Sustainable radiation-curable hybrid offset inks, methods of making the same, and related uses thereof

Abstract

This invention provides radiation-curable hybrid ink and coating compositions containing high levels of biorenewable content and comprising a large amount of inert hard resin. When overprinted with UV varnish, these radiation-curable hybrid ink and coating compositions exhibit good lithographic properties, low roll swell, and low gloss backwash effect. These ink and coating compositions can be used for wet lithographic printing.

Description

Permanent radiation-curable hybrid lithographic ink The present invention relates to high biorenewable content (BRC) radiation-curable hybrid inks and coatings comprising energy-curable monomers, oligomers, and photoinitiators, and raw materials used in conventional lithographic inks, such as oils, alkyds, and hard resins. The radiation-curable hybrid inks and coatings are suitable for application by lithographic printing. Conventional inks for lithographic printing are formulated with vegetable or mineral oils, alkyd resins, and phenolic or hydrocarbon resins. These oils penetrate the substrate to induce physical drying or settling (the "quick-set" effect). However, when printing on non-porous substrates, such as plastic films, the quick-set effect cannot be utilized. For printing on non-porous substrates, inks are formulated with vegetable oils and their esters (known as drying oils) to dissolve hard resins and reduce viscosity. The oils in lithographic inks participate in the drying of the ink through oxidation reactions. A major drawback of conventional lithographic inks is their slow drying speed. Conventional oil- and alkyd-based lithographic inks dry slowly due to substrate penetration (sedimentation) and oxidation. This negatively impacts the productivity achievable by converters. Therefore, there is a need to produce faster-drying inks to increase productivity. Energy-curable inks have also been used in lithography. Energy-curable inks have improved gloss and resistance properties. However, there are disadvantages in using energy-curable inks in lithography. For example, the pigment wetting of energy-curable inks is not as good as that of conventional inks, resulting in problems with print density. In addition, energy-curable inks exhibit low shear viscosity, are less stable emulsions with water, and have higher viscosity. The lack of stability of emulsions with water results in a smaller water balance on the printing press. Higher viscosity can result in picking up fibers or coatings when printing on paper or board. In addition, the classification of raw materials used in energy-curable inks is much more critical for health than in conventional systems. Materials used for radiation polymerization are mainly derived from synthetic processes using petrochemically derived materials. The use of bio-sourced materials is limited in the inks of this technology, which provide energy-curable inks with low BRC values. Typically, inks (conventional or UV-drying) contain waxes to ensure good printing and converting processes by preventing scratches and print degradation. These waxes are usually synthetic and based on micronized polyethylene (PE) and polytetrafluoroethylene (PTFE). The European Chemicals Agency (ECHA) has proposed a regulatory definition for microplastics: "Material consisting of solid polymer particles to which additives or other substances may have been added, wherein ≥1% weight / weight (w / w) of the particles have (i) all dimensions 1 nm ≤ x ≤ 5 mm, or (ii) for fibers, a length of 3 nm ≤ x ≤ 15 mm and a length-to-diameter ratio > 3. Excluded are polymers occurring in nature that have not been chemically modified (except by hydrolysis), as well as (bio)degradable polymers." The regulation of microplastics does not directly affect ink formulations, as the particles are dispersed in a polymeric binder network and are not free. However, for sustainability purposes, high BRC inks should not contain any synthetic waxes such as PE or PTFE waxes. Depending on the requirements of a particular print job, a converter may want to use both conventional and energy-curable lithographic inks. Conventional inks are typically printed on NBR rollers, while energy-curable inks are typically printed on ethylene-propylene-diene-monomer (EPDM) rollers. Energy-curable inks are incompatible with NBR rollers, and conventional inks are incompatible with EPDM rollers. Using incompatible inks causes the rollers to swell, thus compromising print quality. To use both conventional and energy-curable inks on the same press, the converter must switch the rubber rollers and blankets on the press to a hybrid system. Often, to improve the gloss of prints made with conventional inks, converters apply an energy-curable topcoat to the printed substrate. However, these energy-curable topcoats are often incompatible with oil- and alkyd-based inks, resulting in "gloss fallback." Gloss fallback is a phenomenon in which a radiation-curable coating applied over conventional inks loses gloss within a short period of time (usually within a day) after curing. To improve gloss fallback, a water-based primer is typically applied between the print and the energy-curable topcoat. In an attempt to overcome these problems, efforts have been made to develop "hybrid" inks that contain conventional ink components and energy-curable components. Paul Gaevert, Radtech Conference, November 3-5, 2003, Conference Proceedings, Ink performance properties of UV, conventional and hybrid sheet-fed inks", Tony Bean in Radtech Report October 2009, Hybrid Sheetfed lithographic systems – State of the Art;” and Dieter Kleeberg in “ Quality enhancement with hybrid production”, Process 2006 (a publication by the printing press manufacturer KBA) describes hybrid inks. Radiation-curable hybrid inks are radiation-curable inks that also contain the raw materials of conventional inks, such as oils, alkyd resins, and hard resins. Hybrid inks combine different drying characteristics and are preferably dried under UV (ultraviolet) or EB (electron beam) radiation, and can also be dried oxidatively using air or heat. In addition, these inks can be dried by allowing the oil to penetrate into the substrate, like conventional oil-based inks. One advantage of hybrid inks is that they can be directly overprinted with radiation-curable coatings with only a slight loss of gloss (i.e., a slight gloss fall). Therefore, a water-based primer between the ink and the coating, as well as double coaters on the printing press, can be retained. However, since radiation-curable hybrid inks are based on chemically different materials (such as non-polar vegetable oils or minerals) and phenolic or hydrocarbon resins in combination with more polar monomeric acrylates and resins, good compatibility is not easy to achieve. One disadvantage of hybrid inks is that the stability of the hybrid ink must be balanced. In the presence of oxygen, oil-based materials can begin to increase in viscosity due to oxidation, especially in the presence of driers. However, on the other hand, oxygen stabilizes radiation-curable components such as acrylates. A major drawback of currently available hybrid inks is their slow drying speed due to the incorporation of oils and alkyds, which dry slowly through penetration (sedimentation) and oxidation. Since the determining factors for ink drying in these inks are oil sedimentation and alkyd oxidation, converters cannot achieve the productivity (line speeds) associated with 100% radiation-curable inks. This is particularly important for non-porous substrates into which the oil does not penetrate. Therefore, the typical hybrid inks described in the literature contain a large amount of radiation-curable materials, but only relatively small amounts of oils and alkyds. Typical formulations of radiation-curable hybrid inks were given in a radiation technology conference (Paul Geavert, Radtech Europe 2003), where the materials (oils and alkyds) of conventional inks were limited to 15%. Generally speaking, a typical radiation-curable hybrid ink of this technology contains 5 to 15% vegetable oils and alkyd resins, 0 to 15% polyester acrylates, 0 to 10% epoxy acrylates, 0 to 50% vegetable oil acrylates, 5 to 15% acrylic monomers, 14 to 24% pigments, 4 to 8% fillers, 4 to 8% photoinitiators, and less than 1% stabilizers and inhibitors. This is also confirmed in a review article ("Hybrid Sheetfed Lithographic Systems - State of the Art", Tony Bean, Radiation Technology Report 2009), where a typical hybrid ink contains only a small amount of conventional raw materials. The aforementioned formulation ranges exhibit slow curing speeds (low reactivity) and low solvent resistance due to the presence of non-reactive inert oils and alkyds. However, due to the limited amount of conventional materials, these inks exhibit very similar lithographic properties compared to typical UV inks. The lithographic properties of typical UV inks are inferior to those of conventional inks using non-reactive inert oils and alkyds. Therefore, the only advantage of the formulation range mentioned above is that such typical radiation curable hybrid inks can be run on rollers of radiation curable inks as well as those of conventional inks. However, the goal of obtaining substantially better lithography is not achieved. Furthermore, many hybrid inks of the prior art contain compounds that are classified as carcinogenic, mutagenic, or toxic for reproduction (CMR) under EU Classification, Labelling and Packaging of Substances (CLP) Regulation 1272 / 2008. Because these compounds are harmful to human health, it is desirable to identify novel hybrid ink and coating compositions that do not contain CMR compounds and that have comparable properties (such as gloss reduction, tack, viscosity, and curing) to compositions of the prior art. Thus, it can be seen that formulating hybrid inks and coatings containing high-BRC, low-CMR compounds is complex, and optimizing the properties of these inks and coatings is equally complex. From a lithographic perspective, inks containing large amounts of oils, alkyds, and hard resins are advantageous. Conversely, large amounts of radiation-curable monomers and oligomers are advantageous in terms of drying speed, productivity, and gloss reduction. The present invention provides a complex mixture of conventional raw materials and energy-curable raw materials with high BRC content. The inks and coatings of the present invention do not contain synthetic waxes and have good stability over time. These inks exhibit good lithographic properties and can be overprinted with UV varnishes with only slight gloss fallback and good inter-coat adhesion. The inventive hybrid inks and coatings exhibit good lithographic properties compared to 100% radiation-curable inks due to the better pigment wetting of alkyd resins and conventional resins compared to (meth)acrylate monomers and oligomers. The inventive sustainable hybrid inks and coatings of the present invention can be free of carcinogenic, mutagenic, or reprotoxic (CMR) materials. The present invention provides a high BRC lithographic radiation hybrid ink or coating that provides a minimum modern carbon percentage (PMC) of at least 40% and preferably at least 45% according to ASTM D6866 (Method B). The present invention provides a high BRC lithographic radiation hybrid ink or coating composition, comprising: a) 10 wt% to 30 wt% of one or more inert hard resins selected from the group consisting of rosin resins, rosin resin derivatives, hydrocarbon resins, modified hydrocarbon resins, isodiallyl phthalate resins, non-phthalate allyl resins, and combinations thereof; b) 10 to 60% of a non-UV raw material selected from the group consisting of inert hard resins, vegetable oils, vegetable oil esters, alkyd resins, antioxidants, and combinations thereof; and c) 5 wt% to 45 wt% of one or more multifunctional (meth)acrylate monomers and / or oligomers; wherein the ink or coating comprises ≥ 40% BRC, more preferably ≥ 45% BRC. The lithographic radiation hybrid ink or coating composition preferably comprises less than 10 wt% CMR compounds, and more preferably less than 5 wt% CMR compounds, and even more preferably is substantially free of CMR compounds. The present invention also provides a more sustainable composition by replacing synthetic waxes with bio-derived waxes. The present invention also provides a method of printing an object comprising applying the lithographic radiation-curable hybrid ink of the present invention as a UV-coldset lithographic ink or as a UV-heatset lithographic ink. The present invention further provides a printed article comprising the energy-curable hybrid lithographic ink of the present invention. The present invention also provides a conventional concentrated pigment base and energy-curable technology varnish (TV) to simplify the preparation of spot colors by simply mixing the desired pigmented base with TV in the appropriate ratio. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of any subject matter claimed. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one skilled in the art to which this invention belongs. Unless otherwise indicated, all patents, patent applications, published applications and publications, websites, and other published materials mentioned throughout this disclosure are incorporated by reference in their entirety for any purpose. The present invention provides radiation-curable hybrid inks and coatings that have good lithographic properties and low gloss fallback when overprinted with UV-varnishes. These inks can be used for lithographic wet printing. Definition In this application, the use of the singular includes the plural unless otherwise expressly stated. As used herein, the singular form “ one"," "A" and "the" are intended to include the plural forms as well. In this application, the use of "or" means "and / or" unless stated otherwise. As used herein, the term "comprises and / or The term “comprising” specifies the presence of stated features, integers, steps, operations, elements, and / or components, but does not preclude the presence and addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. Furthermore, to the extent that the terms “includes,” “having / has,” “with,” “composed,” “comprised,” or variations thereof are used in the detailed description or claims, such terms are intended to be inclusive in a manner similar to the term “comprising.” As used herein, the term "(meth)acrylate" refers to both acrylate and methacrylate compounds. When the term "acrylate" is used alone, it is understood that it encompasses both acrylate and methacrylate compounds. As used herein, an "energy-curable" or "radiation-curable" ink or coating composition is a composition that can be cured by any suitable source of actinic radiation. Suitable sources of UV radiation include, but are not limited to, high-pressure mercury bulbs, medium-pressure mercury bulbs, xenon bulbs, carbon arc lamps, metal halide bulbs, iron-doped lamps, UV-LED lamps, or sunlight. Other sources of radiation include, but are not limited to, microwaves, infrared, electron beams, visible light, x-rays, lasers, and the like. As used herein, "radiation-curable hybrid inks" or "energy-curable hybrid inks" are ink or coating compositions that contain energy-curable components (such as, but not limited to, acrylate monomers) and also contain raw materials of conventional inks such as, but not limited to, oils, alkyd resins, and hard resins. As used herein, the term "article" or "articles" refers to a substrate or an article. Examples of articles include, but are not limited to, substrates such as paper, plastic, plastic or polymer films, glass, ceramics, metals, composites, and the like; and articles such as publications (e.g., brochures), labels and packaging materials (e.g., cardboard sheets or corrugated board), containers (e.g., bottles, cans), polyolefins (e.g., polyethylene or polypropylene), polyesters (e.g., polyethylene terephthalate), metallized foils (e.g., laminated aluminum foil), metallized polyesters, metal containers, and the like. As used herein, the terms “ink / inks,” “coating / coatings,” and “ink and coating / inks and coatings” are used interchangeably. As used herein, the terms "inert resin" and "inert hard resin" are used interchangeably. The term "monomer" refers to a compound that is capable of polymerization and does not contain multiple monomer units. The term "oligomer" refers to a compound comprising multiple monomeric units. As used herein, the term "oligomer" refers to such a compound having a number average molecular weight of at least 400 Da. The term "non-UV" refers to compounds that are inert and do not react under photoinitiating conditions (e.g., UV light) in the presence of a photoinitiator. The term excludes monomers and oligomers that can be initiated under such conditions, such as (meth)acrylates. Throughout this disclosure, all parts and percentages are by weight (wt % or mass %, based on the total weight of the composition (including any solvent)) and all temperatures are in °C unless otherwise indicated. Unless otherwise indicated, all method steps are performed in the order in which they are listed. Compatibility: As used herein, compatibility of components means that the components are miscible at room temperature (23°C) and do not undergo phase separation for at least one week after mixing. As used herein, solubility and compatibility are used interchangeably. Lithographic: A composition suitable for lithographic printing. Radiation-curable hybrid inks and coatings The present application provides energy curable hybrid inks and coatings suitable for lithographic printing. The inks and coatings of the present invention are balanced radiation curable hybrid inks and coatings containing a mixture of conventional oils, alkyds and inert hard resins. The present invention provides a lithographic radiation-curable hybrid ink or coating composition comprising: a) 10% to 30% by weight of one or more inert hard resins selected from the group consisting of rosin resins, rosin resin derivatives, hydrocarbon resins, modified hydrocarbon resins, isodiallyl phthalate resins, non-phthalate allyl resins, and combinations thereof; and b) 10 to 60% of non-UV raw materials selected from the group consisting of inert hard resins, vegetable oils, vegetable oil esters, alkyd resins, antioxidants, and combinations thereof; and c) 5% to 45% by weight of one or more multifunctional acrylate monomers and / or oligomers d) 0 to 10% of monofunctional (meth)acrylate monomers and / or oligomers; and wherein the ink or coating composition comprises ≥ 40% biorenewable content. Advantages of the Invention The resulting inks and coatings exhibit good lithographic properties and can be overprinted with UV varnishes with only slight gloss fallback and good intercoat adhesion. The inventive hybrid inks exhibit good lithographic properties compared to 100% radiation-curable inks because alkyds and conventional resins wet pigments better than acrylate monomers and oligomers. Due to the inclusion of energy-curable monomers, the inventive hybrid inks also offer faster drying and curing, thereby increasing productivity. The larger amount of conventional acrylate-compatible inert hard resin compared to oils and alkyds helps reduce curing delay and improve compatibility with acrylates. The inventors have now surprisingly observed that with the introduction of large amounts of inert hard resins, such as phenolic rosin resins, maleic rosin resins and / or aromatic hydrocarbon resins, the total amount of conventional ink ingredients in a hybrid ink can be significantly increased, which facilitates lithographic printing while minimally affecting the drying speed. It describes the preparation of conventional varnishes using a large amount of inert hard resins (such as maleic rosin, aromatic hydrocarbon resins, and / or phenolic rosin resins) in a vegetable oil, which may be one or more drying oils, semi-drying oils, and non-drying oils. The compatibility ratios between the conventional materials and the (meth)acrylated monomers and oligomers must be determined. While not being bound by any particular theory, the inventors believe that once the radiation-curable acrylate matrix dries, the inert hard resin (even when present in large quantities) immediately hardens and becomes solid, so drying characteristics (line speed) are not significantly affected. The inks and coatings of the present invention can be run at conventional printing speeds used in the art (e.g., at least 10,500 sheets / hour). Furthermore, a second thing to improve radiation curing is to partially replace or limit the often proposed vegetable oil acrylates, which are notorious for slow radiation curing, by very reactive multifunctional acrylates, such as trifunctional acrylates, including propoxylated glyceryl triacrylate. Contrary to popular belief, oil-modified acrylates must be used in hybrid inks for compatibility reasons due to their compatibility with conventional oils and alkyds. The inventors have discovered that many common multifunctional acrylates (such as propoxylated glyceryl triacrylate) can be used to a large extent. However, it is more difficult to include highly ethoxylated acrylic monomers in large quantities, which can cause some incompatibility due to their polarity. While monofunctional acrylates can be used in the hybrid inks of the present invention, these materials are preferably used at a maximum of 10%, more preferably at a maximum of 5%. Unlike many commercial hybrid inks and coatings that are more like typical UV inks and contain only some conventional materials (e.g., Suncure Hybrite, Sun Chemical), the inks of the present invention contain a considerable amount of conventional ink raw materials to achieve good lithographic performance. The amounts of these materials are balanced in such a way that the majority of the oil and alkyd resin are exchanged for an acrylate-soluble inert hard resin (such as, for example, modified maleic rosin or modified phenolic rosin or hydrocarbon resin) so that the drying speed is not greatly affected. One advantage of the hybrid inks of the present invention is that the lithographic print is positively impacted and exhibits less fogging, less feedback, and a wider water-window than typical 100% radiation curable inks. Another advantage due to the oil-based components is that the color strength and flow of the ink wells are often better than 100% radiation curable inks because oil-based materials (such as alkyd resins) evenly disperse and encapsulate the pigments and result in good color strength and good flow. Because of the intermediate behavior between conventional and UV, this ink can be run on conventional rollers but preferably on combination rollers using a hybrid blanket or UV blanket. The ink of the present invention can be washed preferably with conventional and UV printer wash solutions, which was confirmed during laboratory studies and press trials on a Heidelberg MO & Roland 700 press. The intrinsic viscosity of the hybrid ink and coating of the present invention is Typically, the radiation-curable hybrid inks and coatings of the present invention exhibit a viscosity of 5 to 100 Pa·s at a shear rate of D = 50 1 / s at 23°C. A viscosity of 20 to 60 Pa·s is preferred. The flow of the radiation-curable hybrid inks of the present invention was also determined. Typical flow values ​​measured using an inclined plane test (e.g. an inclined aluminum plate) at 90° inclination and with 1 ml of ink are 2 to 15 cm after 15 minutes. Viscosity The inks of the present invention exhibit a viscosity of 12 to 40 units as measured using an "Inkometer" from Thwing Albert. A more preferred viscosity is < 30 units. Tack can affect print quality. If the viscosity is too high, it can damage substrates such as paper, a phenomenon known as "pickup," where the fibers of the paper substrate are pulled onto the ink blanket. A viscosity that is too low can lead to problems such as insufficient ink feed, transfer, and distribution. Lithographic Performance This mixed ink was run on a Roland 700 press (combination roller from Böttcher and mixing blanket from Trelleborg; 4% Sunfount 480 and 3% IPA fount) at 12,500 sheets / hour on an Invercote G substrate at a 1.45 OD target. The lithographic behavior was similar to a standard lithographic sheetfed ink with an acceptable ink / water balance. Gloss Retrospect To maximize productivity with fast-curing UV inks, inline coating with a UV overprint varnish, which also provides high gloss, is often preferred. However, when conventional sheet-fed inks are overprinted with UV inks and then terminally cured, the initial gloss of the cured coating often decreases by 10 to 25 gloss points within 24 hours. This also depends on the type of substrate and is particularly critical for open-pore, uncoated substrates. This is often counteracted by applying a water-based primer between the conventional ink and the UV overprint varnish. However, this requires a dual coater with an integrated thermal or infrared dryer on the press and a separate water-based coating, which adds additional time and expense to the process. While these drying systems can be used on presses such as the ManRoland 700 Ultima or Heidelberg Speedmaster Duo, they are more of a niche technology. By replacing conventional inks with the radiation-curable hybrid inks of the present invention, this effect can often be avoided, and the gloss reversion effect is minimized without the need for a water-based primer. For the hybrid inks of the present invention, it was found that a balance was achieved with a low gloss fallback effect, thereby giving a stable gloss, which is usually difficult to achieve with water-based coatings. However, these inks showed good lithographic properties. When using the hybrid inks of the present invention, a small amount of gloss fallback may be seen, but preferably, the degree of gloss fallback will be within the preferred range. For high gloss hybrid inks (e.g., those with an initial gloss of >60), the gloss drop is preferably <10 units; more preferably <7 units. Replacement of carcinogenic, mutagenic, or reprotoxic (CMR) compounds Hybrid inks of this technology may contain compounds classified as carcinogenic, mutagenic, or reprotoxic (CMR) under EU Classification, Labelling and Packaging of Substances (CLP) Regulation 1272 / 2008. While the use of such compounds can provide hybrid inks and coatings with advantageous properties, these compounds pose health risks and their use should be avoided. CMR compounds present in hybrid inks of this technology include trimethylolpropane triacrylate (TMPTA), polysilicone diacrylates (such as Ebecryl 350), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (ominirad 379), and multifunctional aminobenzoate derivatives such as 1,3-propylene glycol, 2-ethyl-2-(hydroxymethyl), polymer with oxirane, and 4-(dimethylamino)benzoate (Genopol AB-2). The inventors have discovered hybrid inks that do not contain any CMR compounds and have properties consistent with hybrid inks of the prior art. The ink or coating composition of the present invention may contain less than 20% by weight of compounds classified as carcinogenic, mutagenic, or reprotoxic (CMR), preferably less than 10% by weight of CMR compounds, and even more preferably less than 5% by weight of CMR compounds. Most preferably, the ink or coating composition of the present invention is substantially free of CMR compounds. The inventors have surprisingly discovered that alternative CMR compounds, including the multifunctional acrylate TMPTA described as an essential component of hybrid inks of the present invention, can be replaced by alternative non-CMR compounds. Furthermore, the inventors have discovered that the resulting hybrid inks have properties at least comparable to those of compositions of the present invention comprising CMR compounds. Specifically, the inventors have discovered that (meth)acrylates classified as CMR compounds in compositions of the present invention can be replaced with one or more (meth)acrylate oligomers selected from the group consisting of acrylated oils, epoxy acrylates, oil-modified polyester acrylates, acrylated polyurethanes, acrylated polyacrylates, acrylated polyethers, acrylated amines, and combinations thereof, to provide hybrid inks and coatings with comparable properties. Specifically, the inventors discovered that the ... have at least comparable viscosity, tack, and curing properties to those of inks containing CMR compounds of the present invention. Curing was evaluated using the UV set-off test described in the Examples. More preferably, the CMR compound is replaced with one or more (meth)acrylate oligomers selected from the group consisting of polyester acrylates, acrylated polyurethanes, acrylated polyethers, and combinations thereof. The hybrid ink or coating composition of the present invention has a biorenewable content of at least 40%, and preferably at least 45%, by weight. The inventors surprisingly discovered that replacing the components of the ink of the prior art with alternatives having high BRC provides hybrid inks having properties at least comparable to those of the compositions of the prior art that do not contain the BRC content of the present invention. As used herein, sustainability refers to the BRC content of a material. Thus, improving the sustainability of a package involves increasing the BRC content of the package, for example by replacing an alternative ink or curing ink with the lithographic radiation curable hybrid ink or coating composition of the present invention. The hybrid inks and coatings of the present invention may contain 0 to 40% by weight, such as 0 to 25% by weight, of vegetable oils, vegetable oil esters, and plant alkyd resins; >10% by weight, preferably 10 to 30% by weight, of an inert hard resin; 10 to 40% by weight of a (meth)acrylate oligomer; and 0 to 10% by weight of a (meth)acrylate monomer. These hybrid inks and coatings may contain less than 20% by weight of a compound classified as a CMR. These hybrid inks and coatings may further contain 0 to 40% by weight of a colorant (pigment or dye); 0 to 10% by weight of a bulking agent and filler; 0 to 10% by weight of a photoinitiator; and 0 to 4% by weight of additives. The preferred total amount of vegetable oil, vegetable oil ester, alkyd, and inert hard resin is >10%, more preferably >20%, more preferably >30%, more preferably >40%, and more preferably >50%. The preferred amount of inert hard resin is >10%, more preferably >13%. The hybrid inks and coatings of the present invention preferably comprise 12 to 26 wt% of an inert hard resin, 15 to 25 wt% of vegetable oils, vegetable oil esters, and plant alkyd resins, 15 to 35 wt% of one or more multifunctional (meth)acrylate oligomers, and less than 5 wt% of monofunctional (meth)acrylate monomers and oligomers. The compositions preferably have a biorenewable content of 45% or greater. The hybrid inks and coatings preferably contain less than 5 wt% of compounds classified as CMRs. Preferred hybrid inks and coatings of the present invention comprise 15 to 25 wt% (preferably 15 to 20 wt%) of the vegetable oils, esters, and alkyds as vegetable oils and esters and 3 to 10 wt% as vegetable alkyd resins. The exact formulation will also depend on the targeted ink properties. Ratios of inert resins, vegetable oils, vegetable oil esters and alkyds to (meth)acrylate monomers and oligomers. Inert resins, vegetable oils, vegetable oil esters, and alkyds can be incorporated into the inks or coatings of the present invention in combination with (meth)acrylate monomers and oligomers to provide a ratio of inert resins, vegetable oils, vegetable oil esters, and alkyds to (meth)acrylate monomers and oligomers of 0.1:1.0 to 2.0:0.0, preferably 0.5:1.0 to 2.0:1.0, and more preferably 0.5:1.0 to 1.0:1.0. Inert hard resin The radiation-curable hybrid ink and coating compositions of the present invention comprise 10% to 30% by weight of one or more inert hard resins, based on the total weight of the ink or coating composition, wherein the inert hard resins are selected from the group consisting of rosin resins, rosin resin derivatives, hydrocarbon resins, modified hydrocarbon resins, isodiallyl phthalate resins, non-phthalate allyl resins, and combinations thereof. The inert hard resins used in the present invention are preferably present in an amount of 10% to 30% by weight, such as 12% to 30% by weight, more preferably 12% to 25% by weight, and even more preferably 15% to 25% by weight, such as 15% to 20% by weight. Inert hard resins are typically natural or synthetic amorphous materials that, for the purposes of the present invention, preferably form a tack-free film at room temperature after application to a substrate. Most of these materials are oligomers or polymers. The inert hard resin used in the present invention is selected from the group consisting of rosin resins, rosin resin derivatives, hydrocarbon resins, modified hydrocarbon resins, isodiallylphthalate resins, non-phthalate allyl resins, and combinations thereof. Any of these inert hard resins that is compatible and / or soluble with acrylate monomers and oligomers, vegetable oils, vegetable oil esters, and plant alkyd resins can be used in the hybrid ink of the present invention. Preferred inert hard resins include rosin resin derivatives (such as phenolic rosin resins) as well as isodiallylphthalate resins and non-phthalate allyl resins (such as diallylcycloalkane-based resins). Rosin resin derivatives consist of various isomers with different chemical structures, including derivatives of abietic acid, levopimaric acid, neoabietic acid, palustric acid, dehydroabietic acid, pimaric acid, and isopimaric acid. Rosin resin derivatives used in the present invention can be modified with maleic anhydride (i.e., maleic rosin resin) or fumaric acid and esterified with a polyol (such as glycerol and pentaerythritol). The rosin resin used in the present invention is preferably a phenolic rosin resin. The radiation curable hybrid ink and coating compositions of the present invention may further comprise other resins. For example, the radiation curable hybrid ink and coating compositions of the present invention may comprise one or more resins selected from the group consisting of oil-modified phenolic resins, ketone resins, aldehyde-urea resins, oil-modified polyester resins, melamine resins, epoxy resins, polyurethane resins, acrylic styrene resins and combinations thereof, provided that the resins are soluble / compatible in acrylic monomers, oligomers, oils and alkyds. When present, such additional resins may be present in an amount of 1 wt % to 20 wt % based on the total weight of the ink or coating composition. For example, such additional resins are preferably present in an amount of 1 wt % to 15 wt %; such as 5 wt % to 15 wt %; and more preferably in an amount of 10 wt % to 15 wt %. (Meth)acrylate oligomers The radiation-curable hybrid ink and coating compositions of the present invention further comprise one or more (meth)acrylate oligomers. The one or more (meth)acrylate oligomers are preferably present in an amount of 0.1% to 45% by weight, such as 1% to 30% by weight, based on the total weight of the ink or coating composition. The one or more (meth)acrylate oligomers are more preferably present in an amount of 5% to 40% by weight, such as 10% to 40% by weight, and even more preferably 15% to 35% by weight, based on the total weight of the ink or coating composition. The (meth)acrylate oligomers used in the present invention have a number average molecular weight of at least 400 Da, such as preferably between 400 and 3,000 Daltons or between 1000 and 3000 Da. The (meth)acrylate oligomers used in the present invention preferably have an acrylate functionality > 2, more preferably ≥ 4, and even more preferably ≥ 6. Preferably, the (meth)acrylate oligomers have a viscosity of at least 5 Pa·s when measured according to the method described in the Examples. Examples of suitable acrylate oligomers include, but are not limited to, acrylated oils based on linseed oil, soybean oil, and castor oil, epoxy acrylates, urethane acrylates, oil-modified polyester acrylates (such as Ebecryl 870 (Allnex)), acrylated polyurethanes, acrylated polyacrylates, acrylated polyethers, and acrylated amines, which impart rheology, pigment wetting, transfer, gloss, chemical resistance, and other film properties. Preferred are acrylated oils, polyester acrylates (such as oil-modified polyester acrylates), acrylated polyurethanes, acrylated polyethers, and combinations thereof. The inventors have discovered that replacing lower molecular weight (meth)acrylates (i.e., components having a molecular weight of less than 400 Da) with higher molecular weight oligomeric (meth)acrylates (i.e., components having a number average molecular weight of at least 400 (e.g., 400 to 3000 Da)) results in hybrid ink and coating compositions with improved atomization. The (meth)acrylate monomers and (meth)acrylate oligomers of part c) preferably have a molecular weight of at least 400 Da. (Meth)acrylate monomers The radiation-curable hybrid ink and coating compositions of the present invention may comprise up to 45 wt. %, such as 5 wt. % to 45 wt. %, of one or more multifunctional (meth)acrylate monomers, based on the total weight of the ink or coating composition. Preferably, the radiation-curable hybrid ink and coating compositions of the present invention comprise less than 15 wt. % of one or more multifunctional (meth)acrylate monomers. Examples of monomers suitable for the inks of the present invention include acrylic monomers having 2 to 4 acrylic groups. A non-limiting list of examples of acrylate monomers includes 1,2-ethanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, tripropylene glycol diacrylate, bisphenol-A diacrylate, ethoxylated bisphenol-A-diacrylate, bisphenol-A-diglycidyl ether diacrylate, ethoxylated bisphenol-A-diacrylate, poly(ethylene glycol) diacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate, acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, propoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ethoxylated dipentaerythritol hexaacrylate or a mixture thereof, preferably ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol triacrylate and propoxylated pentaerythritol tetraacrylate, and a combination thereof. The radiation-curable hybrid ink and coating compositions of the present invention may further comprise one or more monofunctional (meth)acrylate monomers. When present, the one or more monofunctional acrylate monomers are typically present in an amount of up to 5 wt %, such as 1 wt % to 5 wt %, preferably up to 4 wt %, and more preferably up to 3 wt %, based on the total weight of the ink or coating composition. (Meth)acrylate monomers useful in the present invention include those derived from vegetable oils (such as soybean acrylate) and fatty acids. However, the use of such monomers is preferably limited. For example, the ink or coating of the present invention may contain less than 10% by weight of vegetable oil (meth)acrylate, preferably less than 5% by weight of vegetable oil (meth)acrylate, and even more preferably, be substantially free of vegetable oil (meth)acrylate. For example, the one or more monofunctional monomers may be present in an amount of 1 wt% to 3 wt%; or 1 wt% to 2 wt%; or 2 wt% to 5 wt%; or 2 wt% to 3 wt%; or 3 wt% to 5 wt%. Suitable monofunctional acrylate monomers include, but are not limited to, tert-butyl cyclohexanol acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, tetrahydrofuranyl acrylate, lauryl acrylate, 2-phenoxyethyl acrylate, isodecyl acrylate, ethoxylated phenyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, isooctyl acrylate, octyldecyl acrylate, polycaprolactone acrylate, ethoxylated nonaphenyl acrylate, isobornyl acrylate, cyclotrimethylolpropane formaldehyde acrylate, stearyl acrylate, behenyl acrylate, alkoxylated lauryl acrylate, combinations thereof, and the like. Lauryl acrylate is preferred. Vegetable oils and vegetable oil esters The radiation-curable hybrid ink and coating compositions of the present invention may further comprise one or more vegetable oils and vegetable oil esters. When present, the one or more vegetable oils and vegetable oil esters may be present in an amount of 0.1% to 35% by weight, based on the total weight of the ink or coating composition. Preferably, the one or more vegetable oils and vegetable oil esters are present in an amount of 10% to 30% by weight, and even more preferably, in an amount of 15% to 25% by weight. The one or more vegetable oils and vegetable oil esters may preferably be present in an amount of 0.1% to 20% by weight; or 0.1% to 15% by weight; or 0.1% to 10% by weight; or 0.1% to 5% by weight; or 0.1% to 1% by weight; or 0.1% to 0.5% by weight; or 0.5% to 25% by weight; or 0.5% to 20% by weight; or 0.5% to 15% by weight; or 0.5% to 10% by weight; or 0.5% to 5% by weight; or 0.5% to 1% by weight; or 1% to 25% by weight; or 1% to 20% by weight; or 1% to 15% by weight; or 1% to 10% by weight; or 1% to 5% by weight; or 5% to 25% by weight; or 5% to 20% by weight; or 5% to 15% by weight; or 5% to 10% by weight. The vegetable oils may be one or more drying oils, semi-drying oils, and non-drying oils. Examples include almond oil, cocoa butter, candlenut oil, castor oil, dehydrated castor oil, coconut oil, corn oil, cottonseed oil, grapeseed oil, hempseed oil, linseed oil, olive oil, palm kernel oil, peanut oil, rapeseed oil, rice bran oil, safflower oil, sunflower oil, sesame oil, soybean oil, pine oil, tung oil, and walnut oil, including combinations thereof and fatty acid esters (such as fatty acid alkyl esters). Alternatively, the oil may be one or more fatty acid alkyl esters such as, for example, rapeseed methyl ester, rapeseed isopropyl ester, octanoic acid methyl ester, isopropyl caprate, lauric acid methyl ester, myristate methyl ester, palmitic acid methyl ester, stearic acid methyl ester, oleic acid ethyl ester, erucic acid methyl ester, ricinoleic acid methyl ester, linolenic acid ethyl ester, linolenic acid methyl ester, or isopropyl palmitate. The radiation-curable hybrid ink or coating composition of the present invention may further comprise one or more alkyd resins. When present, the one or more alkyd resins may be present in an amount of 1% to 15% by weight, based on the total weight of the ink or coating composition. The one or more alkyd resins are preferably present in an amount of 1% to 12% by weight, such as 2% to 10% by weight, more preferably 3% to 8% by weight, and even more preferably 5% to 8% by weight. The one or more alkyd resins may also be present in an amount of 1% to 5% by weight; or 1% to 3% by weight; or 1% to 2% by weight; or 2% to 15% by weight; or 2% to 12% by weight; or 2% to 10% by weight; or 2% to 8% by weight; or 2% to 5% by weight; or 2% to 3% by weight; or 3% to 15% by weight; or 3% to 12% by weight; or 3% to 10% by weight; or 3% to 8% by weight; or 3% to 5% by weight; or 5% to 15% by weight; or 5% to 12% by weight; or 5% to 10% by weight; or 5% to 8% by weight. Alkyds are polyesters modified by the addition of vegetable oils, fatty acids, and other components and are therefore partially derived from vegetable oils (or as used herein, "plant alkyds"). In the inks of the present invention, the alkyds typically have a number average molecular weight of 1,000 to 20,000 Da. The alkyd used in the present invention can be the reaction product between a polyol and an acid or anhydride. The alkyd used in the present invention is a plant alkyd. The alkyd used in the present invention can be modified with fatty acids (saturated or unsaturated) from plants and vegetable oils. Non-limiting examples of such acids include sebacic acid, lauric acid, stearic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, erucic acid, linolenic acid, linolenic acid, linoleic acid, eleostearic acid, eicosapentaenoic acid, arachidonic acid, clupanodonic acid, ricinoleic acid, ricinelaidic acid, versatic acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, combinations thereof, and the like. The alkyd used in the present invention can be prepared from a vegetable oil that has been trans-esterified by adding a polyol. The polyol can be glycerol. The vegetable oil can be pine oil. The alkyd used in the present invention can include soybean oil, sunflower oil, rapeseed oil, corn oil, tung oil, linseed oil, coconut oil, and palm oil. The alkyd used in the present invention can be any combination of the alkyds mentioned above. The lithographic radiation curable hybrid ink or coating composition of the present invention preferably comprises the vegetable oil, the vegetable oil ester and the vegetable alkyd resin in an amount of 0.1 to 30 wt % and more preferably in an amount of 10 to 25 wt %. The radiation-curable hybrid ink and coating compositions of the present invention may further comprise one or more colorants in the form of pigments. When present, the one or more colorants are present in an amount of 1 wt % to 20 wt %, preferably 5 wt % to 18 wt %, and more preferably 10 wt % to 15 wt %, based on the total weight of the ink or coating composition. For example, the one or more colorants may be present in an amount from 1% to 15% by weight; or from 1% to 10% by weight; or from 1% to 5% by weight; or from 1% to 3% by weight; or from 1% to 2% by weight; or from 2% to 20% by weight; or from 2% to 15% by weight; or from 2% to 10% by weight; or from 2% to 5% by weight; or from 2% to 3% by weight; or from 5% to 20% by weight; or from 5% to 15% by weight; or from 5% to 10% by weight; or from 10% to 20% by weight; or from 10% to 15% by weight; or from 15% to 20% by weight. Pigments suitable for use in the present invention include conventional organic or inorganic pigments. Representative pigments include, but are not limited to, Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 63, Pigment Yellow 65, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 75, Pigment Yellow 83, Pigment Yellow 97, Pigment Yellow 98, Pigment Yellow 106, Pigment Yellow 111, Pigment Yellow 114, Pigment Yellow 121, Pigment Yellow 126, Pigment Yellow 127, Pigment Yellow 136, Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 174, Pigment Yellow 176, Pigment Yellow 188, Pigment Yellow 194, Pigment Orange 5, Pigment Orange 13, Pigment Orange 16, Pigment Orange 34, Pigment Orange 36, Pigment Orange 43, Pigment Orange 61, Pigment Orange 6 2. Pigment Orange 64, Pigment Red 2, Pigment Red 9, Pigment Red 14, Pigment Red 17, Pigment Red 22, Pigment Red 23, Pigment Red 37, Pigment Red 38, Pigment Red 41, Pigment Red 42, Pigment Red 48:2, Pigment Red 53:1, Pigment Red 57:1, Pigment Red 81:1, Pigment Red 112, Pigment Red 122, Pigment Red 170, Pigment Red 184, Pigment Red 210, Pigment Red 238, Pigment Red 266, Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 61, Pigment Green 7, Pigment Green 36, Pigment Violet 1, Pigment Violet 19, Pigment Violet 23, Pigment Black 7, combinations thereof, and the like. Photoinitiator If cured by UV light, the radiation-curable hybrid ink and coating compositions of the present invention may further comprise one or more photoinitiators. When present, the one or more photoinitiators may be incorporated in an amount of 0.1% to 20% by weight, based on the total weight of the ink or coating composition. For example, the one or more photoinitiators are preferably present in an amount of 0.1% to 15% by weight, such as 0.5% to 15% by weight, or more preferably 1% to 10% by weight, such as even more preferably 4% to 8% by weight. The photoinitiators may also be present in an amount of 0.1% to 3% by weight; or 0.1% to 1% by weight; or 0.1% to 0.5% by weight; or 0.5% to 20% by weight; or 0.5% to 15% by weight; or 0.5% to 10% by weight; or 0.5% to 5% by weight; or 0.5% to 1% by weight; or 1% to 20% by weight; or 1% to 15% by weight; or 1% to 10% by weight; or 1% to 5% by weight; such as 1% to 3% by weight; or 1% to 2% by weight. Examples of suitable photoinitiators include, but are not limited to, benzophenones, benzilketales, dialkoxyacetophenones, hydroxyalkyl-acetophenones, aminoalkylphenones, acylphosphinoxides, and thioxanthones, such as benzophenone, methylbenzophenone, 4-phenylbenzophenone, 4,4'-bis(dimethylamino)-benzophenone, 4,4'-bis(diethylamino)-benzophenone, 2,2-dimethoxy-2-phenylacetophenone. , dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-methyl-1-[4(methoxythio)-phenyl]-2-morpholinopropan-2-one, diphenylacylphenylphosphine oxide, diphenyl(2,4,6-trimethylbenzyl)phosphine oxide, 2,4,6-trimethylbenzylethoxyphenylphosphine oxide, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, or mixtures thereof. For EB-curable inks, no photoinitiator is required. Preferred photoinitiators include type II photoinitiators thioxanthones such as 2-isopropylthioxanthone and 2,4-diethylthioxanthone, type II photoinitiator 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and type I photoinitiators based on phosphinates such as ethyl (2,4,6-trimethylbenzyl)-phenyl-phosphinate. For inks designed for food packaging, migrating low molecular weight monomeric photoinitiators can be minimized or completely replaced by oligomeric or polymeric photoinitiators. Suitable photoinitiators are, for example, photoinitiators containing oligomeric benzophenone derivatives, such as, for example, Omnipol BP from IGM Resins, oligomeric amines, such as, for example, Genopol AB-1 from the Rahn Group, or oligomeric type I photoinitiators, such as Omnipol 910 from IGM. Other optional additives To prevent premature polymerization of double bonds in oils and alkyd resins, antioxidants may be added. Exemplary antioxidants include ascorbic acid, astaxanthin, carotene, chroman (3,4-dihydro-2H-1-benzopyran), hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, vitamin E and vitamin E analogs, mono-tert-butylhydroquinone (MTBHQ), and butylated hydroxytoluene (BHT). Preferred antioxidants are MTBHQ and BHT. When present, the antioxidant is typically present in an amount of 0.1 to 4 wt % based on the total weight of the ink or coating composition. For example, the one or more antioxidants may be present in an amount of 0.1 to 3 wt %; preferably 0.1 to 2 wt %; or more preferably 0.1 to 1.1 wt %. The antioxidant may also be present in an amount such as 0.1% to 0.5% by weight; or 0.5% to 4% by weight; or 0.5% to 3% by weight; or 0.5% to 2% by weight; or 0.5% to 1% by weight; or 1% to 4% by weight; or 1% to 3% by weight; or 1% to 2% by weight; or 2% to 4% by weight; or 2% to 3% by weight; or 3% to 4% by weight. To accelerate the drying of oils and alkyds, the ink may contain one or more driers, which are typically fatty acid salts, such as heavy metal salts of organic carboxylic acids (e.g., manganese). Examples of such heavy metal salts of organic carboxylic acids include, but are not limited to, manganese linoleate, manganese hexadecanoate, or manganese octoate (e.g., see U.S. Patents 5,156,674; 6,899,756; and 7,811,367). The driers may be any commercially available metal driers. When present, the one or more driers are typically present in an amount of 0.1% to 3% by weight, based on the total weight of the ink or coating composition. For example, the one or more desiccants may be present in an amount of 0.1% to 2% by weight; or 0.1% to 1% by weight; or 0.1% to 0.5% by weight; or 0.5% to 3% by weight; or 0.5% to 2% by weight; or 0.5% to 1% by weight; or 1% to 3% by weight; or 1% to 2% by weight; or 2% to 3% by weight. The mixed ink and coating of the present invention may further contain common additives to change the flow, surface tension, gloss, pigment wetting and wear resistance of the cured coating or printed ink. Such additives included in the ink or coating are generally surfactants, waxes, shelf life stabilizers, etc. and combinations thereof. These additives can be used as leveling agents, shelf life stabilizers, wetting agents, slip agents, flow agents and dispersants. Preferred additives include fluorocarbon surfactants, polysilicone and organic polymer surfactants. Examples include the Tegorad product line (Tegorad is a trade name and is a commercially available product of Tego Chemie, Essen, Germany) and the Solsperse product line (Solsperse is a trade name and is a commercially available product of Lubrizol Company). When present, these one or more additives are generally present in an amount of 0.1% by weight to 4% by weight based on the total weight of the ink or coating composition. For example, the one or more antioxidants may be present in an amount of 0.1% to 3% by weight; or 0.1% to 2% by weight; or 0.1% to 1% by weight; or 0.1% to 0.5% by weight; or 0.5% to 4% by weight; or 0.5% to 3% by weight; or 0.5% to 2% by weight; or 0.5% to 1% by weight; or 1% to 4% by weight; or 1% to 3% by weight; or 1% to 2% by weight; or 2% to 4% by weight; or 2% to 3% by weight; or 3% to 4% by weight. The synthetic hybrid inks and coatings of the present invention may contain 1 to 15% by weight of one or more bio-based waxes. Preferably, the synthetic hybrid inks and coatings of the present invention contain 2 to 10% by weight of one or more bio-based waxes. Bio-sourced waxes useful in the present invention include those based on carnauba, sugarcane, polylactic acid, rice bran, hydrogenated castor oil, and poly-(hydroxybutyrate-co-hydroxyvalerate) PHVB. The radiation-curable hybrid inks of the present invention may further contain conventional builders, such as clay, talc, calcium carbonate, magnesium carbonate, or silica, to adjust water pickup, atomization, and color strength. When present, the one or more builders or fillers are typically present in an amount of 1% to 10% by weight, based on the total weight of the ink or coating composition. For example, the one or more bulking agents or fillers may be present in an amount of 1% to 8% by weight; or 1% to 5% by weight; or 1% to 4.5% by weight; or 1% to 4% by weight; or 1% to 3.5% by weight; or 1% to 3% by weight; or 1% to 2.5% by weight; or 1% to 2% by weight; or 1% to 1.5% by weight; or 2% to 10% by weight; or 2% to 8% by weight; or 2% to 5% by weight; or 2% to 4.5% by weight; or 2% to 4% by weight; or 2% to 3.5% by weight; or 2% to 3% by weight; or 2% to 2.5% by weight; or 3% to 10% by weight; or 3% to 8% by weight; or 3% to 5% by weight; or 3% to 4.5% by weight; or 3% to 4% by weight; or 3% to 3.5% by weight; or 4% to 10% by weight; or 4% to 8% by weight; or 4% to 5% by weight. The synthetic hybrid inks and coatings of the present invention preferably contain less than 5% by weight of synthetic waxes, such as PE or PTFE waxes. More preferably, the synthetic hybrid inks and coatings of the present invention are substantially free of synthetic waxes, such as PE or PTFE waxes. Printed objects The present invention also provides a printed article comprising the lithographic radiation-curable hybrid ink or coating composition of the present invention and a substrate. Examples of such articles include, but are not limited to, those comprising a substrate selected from paper, plastic, plastic or polymer film, glass, ceramic, metal, composites, and the like. Such articles also include articles such as publications (e.g., brochures), labels and packaging materials (e.g., cardboard or corrugated board), containers (e.g., bottles, cans), polyolefins (e.g., polyethylene or polypropylene), polyesters (e.g., polyethylene terephthalate), metallized foils (e.g., laminated aluminum foil), metallized polyesters, metal containers, and the like. The substrate to be printed can consist of any typical substrate material, such as paper and cardboard. The substrate can be a paper printing stock commonly used for publications or can be a packaging material in the form of cardboard sheets or corrugated board. The radiation-curable inks and coatings of the present invention can be cured by an actinic light source (such as, for example, UV light) provided by a high-pressure mercury bulb, a medium-pressure mercury bulb, a xenon bulb, a carbon arc lamp, a metal halide bulb, a UV-LED lamp, or sunlight. The wavelength of the applied radiation is preferably in the range of 200 to 500 nm, more preferably 250 to 350 nm. The UV energy is preferably in the range of 30 to 3,000 mJ / cm 2 and more preferably 50 to 500 mJ / cm 2 Furthermore, the bulb may be appropriately selected according to the absorption spectrum of the radiation-curable composition. Alternatively, the actinic radiation may include electron beam radiation (EB). Commercially, EB-driers are available from, for example, Energy Science, Inc., Wilmington, Mass., or from Advanced Electron Beams Inc. (AEB), Wilmington, Mass. The absorbed energy (also called dose) is measured in kilo-Grays (kGy) (one kGy equals 1,000 joules per kilogram). Typically, the electron beam dose should be in the range of 10 kGy to 40 kGy for complete curing. For the radiation-curable compositions of the present invention, preferably, a radiation dose of 20 to 30 kGy at an oxygen level of < 200 ppm is generally sufficient to achieve dry, solvent-resistant inks. If necessary, an infrared or thermal dryer on the printing press can be used to accelerate the settling of the oil component. Preparation of radiation-curable hybrid inks and coatings The ink can be prepared by typical procedures known in the art, typically by dry milling or using a flush, color concentrate, or base. In a typical dry milling process for inks, the desired amount of dry pigment is mixed with conventional oils, alkyd resins, and inert hard resins dissolved in vegetable oil in a dissolver or mixer for 15 to 30 minutes to wet out all the pigment. The pre-mix is ​​then milled on a triple-roll mill (or other grinding mill) at a pressure of 1 to 4 MPa and a temperature of 20 to 40°C until the desired milling specifications are met. The photoinitiator can be added as a solution or paste before or after milling. The pigment can be introduced as a wash. In the "wash process," the wet pigment press cake is "washed" in a high-shear grinding device, such as a sigma blade mixer. Oil, varnish, alkyd, and / or other non-aqueous hydrophobic vehicle are added, and the pigment is ultimately washed into the organic phase, leaving the aqueous phase free of pigment. A considerable portion of the water can then be discarded. To remove residual water, heat and vacuum are typically applied. The resulting product is called a "wash paste" or pigment concentrate (base). The pigment concentrate is then diluted with a solution of acrylate monomers, oligomers, optional photoinitiator, and an inert hard resin (varnish). From a versatility point of view, this is preferred. Color concentrates for coldset inks, heatset inks, or sheet-fed inks are highly appreciated by formulators, provided they can also be used in UV-hybrid inks. Examples The following examples illustrate specific aspects of the present invention and are not intended to limit the scope of the present invention in any manner and should not be interpreted as such. Measurement Method Molecular Weight: The molecular weight of a non-polymeric or oligomeric compound (e.g., a monomer) is defined and calculated from the molecular structure of the compound. Typically, this is given in the monomer supplier's technical data sheet or can be found on the European Chemical Agency (ECHA) website. The molecular weights of oligomeric and polymeric species were determined by gel permeation chromatography (GPC) on a Hewlett-Packard 1050 series HPLC system equipped with two GPC Ultrastyragel columns 103 and 104 Å (5 μm mixed mode, 300 mm x 19 mm, Waters Millipore Corporation, Milford, MA, USA) and THF as the mobile phase. The column temperature was 40°C. The molecular weights were calculated by comparison with polystyrene standards. The skilled artisan will appreciate that this definition of molecular weight applies to polymeric materials that typically have a distribution of molecular weights. Unless otherwise stated, the molecular weights reported herein for oligomers and polymers are number average molecular weights. Biobased / biorenewable content Biobased / biorenewable carbon content (BRC) is determined using the standard method described in ASTM D6866 ("Standard Test Methods for Determining the Biobased Content of Natural Range Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry Analysis"), Method B. See "Understanding biobased carbon content," Society of the Plastics Industry Bioplastics Council (February 2012). The application of ASTM D6866 to determine "biobased content" is based on the same concepts as radiocarbon dating, but without the use of age equations. The ratio of the amount of radiocarbon (14C) in an unknown sample to the amount of radiocarbon (14C) in a modern reference standard is determined. Fossil carbon contains no radiocarbon. The greater the amount of "new" carbon, the more 14C it contains. This ratio is reported as a percentage of the total carbon (which is modern carbon), using units such as "pMC" (percent modern carbon) or BRC (expressed as a percentage). Some suppliers may assess the percentage of biobased content based on weight, based on the "recipe" used by the manufacturer (i.e., how much natural material (such as cellulose) is present in a varnish containing cellulose and copolyester). However, it should be noted that the weight percentage includes the contribution not only from carbon but also from the weight of other elements in the material. For the purposes of this invention, the BRC content refers to the BRC, evaluated using ASTM D6866, Method B. Carcinogenic, Mutagenic or Reprotoxic (CMR) Compounds CMR compounds are classified according to EU Classification, Labelling and Packaging of Substances (CLP) Regulation 1272 / 2008. CMR compounds are those compounds that fall within categories 1A, 1B and 2 of this EU classification. Phenol-modified rosin resin can be prepared by esterification of glycerol (or pentaerythritol) with a polycondensate of rosin, phenol (or bisphenol A) and formaldehyde. Viscosity was measured at 23°C using an MCR301 cone and plate rheometer from Anton Paar GmbH at shear rates of D = 2 to 50 1 / s. The viscosity value (Pa.s) at D = 50 1 / s and the yield value at D = 2 1 / s were recorded. Inkometer viscosity was measured using a calibrated "Inkometer" from Thwing Albert. 3 The ink was placed on an EPDM rubber distribution roller and distributed at a roller speed of 150 rpm for 15 seconds and then at 800 rpm for 60 seconds. Integrated tactile tack (iTack) was also determined using an Alphatack from Novomatics at 30°C and 800 rpm using 100 µL of sample. The measured value (iTack value) was read after 60 seconds. The flow is measured using a vertically positioned aluminum plate at 90° with 1 ml of ink placed on it. The distance (in cm) that the ink runs down the plate after 15 minutes is recorded. Fogging is assessed in two ways. Fogging quotations are determined by visual assessment against an internal scale made with real examples. Firstly, visual assessment is used (visual quotations) and values ​​between 0 (perfect), 1 (excellent), 2 (good), 3 (acceptable), 4 (poor) and 5 (very poor) are obtained. Results of less than 3 are considered acceptable. Secondly, an "Inkometer" from Thwing Albert is used, using 3.5 g of ink placed on an EPDM rubber distribution roller at 32°C, distributed for 15 seconds at a roller speed of 150 rpm and then at 2000 rpm for 5 minutes. During the test, a blank paper sheet is placed behind the roller. The inkometer measures the optical density (OD) of the ink on the paper sheet. Gloss Gloss was measured using a Micro Gloss Instrument from BYK-Gardner set at a 60 degree angle. Gloss is reported in gloss units. The curing of a print is assessed by how much ink from the cured print is transferred (re-printed) to another sheet of paper under high pressure. This simulates the conditions in large paper stacks or rolls of substrate where freshly cured prints are stored under pressure. Ideally, no ink is transferred. Typically, the transfer of the experimental ink to a test paper is compared with the transfer of a control UV ink to a test paper, where the control ink is intended for the same application. The amount of ink that prints back at a defined UV dose is a measure of reactivity and the achievable curing speed (productivity). The curing of the ink was evaluated by the reverse printing test using the following method: The ink was applied to the surface of a cardboard substrate with a print proofer at an appropriate optical density (OD). The OD was determined by a densitometer. Suitable printing optical densities for lithographic inks are 0.9 to 1.5 (yellow), 1.0 to 1.65 (cyan), 1.0 to 1.5 (magenta), and 1.1 to 1.9 (black), depending on the substrate. UV-curing was performed directly on the paper using a 200-watt Fusion H-bulb at a line speed of 400 feet per minute, delivering 33 mJ / cm 2 After the UV-dose, the cardboard substrate (Invercote G – 3 x 3 cm 2 ) was applied to the reverse side of the cured ink sample. Both were introduced on the printing press and 1000 bar (10 tons (1000 Kg) / cm 2 Once this pressure is reached (1-second pressure time), the print is released. The set-off material (transfer ink) on the board substrate is measured using a Techkon densitometer and compared with a control ink. By comparing with the control ink, under the same curing conditions and printing density, the ink with a lower value on the densitometer indicates better curing. Densitometer readings below 0.50 are generally considered good values. The fineness of the ink grind is a key parameter that describes the dispersion quality of the solid pigment particles in the ink. A fineness meter is used to test the fineness of the pigment particles. The meter consists of a steel block with channels of varying depth machined into it. The depth starts at a convenient depth for the type of ink being measured and gradually becomes shallower until it is flush with the steel block surface. The depth of the groove is marked on an adjacent graduated scale. The ink to be tested is poured into the deep end of the groove and scraped toward the shallow end using a flat metal scraper. At the 4 μm point on the graduated scale, the ink track is inspected for the number of large irregularities (the first number in parentheses) and the number of small irregularities (the second number in parentheses). A score of 0 / 0 means that neither large particles nor small irregularities are observed, and the ink is considered acceptable. All inks according to the present invention have acceptable ink grinding characteristics with particle sizes below 15 μm. Two methods were used to test stability. The first method uses a Turbiscan static multi-light scattering (SMLS) analyzer to detect particle migration and size changes. The analyzer uses an oven set at 50°C, in which samples of equal concentration are placed. Two synchronous detectors are used to analyze the backscattering (BS) and transmission (T) signals of the laser light incident on the sample, where the entire length of the sample is scanned and measurements are taken regularly over a period of up to 9 days and 20 hours. The change in backscattering over time (ΔBS (%)) indicates instability in the ink, where larger changes correspond to greater instability (due to particle settling). The Turbiscan Stability Index (TSI) is determined from the sum of the changes in T and BS over the entire height of the sample and plotted as a function of time. A lower TSI indicates increased stability of the sample. The second method utilizes a rheolaser technique based on multi-speckle diffuse wave spectroscopy (MS-DWS) to analyze the rheological properties of samples without mechanical stress (via passive microrheology). During six temperature cycles, the backscattering (BS) of laser light from samples of the same concentration is measured. The same temperature ramp rate is used in each of the six cycles that constitute an experiment. The reaction is measured as microdynamics (mD) (in Hz). Three different temperature ramp rates are used: a) 10 to 50°C at 10°C / min, b) 10 to 50°C at 5°C / min, and c) 10 to 40°C at 10°C / min. The obtained spot images are mathematically analyzed to obtain a characteristic time as a function of time. The characteristic time is inversely calculated to obtain mD and the results are plotted as a function of time. Consistent mD responses across multiple cycles indicate stability. In contrast, mD responses that increase or decrease with increasing cycle number indicate a lack of stability. Examples 1 and 2. Cyan mixed ink containing 16 to 22% inert hard resin Inventive cyan hybrid inks were prepared by dry milling on a triple roll mill (3 passes at 2 MPa (25° C.)) with the composition shown in Table 1 (16% to 22% inert hard resin). Table 1: Examples 1 and 2 1 44.5 wt% modified phenolic resin, 12.5 wt% linseed oil, 21 wt% soybean oil, 21.5 wt% soybean oil methyl ester, 0.5 wt% antioxidant solution (20 wt% BHT contained in soybean oil) 240 wt% diallyl phthalate resin dissolved in 15 wt% lauryl acrylate and 45 wt% propoxylated glyceryl triacrylate (GPTA). GPTA is 3.5 times propoxylated and has 430 gmol -1 molecular weight (i.e. oligomerization). 3 Ebecryl Leo 10801, number average molecular weight = 1500 g / mol (i.e., oligomeric). 4 Genomer 4293: Bio-based, number average molecular weight = 2300 g / mol (also known as oligomeric). 5 Plant wax compound: 40 wt% rice bran wax + 60 wt% hexafunctional polyester acrylate (Ebecryl Leo 10801, number average molecular weight = 1500 g / mol) (i.e., oligomeric). The properties of the inks of Examples 1 and 2 were tested as described above. The results are shown in Table 1A. Table 1A. Properties of Examples 1 and 2 1 The optical density of the printed ink on the printed substrate. The inks of Examples 1 and 2 exhibit typical values ​​for viscosity (20 to 60 Pas), flow (1.5 to 7 cm), and tack (10 to 40 units (inkometer) and 200 to 500 units (Lithotack)) for UV lithographic inks as shown in Table 1A. Table 2: Example 3 with conventional color bases Next, the magenta base was transferred to a triple roll mill and passed through once at 2 MPa (25° C.). Table 3 below shows the composition of the finished ink (13% inert hard resin, 6.2% alkyd and 18% oil and ester components): Table 3: Example 4 Finished Ink 3 Ebecryl Leo 10801, number average molecular weight = 1500 g / mol 5 Plant wax compound: 40 wt% rice bran wax + 60 wt% hexafunctional polyester acrylate (Ebecryl Leo 10801, number average molecular weight = 1500 g / mol (i.e., oligomeric)) The properties of Example 4 were tested as described above. The results are shown in Table 3A. Table 3A. Properties of Example 4 Examples 5. Made from a color base and then UV outside Mixed ink for coating (15% Inert hard resin ) The hybrid ink is made from a cyan universal base (color concentrate) that can be used to prepare sheet-fed inks, heat-set and cold-set inks, and acrylic lightening varnishes by mixing in a dissolver at 40-45° C. for 20 minutes (50% of a combined inert hard resin and alkyd resin and vegetable and mineral oil) and grinding on a triple-roll mill. The purpose of this experiment was to show that the ink of the invention can be overprinted with a UV overprint varnish while exhibiting good visual laydown and printing properties. Table 4: Example 5 Finished ink formulation 6 25% inert hard resin (phenolic modified rosin), 10% alkyd resin, 37% vegetable oil and 28% pigment PB15:3 7 25% inert hard resin (phenolic modified rosin), 15% alkyd resin, 35% vegetable oil and 25% pigment PV23 8 Acrylate lightened varnish: polyester hexafunctional acrylate (Ebecryl Leo 10801, number average molecular weight = 1500 g / mol) (i.e., oligomeric); 54.0% photoinitiator (PI) compound and 16% amine synergist, 16% wax compound, 8% build-up agent, and 6% additives. The photoinitiator (PI) compound and the amine synergist include a mixture of phosphine oxides, α-amino ketones, thioxanthones such as 2,4-dimethylthioxanthones, multifunctional aminobenzoate derivatives, and poly(ethylene glycol) bis(p-dimethylaminobenzoate). The properties of Example 5 were tested as described above. The results are shown in Table 6. Table 4A. Properties of Example 5 The ink was printed on a Roland 700 press (combination roller from Böttcher and hybrid blanket from Trelleborg; 4% Sunfount 480 and 3% IPA fount) at 12500 sheets / hour on an Invercote G substrate at a 1.45 OD target. The ink was immediately overprinted with UV-overprint varnish 44HC150 (Sun Chemical) using an anilox roller @ 140 lines and 150 mJ / cm 2 Terminal cure. Gloss was determined as described above. Gloss regression was indicated by the decrease in gloss over time. A decrease of less than 10 gloss units indicated that the gloss regression was within the optimal range. Table 5: Gloss regression results Table 5 demonstrates that the present mixed ink does not show any gloss regression. Examples 6. By conventional sheet-type color base and containing 20% Cyan mixed ink made from gelled acrylic varnish of inert resin The mixed ink shown in Table 6 is made from a cyan conventional sheet ink base and a gelled acrylate varnish containing 20% ​​inert resin. Table 6: Example 6 9 71.4% fatty acid modified polyester acrylate (Agisyn 716, having a molecular weight of 1100 g / mol (i.e., oligomeric); hexafunctional), 24% inert resin used in the present invention, 2.6% gelling agent in sunflower oil, 2% stabilizer The properties of Example 6 were tested as described above. The results are shown in Table 6A. Table 6A. Properties of Example 6 Stability testing The ink of Example 1 (herein referred to as Agricure) was tested along with a comparative ink (Starluxe) which contained only acrylate monomers and oligomers but was not a hybrid ink and therefore did not contain conventional inert resin components. Turbiscan analysis of Example 1 (AgriCure) detected no significant change in ΔBS (%) for Example 1. In contrast, Turbiscan analysis of Starluxe, which became opaque / clear during the experiment, detected an increased change in ΔBS (%). Figure 1 depicts the TBI of both Example 1 and Starluxe, showing how Starluxe evolved more during the experiment, with a higher TSI after 3 days. RheoLaser Figure 2 depicts the results of a Starluxe RheoLaser analysis under the same conditions, which shows considerably greater variation and noise. Noise typically indicates exudation (where the liquid layer is on top). In contrast, Figure 2 depicts the results of a RheoLaser analysis of Example 1 (Agricure) using six temperature cycles between 10 and 50°C using a 10°C / min heating rate. Minor variations in the mD response were detected. Figure 4 depicts the overall percent change (corresponding to the percent change of the first peak normalized to the first peak of the first cycle). The change for Starluxe starts slowly but increases rapidly after 4 cycles until the overall percent change is greater than that of Example 1 after 6 cycles. Figure 5 depicts how similar results were obtained when the analysis was repeated between 10 and 50°C at a heating rate of 5°C / min. Figure 6 depicts the results obtained when the analysis was repeated between 10 and 40°C at a heating rate of 10°C / min. Again, significantly greater variation and noise were detected for the Starluxe relative to Example 1. In this experiment, some initial variation of Example 1 was observed before the sample stabilized after 1 hour. FIG7 depicts the results of each of the above-mentioned RheoLaser experiments, demonstrating that, for each set of experimental conditions, Example 1 had improved stability compared to Starluxe (after 6 cycles) when tested under the same conditions, indicating that Example 1 had improved stability relative to Starluxe. The present invention has been described in detail, including preferred embodiments thereof. However, it will be apparent that those skilled in the art, after considering this disclosure, may make modifications and / or improvements to the present invention that fall within the spirit and scope of the present invention. Numbered embodiments of the present invention ( Composition illustrate Part of ) 1. A lithographic radiation-curable hybrid ink or coating composition comprising: a) 10% to 30% by weight of one or more inert hard resins selected from the group consisting of rosin resins, rosin resin derivatives, isodiallyl phthalate resins, and combinations thereof; b) 10% to 60% of non-UV raw materials, which may be inert hard resins, plant oils and esters, plant alkyd resins, and antioxidants; and c) 5% to 45% by weight of one or more multifunctional acrylate monomers and oligomers; and d) 0% to 10% of monofunctional acrylate monomers and oligomers; wherein the ink or coating composition comprises ≥ 40% BRC. 2. The lithographic radiation curable hybrid ink or coating composition of Example 1, wherein the ink or coating composition comprises ≥ 45% BRC. 3. The lithographic radiation curable hybrid ink or coating composition of embodiment 1, wherein the one or more inert hard resins are present in an amount of 10 wt % to 20 wt %. 4. The lithographic radiation curable hybrid ink or coating composition of embodiment 1, wherein the one or more inert hard resins are present in an amount of 10 wt % to 15 wt %. 5. The lithographic radiation curable hybrid ink or coating composition of embodiment 1, wherein the one or more inert hard resins are selected from the group consisting of maleic rosin resins and combinations thereof. 6. The lithographic radiation curable hybrid ink or coating composition of embodiment 1, wherein at least one of the inert hard resins is an isodiallyl phthalate resin soluble in an acrylate monomer. 7. The lithographic radiation curable hybrid ink or coating composition of embodiment 1, wherein the one or more inert hard resins are compatible with, soluble in, or compatible and soluble in the acrylate monomers and oligomers, oils, and alkyd resins. 8. The lithographic radiation-curable hybrid ink or coating composition of any one of Examples 1 to 6, further comprising one or more resins selected from the group consisting of oil-modified phenolic resins, ketone resins, aldehyde-urea resins, oil-modified polyester resins, melamine resins, epoxy resins, polyurethane resins, acrylic styrene resins, and combinations thereof. 9. The lithographic radiation curable hybrid ink or coating composition of embodiment 1, wherein the one or more multifunctional acrylate monomers are present in an amount of 5 wt % to 35 wt %. 10. The lithographic radiation curable hybrid ink or coating composition of embodiment 1, wherein the one or more multifunctional acrylate monomers are present in an amount of 5 wt % to 25 wt %. 11. The lithographic radiation curable hybrid ink or coating composition of any one of embodiments 1 to 9, wherein the one or more multifunctional acrylate monomers are selected from 1,2-ethanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, tripropylene glycol diacrylate, bisphenol-A diacrylate, ethoxylated bisphenol-A diacrylate, bisphenol-A diglycidyl ether diacrylate, ethoxylated bisphenol-A diacrylate, poly(ethylene) glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, propoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ethoxylated dipentaerythritol hexaacrylate, and combinations thereof. 12. The lithographic radiation curable hybrid ink or coating composition of any one of embodiments 1 to 10, further comprising 0.1 to 30 wt % of one or more inks, alkyd resins, or combinations thereof. 13. The lithographic radiation curable hybrid ink or coating composition of embodiment 11, wherein the one or more oils, alkyd resins, or combinations thereof are present in an amount of 1 wt % to 15 wt %. 14. The lithographic radiation curable hybrid ink or coating composition of embodiment 11 or 12, wherein the one or more oils are selected from the group consisting of vegetable oils, fatty acid alkyl esters, or combinations thereof. 15. The lithographic radiation curable hybrid ink or coating composition of embodiment 13, wherein the one or more vegetable oils are selected from the group consisting of drying oils, semi-drying oils, non-drying oils, and combinations thereof. 16. The lithographic radiation curable hybrid ink or coating composition of any one of embodiments 1 to 15, further comprising 0.1 wt % to 20 wt % of one or more acrylate oligomers. 17. The lithographic radiation curable hybrid ink or coating composition of embodiment 15, wherein the one or more acrylate oligomers are present in an amount of 1 wt % to 10 wt %. 18. The lithographic radiation curable hybrid ink or coating composition of any of embodiments 15 or 16, wherein each of the one or more acrylate oligomers independently has a number average molecular weight of 400 to 3,000 Daltons and an acrylate functionality equal to or greater than 2. 19. The lithographic radiation-curable hybrid ink or coating composition of any one of embodiments 15 to 17, wherein the one or more acrylate oligomers are selected from the group consisting of acrylated oils, epoxy acrylates, oil-modified polyester acrylates, acrylated polyurethanes, acrylated polyacrylates, acrylated polyethers, acrylated amines, and combinations thereof. 20. The lithographic radiation curable hybrid ink or coating composition of any one of embodiments 1 to 18, further comprising 0.1 wt % to 10 wt % of one or more multifunctional acrylate monomers. 21. The lithographic radiation curable hybrid ink or coating composition of embodiment 19, wherein the one or more monofunctional acrylate monomers are present in an amount of 1 wt % to 15 wt %. 22. The lithographic radiation curable hybrid ink or coating composition of any one of embodiments 1 to 20, further comprising 0.1 wt % to 40 wt % of one or more colorants. 23. The lithographic radiation curable hybrid ink or coating composition of embodiment 21, wherein the one or more colorants are present in an amount of 1 wt % to 20 wt %. 24. The lithographic radiation curable hybrid ink or coating composition of embodiment 21 or 22, wherein the one or more colorants are selected from the group consisting of inorganic pigments, organic pigments, and combinations thereof. 25. The lithographic radiation curable hybrid ink or coating composition of any one of embodiments 1 to 23, further comprising 0.1 wt% to 10 wt% of one or more bulking agents or fillers. 26. The lithographic radiation curable hybrid ink or coating composition of embodiment 24, wherein the one or more extenders or fillers are present in an amount of 1 wt % to 5 wt %. 27. The lithographic radiation curable hybrid ink or coating composition of embodiment 24 or 25, wherein the one or more extenders or fillers are selected from the group consisting of clay, talc, calcium carbonate, magnesium carbonate, silica, and combinations thereof. 28. The lithographic radiation curable hybrid ink or coating composition of any one of embodiments 1 to 26, further comprising 0.1 to 20 wt% of one or more photoinitiators. 29. The lithographic radiation curable hybrid ink or coating composition of embodiment 27, wherein the one or more photoinitiators are present in an amount of 1 wt % to 10 wt %. 30. The lithographic radiation curable hybrid ink or coating composition of embodiment 27 or 28, wherein the one or more photoinitiators are selected from the group consisting of oligomeric photoinitiators, polymeric photoinitiators, and combinations thereof. 31. The lithographic radiation curable hybrid ink or coating composition of any one of embodiments 27 to 29, wherein at least one of the photoinitiators is an oligomeric benzophenone derivative. 32. The lithographic radiation curable hybrid ink or coating composition of any one of embodiments 1 to 30, further comprising 0.1 wt % to 3 wt % of one or more drying agents. 33. The lithographic radiation curable hybrid ink or coating composition of embodiment 31, wherein the one or more drying agents are each independently selected from the group consisting of fatty acid salts, heavy metal salts of organic carboxylic acids, and combinations thereof. 34. The lithographic radiation curable hybrid ink or coating composition of any one of embodiments 1 to 32, further comprising 0.1 wt % to 5 wt % of one or more additives. 35. The lithographic radiation curable hybrid ink or coating composition of embodiment 33, wherein the one or more additives are selected from the group consisting of surfactants, dispersants, degassing agents, waxes, shelf-life stabilizers, wetting agents, slip agents, flow agents, fluorocarbon surfactants, silicones, organic polymeric surfactants, or combinations thereof. 36. A printed article comprising the lithographic radiation curable hybrid ink or coating composition of any one of embodiments 1 to 34. FIG1 depicts the TSI results of Example 1 and Starluxe. FIG2 depicts the results of a Starluxe RheoLaser analysis using six temperature cycles between 10 and 50° C. at a heating rate of 10° C. / min. FIG3 depicts the results of RheoLaser analysis of Example 1 using six temperature cycles between 10 and 50° C. using a 10° C. / min heating rate. FIG4 depicts the overall percent change (corresponding to the percent change of the first peak normalized to the first peak of the first cycle). FIG5 depicts the results of RheoLaser analysis of Example 1 and Starluxe using six temperature cycles between 10 and 50° C. at a heating rate of 5° C. / min. FIG6 depicts the results of RheoLaser analysis of Example 1 and Starluxe using six temperature cycles between 10 and 40° C. using a 10° C. / min ramp rate. FIG7 depicts the results of all RheoLaser experiments.

Claims

1. A lithographic radiation-curable hybrid ink or coating composition comprising: a) 10% to 30% by weight of one or more inert hard resins selected from the group consisting of rosin resins, rosin resin derivatives, hydrocarbon resins, modified hydrocarbon resins, isodiallyl phthalate resins, non-phthalate allyl resins, and combinations thereof; b) 10% to 60% by weight of a non-UV raw material selected from the group consisting of vegetable oils, vegetable oil esters, alkyd resins, antioxidants, and combinations thereof, wherein the non-UV raw material is an inert and non-reactive compound under photoinitiation conditions; and c) 5% to 45% by weight of one or more polyfunctional (meth)acrylate monomers and / or oligomers; d) 0% to 10% by weight of monofunctional (meth)acrylate monomers and / or oligomers; and wherein the hybrid ink or coating composition comprises ≥ 40% biorenewable content, wherein the biorenewable content is measured according to the standard method described in ASTM D6866.

2. The lithographic radiation-curable mixed ink or coating composition of claim 1, which contains less than 5% by weight of vegetable oil (meth)acrylate.

3. The lithographic radiation-curable mixed ink or coating composition of claim 1 or 2, comprising 15% to 35% by weight of vegetable oil and vegetable oil esters.

4. A lithographic radiation-curable mixed ink or coating composition as claimed in item 1 or 2, wherein the weight ratio of the amount of vegetable oil, vegetable oil esters and alkyd resin to the amount of (meth)acrylate monomer and oligomer is at least 0.5:1.

0.

5. A lithographic radiation-curable mixed ink or coating composition as claimed in item 1 or 2, comprising 0 to 20% by weight of one or more photoinitiators.

6. A lithographically curable mixed ink or coating composition as requested in item 1 or 2, wherein component b) is selected from the group consisting of vegetable oils, vegetable oil esters, alkyd resins and combinations thereof.

7. A lithographic radiation-curable hybrid ink or coating composition as claimed in claim 1 or 2, wherein the hybrid ink or coating composition contains ≥ 45% biorenewable content.

8. A lithographic radiation-curable mixed ink or coating composition as claimed in claim 1 or 2, comprising less than 20% by weight of a compound classified as carcinogenic, mutagenic, or reproductively toxic (CMR), wherein such CMR compound is selected from the group consisting of trimethylolpropane triacrylate, polysiloxane diacrylate, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-but-1-one, and combinations thereof.

9. The lithographic radiation-curable mixed ink or coating composition of claim 8, wherein the CMR compound is trimethylolpropane triacrylate.

10. A lithographic radiation-curable mixed ink or coating composition as claimed in claim 1 or 2, wherein the one or more inert hard resins in portion a) are present in an amount of 10% to 25% by weight.

11. A lithographic radiation-curable mixed ink or coating composition as claimed in claim 1 or 2, wherein a portion of the inert hard resin is selected from the group consisting of isodarilyl phthalate resins, non-phthalate allyl resins, rosin resin derivatives, and combinations thereof.

12. A lithographic radiation-curable mixed ink or coating composition as claimed in claim 1 or 2, wherein a portion of the one or more inert hard resin system is compatible with, soluble in, or compatible with and soluble in a portion of the (meth)acrylate monomer and oligomer, and a portion of the vegetable oil, vegetable oil ester and alkyd resin, respectively.

13. A lithographic radiation-curable mixed ink or coating composition as claimed in claim 1 or 2, wherein the (meth)acrylate oligomers in portion c) are present in an amount from 0.1% to 45% by weight.

14. A lithographic radiation-curable hybrid ink or coating composition as claimed in claim 1 or 2, wherein the (meth)acrylate oligomers in portion c) have a number average molecular weight of at least 400 Daltons, and wherein at least 95% by weight of the (meth)acrylate oligomers present in the hybrid ink or coating composition have an acrylate functionality equal to or greater than 2.

15. A lithographic radiation-curable mixed ink or coating composition as claimed in claim 1 or 2, wherein a portion of c) of the (meth)acrylate oligomers is selected from the group consisting of acrylated oils, epoxy acrylates, polyester acrylates, acrylated polyurethanes, acrylated polyacrylates, acrylated polyethers, acrylated amines, and combinations thereof, and wherein a portion of c) of the one or more polyfunctional (meth)acrylate monomers is present in an amount of up to 35% by weight.

16. A lithographic radiation-curable mixed ink or coating composition as claimed in claim 1 or 2, wherein a portion of b) of the vegetable oils, vegetable oil esters and alkyd resins are present in an amount from 0.1% to 30% by weight.

17. A lithographic radiation-curable mixed ink or coating composition as claimed in claim 1 or 2, wherein the vegetable oil esters are alkyl esters of vegetable oil fatty acids.

18. A lithographic radiation-curable mixed ink or coating composition as claimed in claim 1 or 2, wherein the vegetable oils are selected from the group consisting of drying oils, semi-drying oils, non-drying oils, and combinations thereof.

19. A lithographic radiation-curable mixed ink or coating composition as claimed in claim 1 or 2, comprising 0.1% to 10% by weight of portion d) of a monofunctional (meth)acrylate monomer.

20. A lithographic radiation-curable mixed ink or coating composition as claimed in claim 1 or 2, comprising 1 to 10% by weight of one or more photoinitiators, wherein the one or more photoinitiators are selected from the group consisting of oligomeric photoinitiators, polymeric photoinitiators and combinations thereof.

21. The lithographic radiation-curable mixed ink or coating composition of claim 1 or 2, comprising 1 to 15% by weight of one or more bio-based waxes, wherein the one or more bio-based waxes are selected from the list of waxes based on carnauba, waxes based on sugarcane, waxes based on polylactic acid, waxes based on rice bran, waxes based on hydrogenated castor oil, waxes based on poly-(hydroxybutyrate-copolymer-hydroxyvalerate), and combinations thereof.

22. The lithographic radiation-curable mixed ink or coating composition of claim 1 or 2 is substantially free of mineral oil.

23. A lithographic radiation-curable mixed ink or coating composition, such as that in claim 1 or 2, contains less than 5% by weight of synthetic wax.

24. A printed article comprising a lithographic radiation-curable mixed ink or coating composition as claimed in any one of claims 1 to 23 and a substrate, wherein the printed article forms part of a packaged article.

25. A method for manufacturing a lithographic radiation-curable mixed ink or coating composition as claimed in any one of claims 1 to 23, comprising the following steps: a) Provide: i) one or more inert hard resins selected from the group consisting of rosin resins, rosin resin derivatives, hydrocarbon resins, modified hydrocarbon resins, isodiallyl phthalate resins, non-phthalate allyl resins, and combinations thereof; ii) non-UV raw materials selected from the group consisting of vegetable oils, vegetable oil esters, alkyd resins, antioxidants, and combinations thereof; and iii) one or more polyfunctional (meth)acrylate monomers and / or oligomers; and b) mix the components provided in step (a) together to prepare the mixed ink or coating composition.

26. A method for printing a radiation-curable mixed ink or coating composition by lithography as claimed in any one of claims 1 to 23, comprising the following steps: a) Provide a lithographic radiation-curable mixed ink or coating composition as described in any of claims 1 to 23; b) Print the lithographic radiation-curable mixed ink or coating composition onto a substrate; and c) Cur the lithographic radiation-curable mixed ink or coating composition.

27. The method of claim 26, wherein the curing system is performed using UV irradiation or wherein the curing system is performed using electron beam radiation.

28. Use of a lithographic radiation-curable mixed ink or coating composition as claimed in any one of claims 1 to 23 for improving the sustainability of packaging.

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