits poor hot water resistance, scratch resistance, and gloss.

Claims

1. a) mixing at least one ethylenically unsaturated compound (A) with at least one reactive ionic external emulsifier (B) having the general formula (I): D-O-(R １ O) ｎ -X (I) (In the formula, D is a moiety containing an ethylenically unsaturated group (E), R １ is a straight or branched chain C ２ ~C ６ is an alkylene group, X is an ionic moiety; n is in the range of 4 to 50 and mixing with a reactive ionic external emulsifier (B) represented by b) adding water to the premix until phase inversion occurs; The aqueous radiation-curable composition is obtained by

2. 10. The aqueous radiation curable composition of claim 1, wherein n is 50 or less, 45 or less, 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or even 10 or less.

3. 3. The aqueous radiation curable composition of claim 1, wherein the ethylenically unsaturated group (E) is selected from the group consisting of allyl, vinyl, propenyl, allyloxy, vinyloxy, propenyloxy, allyloxymethyl vinyloxymethyl, propenyloxymethyl, (meth)acryloyl, and any combination or mixture thereof.

4. 4. The aqueous radiation curable composition of claim 1, wherein the ionic moiety (X) is an anionic moiety, preferably selected from the group consisting of sulfate groups, sulfonate groups, phosphate groups, phosphonate groups, phosphite groups, and any combination or mixture thereof.

5. 5. The aqueous radiation curable composition according to claim 1, wherein the moiety (D) is selected from the group consisting of a linear or branched alkyl group, a linear or branched aryl group, a linear or branched alkyl ether group, and a linear or branched aryl ether group, all of which are further substituted with the ethylenically unsaturated group (E).

6. The moiety (D) is represented by the general formula (II): R ３ -O-CH ２ -CHR ２ - (II) (In the formula, R ２ is -CH ２ -O-CH ２ -CH=CH ２ and R ３ is a straight or branched chain (C ８ ~C １４ ) alkyl groups, especially straight chain (C １０ ~C １２ ) alkyl group) Or general formula (III): ( ３ . ２ || ２ (). (In the formula, R ２ is -CH ２ -O-CH ２ -CH=CH ２ and R ３ is a straight or branched chain (C ８ ~C １４ ) alkyl groups, especially straight chain (C １０ ~C １２ ) alkyl group) Or general formula (IV): 【Chemistry 1】 (In the formula, (E) is -CH=CR ４ -CH ３ ,or -CH ２ -CR ４ =CH ２ and R ４ is H or a straight or branched chain (C １ ~C ６ ) alkyl group, (R ５ )teeth, 【Chemistry 2】 and m １ and m ２ and n is independently 1 or 2.

7. 7. The composition according to claim 1, wherein the reactive ionic external emulsifier (B) is selected from the group consisting of (ethylenically unsaturated derivatives of) polyoxyethylene alkyl ether sulfate (ammonium) salts and polyoxyethylene aryl ether sulfate (ammonium) salts, in particular polyoxyethylene styrenated phenyl ether sulfate (ammonium) salts.

8. The reactive ionic external emulsifier (B) 【Transformation 3】 and 【Chemistry 4】 (In the formula, m ３ is 1 or 2, R ３ and n is as defined in claims 1 and 6.

9. 9. The aqueous radiation curable composition according to claim 1, wherein the ethylenically unsaturated compound (A) further comprises ionic functional groups which are at least partially neutralized by a neutralizing agent (C).

10. 10. The aqueous radiation curable composition of claim 9, wherein the ionic functional groups are acidic functional groups, in particular selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, and any combination or mixture thereof.

11. 11. The aqueous radiation curable composition of any one of claims 1 to 10, having a particle size of 800 nm or less, 600 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, 100 nm or less, or even 80 nm or less, as determined by DLS measurements according to the test methods described in the experimental section.

12. 12. The aqueous radiation curable composition of any one of claims 1 to 11, having a solids content of more than 30 wt%, more than 35 wt%, more than 40 wt%, more than 45 wt%, more than 50 wt%, more than 55 wt%, more than 60 wt%, or even more than 65 wt%, as determined by gravimetry according to the test methods described in the experimental section.

13. A coating composition comprising the aqueous radiation curable composition of any one of claims 1 to 12.

14. 1. A method for producing an aqueous radiation curable composition, comprising: a) mixing at least one ethylenically unsaturated compound (A) according to any one of claims 1 to 10 with at least one reactive ionic external emulsifier (B) according to any one of claims 1 to 8, thereby obtaining a premix; b) adding water to the premix until phase inversion occurs; A method comprising:

15. 14. Use of the aqueous radiation curable or coating composition according to any one of claims 1 to 13 in computer, communication and consumer electronics applications, dual cure applications, coating applications, composite applications, three-dimensional (3D) applications, (inkjet) printing applications, adhesive applications, paper impregnation applications or thick pigmentation systems.

Images