Sustainable Radiation Curable Hybrid Offset Inks

Abstract

The present invention provides a radiation curable hybrid ink and coating composition with high bio-renewable content, including a large amount of inert hard resin. The radiation hybrid ink and coating composition has good lithographic properties, low roller swell, and low glossback effect when overprinted with UV varnish. The ink and coating composition is useful for lithographic wet printing.

Description

[Technical field]

[0001] The present invention relates to high bio-renewable content (BRC) radiation curable hybrid inks and coatings comprising energy curable monomers and oligomers and photoinitiators, as well as raw materials used in conventional offset inks such as oils, alkyd resins and hard resins. The radiation curable hybrid inks and coatings are suitable for application by lithographic printing. [Background technology]

[0002] Conventional inks for lithographic printing are formulated with vegetable or mineral oils, alkyd resins, and phenolic or hydrocarbon resins. The oil penetrates the substrate and induces physical drying or solidification (the "quick-set" effect). However, when printing on non-porous substrates such as plastic films, the quick-set effect cannot be used. For printing on non-porous substrates, the inks are formulated with vegetable oils and their esters (known as drying oils) to dissolve the hard resins and reduce the viscosity. The oil in lithographic inks is responsible for the drying of the ink by oxidation reactions.

[0003] The main drawback of conventional lithographic inks is their slow drying speed. Conventional lithographic inks based on oils and alkyds dry slowly due to penetration (hardening) and oxidation of the substrate. This has a negative impact on the productivity that a converter can achieve. Therefore, there is a need to produce faster drying inks to improve productivity.

[0004] Energy curable inks are also used in lithographic printing. Energy curable inks have improved gloss and resistance properties. However, there are drawbacks to using energy curable inks in lithographic printing. For example, the pigment wetting of energy curable inks is not as good as conventional inks, resulting in print density problems. In addition, energy curable inks show problems with low shear viscosity, less stable emulsions with water, and higher tack. The lack of stability in emulsions with water results in a smaller water balance on the printing press. Higher tack can lead to picking of fibers or coatings when printing on paper or paperboard. In addition, the classification of raw materials used in energy curable inks is much more important for health than conventional systems. Materials used in radical polymerization are mainly derived from synthetic processes that use petrochemically derived materials. The use of biosourced materials is limited in inks in the art that provide energy cured inks with low BRC values.

[0005] Generally, inks, either conventionally dried or UV dried, contain waxes to enable a good printing and conversion process by avoiding scratches and print degradation. These waxes are usually synthetic waxes based on microparticulated polyethylene (PE) and polytetrafluoroethylene (PTFE). The European Chemicals Agency (ECHA) has proposed a regulatory definition of microplastics as "materials consisting of solid polymer-containing particles, optionally with additives or other substances added, in which 1% weight (w / w) or more of the particles have (i) a length in all dimensions of 1 nm ≦ x ≦ 5 mm, or (ii) for fibres 3 nm ≦ x ≦ 15 mm and a length to diameter ratio greater than 3. Naturally occurring polymers that are not chemically modified (other than by hydrolysis) are excluded, as are (bio)degradable polymers." The regulation of microplastics does not directly affect the ink formulation, since the particles are dispersed in a polymerized binder network and are not free. However, from a sustainable development perspective, high BRC inks should not contain synthetic waxes such as PE or PTFE waxes.

[0006] Depending on the requirements of a particular print job, converters may want to use both conventional and energy curable litho printing inks. Conventional inks are typically printed with N-Buna-Nitrile Rubber (NBR) rollers, while energy curable inks are typically printed with Ethylene-Propylene-Diene-Monomer (EPDM) rollers. Energy curable inks are not compatible with NBR rollers and conventional inks are not compatible with EPDM rollers. Using incompatible inks will cause the rollers to swell and print quality to deteriorate. In order to use both conventional and energy curable inks on the same press, converters must switch to a hybrid system of rubber rollers and blankets on the printing press.

[0007] Often, to improve the gloss of prints made with conventional inks, converters apply an energy-curable topcoat over the printed substrate. However, energy-curable topcoats are typically not compatible with oil- and alkyd-based inks, resulting in "gloss-back." Gloss-back is a phenomenon in which a radiation-curable coating applied over conventional ink loses gloss within a short period of time after curing, typically within a day. To improve gloss-back, it is generally necessary to apply a water-based primer between the print and the energy-curable topcoat.

[0008] In an attempt to overcome these problems, efforts have been made to develop "hybrid" inks that contain both conventional ink components and energy curable components. Hybrid inks are described by Paul Gaevert at Radtech Conference Nov. 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" in Process 2006 (published by Pressmaker KBA).

[0009] Radiation curable hybrid inks are radiation curable inks that also contain ingredients from conventional inks such as oil, alkyd resins, and hard resins. Hybrid inks combine different drying properties and preferably dry under UV (ultraviolet) or EB (electron beam) radiation, as well as by oxidation with air or thermal drying. In addition, the ink can be dried by penetration of the oil into the substrate, similar to oil-based conventional inks. One advantage that can be observed with hybrid inks is that they can be directly overprinted with radiation curable coatings with only a slight loss of gloss (i.e., slight gloss back). As a result, aqueous primers between the ink and the coating, as well as double coaters on the press, can be omitted.

[0010] However, because 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.

[0011] One drawback of hybrid inks is that their stability 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, while oxygen stabilizes radiation-curable components such as acrylates.

[0012] The main drawback of currently available hybrid inks is their slower drying rate due to the incorporation of oils and alkyds, which dry slowly by penetration (solidification) and oxidation. Because the determining factor for ink drying in these inks is the solidification of the oil and the oxidation of the alkyd, converters do not achieve the productivity (line speeds) associated with 100% radiation curable inks. This is especially important for non-porous substrates where oil cannot penetrate.

[0013] As a result, typical hybrid inks as described in the literature contain a large amount of radiation curable materials, but only smaller amounts of oils and alkyds. A typical radiation curable hybrid ink formulation is presented in the proceedings of the Radtech conference (Paul Geavert, Radtech Europe 2003), where the materials of conventional inks (oils and alkyds) are limited to 15%. In general, a typical radiation curable hybrid ink in the art contains 5-15% vegetable oil and alkyd resins, 0-15% polyester acrylates, 0-10% epoxy acrylates, 0-50% vegetable oil acrylates, 5-15% acrylic monomers, 14-24% pigments, 4-8% fillers, 4-8% 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, Radtech report 2009) where typical hybrid inks contain only small amounts of conventional raw materials.

[0014] The above formulation ranges exhibit slower cure speeds (low reactivity) and lower solvent resistance due to the presence of non-reactive inert oils and alkyds, but due to the limited amount of conventional materials, these inks exhibit very similar lithographic performance compared to typical UV inks, whose lithographic performance is inferior to conventional inks that use non-reactive inert oils and alkyds.

[0015] Thus, the only advantage of the above formulation ranges is that such typical radiation curable hybrid inks can be run on both rollers for radiation curable inks and rollers for conventional inks, but the goal of obtaining substantially better lithographic printing is not achieved.

[0016] Furthermore, many hybrid inks in the art contain compounds classified as carcinogenic, mutagenic or toxic for reproduction (CMR) under the EU Classification, Labelling and Packaging of substances (CLP) Regulation 1272 / 2008. Because these compounds are harmful to human health, it is desirable to identify new hybrid ink and coating compositions that do not contain CMR compounds and have properties, such as gloss back, tack, viscosity and cure, comparable to compositions in the art.

[0017] It can therefore be seen that the requirements required from the formulation of high BRC, low CMR compound-containing hybrid inks and coatings are very complex, and optimizing the properties of these inks and coatings is similarly complex. From a lithographic printing standpoint, it is advantageous to have inks that contain large amounts of oils, alkyds, and hard resins. Conversely, from a drying speed, productivity, and glossback standpoint, it is preferable to have high amounts of radiation curable monomers and oligomers. Summary of the Invention

[0018] The present invention provides a complex mixture of conventional energy cured raw materials with high BRC content. The inks and coatings of the present invention are synthetic wax free and have good stability over time. The inks show good lithographic properties, can be overprinted with UV varnish with only slight gloss back and have good intercoat adhesion. The hybrid inks and coatings of the present invention show good lithographic properties compared to 100% radiation cured inks due to better pigment wetting of alkyds and conventional resins compared to (meth)acrylate monomers and oligomers. The sustainable hybrid inks of the present invention and the coatings of the present invention may not contain carcinogenic, mutagenic or reproductively toxic (CMR) materials.

[0019] The present invention provides a high BRC lithographic radiation hybrid ink or coating that provides a minimum modern carbon percent (PMC) according to ASTM D6866 (Method B) of at least 40%, preferably at least 45%.

[0020] The present invention relates to the following: 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) 10-60% 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 (meth)acrylate monomers and / or oligomers; a high BRC lithographic radiation hybrid ink or coating composition comprising: The ink or coating preferably comprises 40% or more BRC, more preferably 45% or more BRC.

[0021] The lithographic radiation hybrid ink or coating composition preferably contains less than 10% by weight of CMR compounds, more preferably less than 5% by weight of CMR compounds, and even more preferably is substantially free of CMR compounds.

[0022] The present invention also provides more sustainable compositions that use bio-sourced waxes instead of synthetic waxes.The present invention also provides a method of printing an article 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.

[0023] The present invention further provides a printed article comprising the energy curable hybrid lithographic printing ink of the present invention. The present invention also provides a conventional concentrated pigment base and energy curable technical varnish (TV) to simplify spot color preparation by simply mixing the required color base with the TV in the appropriate ratio. [Brief description of the drawings]

[0024] [Figure 1] FIG. 1 shows the TSI of both Example 1 and Starluxe, and how Starluxe evolved further over the course of the experiment. [Diagram 2] Figure 2 shows the results of a RheoLaser analysis of Starluxe under the same conditions. [Diagram 3] FIG. 3 shows the results of the RheoLaser analysis of Example 1 (Agricure) for six temperature cycles from 10 to 50° C. using a ramp rate of 10° C. / min. [Figure 4] FIG. 4 shows the overall variation (corresponding to the percentage variation of the first peak normalized to the first peak of the first cycle). [Diagram 5] Figure 5 shows how similar results were obtained when the analysis was repeated from 10 to 50 °C at a ramp rate of 5 °C / min. [Figure 6]Figure 6 shows the results obtained when the analysis was repeated from 10 to 40 °C at a ramp rate of 10 °C / min. [Figure 7] FIG. 7 shows the results of each of the RheoLaser experiments described above. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the subject matter claimed.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. 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 unless otherwise stated.

[0027] The present invention provides radiation curable hybrid inks and coatings that have good lithographic properties and low glossback effect when overprinted with a UV varnish. The inks are useful for lithographic wet printing.

[0028] definition - In this application, the use of the singular includes the plural unless specifically stated otherwise. As used herein, the singular forms "a," "an," and "the" are intended to include the plural as well, unless the context clearly dictates otherwise. - In this application, the use of "or" means "and / or" unless stated otherwise. - As used herein, the terms "comprises" and / or "comprising" specify the presence of stated features, integers, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. Furthermore, wherever the terms "includes," "having," "has," "with," "composed," "comprised," or variations thereof, are used in either the detailed description or the claims, such terms are intended to be as inclusive as 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 to encompass 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 UV radiation sources include, but are not limited to, high voltage mercury bulbs, medium voltage mercury bulbs, xenon bulbs, carbon arc lamps, metal halide bulbs, iron doped lamps, UV-LED lamps or sunlight. Other radiation sources include, but are not limited to, microwave, infrared, electron beam, visible light, x-ray, laser, etc. - As used herein, a "radiation curable hybrid ink" or "energy curable hybrid ink" is an ink or coating composition that contains energy curable components (such as, but not limited to, acrylate monomers) and also contains ingredients from traditional 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 a product of manufacture. Examples of articles include, but are not limited to, substrates such as paper, plastic, plastic or polymeric films, glass, ceramic, metal, composites, and the like; and products of manufacture such as publications (e.g., brochures), labels, 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", "ink and coating", and "inks and coatings" are used interchangeably. As used herein, the terms "inactive resin" and "inactive hard resin" are used interchangeably. - The term "monomer" refers to a compound that can be polymerized 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 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 photoinitiation conditions, e.g., UV light in the presence of a photoinitiator. This term excludes monomers and oligomers that can be initiated under such conditions, e.g., (meth)acrylates. -Throughout this disclosure, all parts and percentages are by weight (weight % or mass % based on the total weight of the composition including any solvent) unless otherwise indicated, and all temperatures are in °C. -Unless otherwise indicated, all method steps are to be performed in the order listed. - Compatibility: As used herein, compatibility of ingredients means that the ingredients are miscible at room temperature (23°C) and do not undergo phase separation for at least one week after mixing. As used herein, soluble and compatible are used interchangeably. - For lithographic printing: compositions suitable for use in lithographic printing.

[0029] 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 traditional oils and alkyds with inert hard resins.

[0030] The present invention relates to the following: 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) 10-60% 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) 0-10% of monofunctional (meth)acrylate monomers and / or oligomers; A lithographic radiation curable hybrid ink or coating composition is provided, comprising The ink or coating composition comprises greater than or equal to 40% bio-renewable content.

[0031] Advantages of the Invention The resulting inks and coatings exhibit good lithographic properties, can be overprinted with UV varnish with only slight gloss back, and exhibit good intercoat adhesion. The hybrid inks of the present invention exhibit good lithographic properties versus 100% radiation curable inks due to better pigment wetting of alkyd and conventional resins versus acrylate monomers and oligomers. The hybrid inks of the present invention also provide faster drying and curing due to the inclusion of energy curable monomers, increasing productivity. The higher amount of conventional acrylate compatible inactive hard resin versus oil and alkyd helps reduce cure retardation and increase compatibility with acrylates.

[0032] The inventors have unexpectedly observed that by introducing 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 components in the hybrid ink can be significantly increased, with little effect on drying speed and advantageous for lithographic printing.

[0033] It refers to making a conventional varnish containing a large amount of inert hard resin such as maleic rosin, aromatic hydrocarbon resin, and / or phenolic rosin resin in vegetable oil, which can be one or more of drying oil, semi-drying oil, and non-drying oil. The compatibility ratio must be determined between the conventional material and the (meth)acrylated monomers and oligomers.

[0034] Without being bound to any particular theory, the inventors believe that the inert hard resin, even when present in large quantities, quickly becomes hard and solid when the radiation curable acrylate matrix dries, so that the drying characteristics (line speed) are not significantly affected. The inks and coatings of the present invention can be run at conventional press speeds used in the art, such as at least 10,500 sheets / hour.

[0035] Furthermore, a second problem for improving radiation curing is the partial replacement or limitation of the often proposed vegetable oil acrylates, which are known to be slow to cure, by highly reactive multifunctional acrylates, such as trifunctional acrylates including propoxylated glycerol triacrylate.

[0036] Contrary to the common belief that for compatibility reasons, oil-modified acrylates must be used in hybrid inks because they are compatible with conventional oils and alkyds, the inventors have found that many common multifunctional acrylates, such as propoxylated glycerol triacrylate, can be used to a large extent. However, it is more difficult to include large amounts of highly ethoxylated acrylic monomers, which may cause some incompatibility due to their polarity. It is possible to use monofunctional acrylates in the hybrid inks of the present invention, but these materials are preferably used at a maximum of 10%, more preferably at a maximum of 5%.

[0037] Unlike many commercial hybrid inks and coatings (e.g. Suncure Hybrite, Sun Chemical), which are actually closer to a typical UV ink and contain only some conventional materials, the inks of the present invention contain a significant amount of conventional ink ingredients to obtain good lithographic performance. The amount of materials is balanced such that a good portion of the oil and alkyd resins are exchanged for acrylate soluble inert hard resins such as modified maleic rosin or modified phenolic rosin or hydrocarbon resins, so that the drying speed is not significantly affected.

[0038] The advantages of the hybrid inks of the present invention are that lithographic printing is positively impacted, with less misting, less feedback and a wider water window than typical 100% radiation curable inks.

[0039] Another advantage attributed to oil-based ingredients is that the color strength and flow from the ink ducts is often better than 100% radiation curable inks because the oil-based materials, such as alkyd resins, disperse and encapsulate the pigments evenly, resulting in good color strength and good flow.

[0040] Due to the intermediate behavior between conventional and UV, the inks can be run on presses on conventional rollers, but preferably on presses on combi rollers using hybrid or UV blankets. The inks of the present invention can preferably be washed with both conventional and UV press washing solutions, which was confirmed during laboratory studies and press testing on a Heidelberg MO&Roland 700 press.

[0041] Properties of the Hybrid Inks and Coatings of the Present Invention viscosity Typically, the radiation curable hybrid inks and coatings of the present invention exhibit a viscosity of 5-100 Pa.s at a shear rate of D=50 1 / s at 23° C. A viscosity of 20-60 Pa·s is preferred. The flow of the radiation curable hybrid inks of the present invention is also measured. Typical values ​​for flow are 2-15 cm after 15 minutes when measured using an inclined plane test (e.g. an inclined aluminum plate) with 1 ml of ink at a 90 degree inclination.

[0042] tack The inks of the present invention exhibit a tack of 12-40 units as measured using a Thwing Albert "Inkometer." A more preferred tack is less than 30 units. Tack affects print quality. If the tack is too high, there can be damage to substrates such as paper, known as "picking," where fibers of the paper substrate are pulled onto the ink blanket. If the tack is too low, problems such as poor ink feed, transfer and distribution can occur.

[0043] Lithographic printing performance The hybrid inks of the present invention run on a Roland 700 press (Bottcher combi roller and Trelleborg hybrid blanket; 4% Sunfount 480 and 3% IPA front) at 12500 sheets / h on Invercote G substrate with a target of 1.45 OD. The lithographic behavior is similar to standard offset sheet-fed inks with acceptable ink / water balance.

[0044] Grossback To take advantage of the highest productivity of fast curing UV inks, in-line coating with a UV overprint coating that also provides high gloss is often preferred. However, when a conventional sheet-fed ink is overprinted with a UV ink and final cured, the initial gloss of the cured coating often drops by 10 to 25 gloss points within 24 hours. This also depends on the type of substrate, and is particularly important on open porous, uncoated substrates. This is often countered by applying a water-based primer between the conventional ink and the UV overprint varnish. However, this requires a double coater with an integrated thermal or infrared dryer and additional water-based coating on the press, which adds additional time and expense to the process. These drying systems are available for presses such as the ManRoland 700 Ultima or Heidelberg Speedmaster Duo, but are a more niche technology. This can often be avoided by using the radiation curable hybrid inks of the present invention instead of conventional inks, resulting in low gloss-back effects without the need for water-based primers. With the hybrid inks of the present invention, a balance has been found where low gloss-back effects are achieved and provide a stable gloss, which is typically difficult to achieve with water-based coatings. Nevertheless, the inks exhibit good lithographic performance. Also, a small amount of gloss back may be observed with the hybrid inks of the present invention, but preferably the amount of gloss back is within the preferred range. For high gloss hybrid inks (e.g., initial gloss >60), a loss of gloss of less than 10 units is preferred; more preferably less than 7 units.

[0045] Replacement of Carcinogenic, Mutagenic and Reproductive Toxic (CMR) Compounds Hybrid inks of the art may contain compounds classified as carcinogenic, mutagenic or toxic for reproduction (CMR) under EU Classification, Labelling and Packaging of substances (CLP) Regulation 1272 / 2008. Although the use of such compounds may provide hybrid inks and coatings with advantageous properties, these compounds are harmful to health and therefore their use should be avoided. CMR compounds present in hybrid inks of the art include trimethylolpropane triacrylate (TMPTA), silicone diacrylates such as Ebecryl 350, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (ominirad 379), and polyfunctional aminobenzoate derivatives such as 1,3-propanediol, 2-ethyl-2-(hydroxymethyl), polymers with oxirane, 4-(dimethylamino)benzoate (Genopol AB-2).

[0046] The present inventors have discovered a hybrid ink that is free of CMR compounds and has properties consistent with hybrid inks in the art. The ink or coating composition of the present invention may contain less than 20% by weight of compounds classified as carcinogenic, mutagenic or reproductively toxic (CMR), preferably less than 10% by weight of CMR compounds, or even more preferably less than 5% by weight of CMR compounds. The ink or coating composition of the present invention is most preferably substantially free of CMR compounds.

[0047] The inventors have surprisingly found that the CMR compounds, including the multifunctional acrylate TMPTA, described in the art as an essential component of hybrid inks, can be replaced by alternative non-CMR compounds, and further, the inventors have found that the resulting hybrid inks have properties at least equivalent to those of the art compositions that contain CMR compounds.

[0048] In particular, the inventors have discovered that (meth)acrylates classified as CMR compounds can be replaced in art compositions by 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, particularly at least comparable tack, viscosity, and cure, as compared to art inks containing CMR compounds. Cure is evaluated using the UV set-off test described in the examples.

[0049] 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.

[0050] Bio-renewable content The hybrid ink or coating compositions of the present invention have a bio-renewable content of at least 40%, preferably at least 45% by weight. The inventors have surprisingly found that by replacing components of prior art inks with alternatives having a high BRC, hybrid inks are provided that have properties at least equivalent to prior art compositions that do not contain the BRC content of the present invention.

[0051] As used herein, sustainability refers to the BRC content of a material. Improving the sustainability of packaging thus relates to increasing the BRC content of the packaging, for example, by using the lithographic radiation curable hybrid ink or coating composition of the present invention instead of an alternative ink or coating.

[0052] Ingredients and their preferred amounts Hybrid Inks and Coatings The hybrid inks and coatings of the present invention may comprise vegetable oils, vegetable oil esters and vegetable alkyd resins in an amount of 0-40% by weight, for example 0-25% by weight; inert hard resins in an amount of >10% by weight, preferably 10-30% by weight; (meth)acrylate oligomers in an amount of 10-40% by weight; and (meth)acrylate monomers in an amount of 0-10% by weight. The hybrid inks and coatings may comprise less than 20% by weight of compounds classified as CMR. The hybrid inks and coatings may further comprise colorants (pigments or dyes) in an amount of 0-40% by weight; extenders and fillers in an amount of 0-10% by weight; photoinitiators in an amount of 0-10% by weight; and additives in an amount of 0-4% by weight.

[0053] The preferred total amount of vegetable oil, vegetable oil and ester, alkyd and inert hard resin is >10%, more preferably >20%, more preferably >30%, more preferably >40%, more preferably >50%. The preferred amount of inert hard resin is >10%, more preferably >13%.

[0054] The hybrid inks and coatings of the present invention preferably comprise 12-26 wt.% inert hard resins, 15-25 wt.% vegetable oils, vegetable oil esters and vegetable alkyd resins, 15-35 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 bio-renewable content of 45% or more. The hybrid inks and coatings preferably comprise less than 5 wt.% of compounds classified as CMR.

[0055] Of the 15% and 25% by weight vegetable oils, vegetable oil esters and alkyds, in the preferred hybrid inks and coatings of the invention, preferably 15-20% by weight are vegetable oils and vegetable oil esters and 3-10% by weight are vegetable alkyd resins. The exact formulation also depends on the targeted ink properties.

[0056] Ratio of inactive resins, vegetable oils, vegetable oil esters and alkyds to (meth)acrylate monomers and oligomers. Inactive resins, vegetable oils, vegetable oil esters and alkyds may be incorporated into the inks or coatings of the present invention in combination with (meth)acrylate monomers and oligomers to provide a ratio of inactive 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, more preferably 0.5:1.0 to 1.0:1.0.

[0057] inert hard resin The radiation curable hybrid ink and coating compositions of the present invention comprise from 10% to 30% by weight of one or more inactive hard resins, based on the total weight of the ink or coating composition, the inactive hard resin being 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 inactive hard resins for use in the present invention are preferably present in an amount of from 10% to 30% by weight; for example, from 12% to 30% by weight, more preferably from 12% to 25% by weight, even more preferably from 15% to 25% by weight, for example from 15% to 20% by weight.

[0058] Inert hard resins are typically, for purposes of the present invention, natural or synthetic amorphous materials that preferably form tack-free films at room temperature after application to a substrate. Most of these materials are oligomers or polymers.

[0059] The inactive hard resins for use in the present invention 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. Any of these inactive hard resins that are compatible and / or soluble with acrylate monomers and oligomers, vegetable oils, vegetable oil esters, and vegetable alkyd resins can be used in the hybrid inks of the present invention. Preferred inactive hard resins include rosin resin derivatives, such as phenolic rosin resins, and isodiallyl phthalate resins and non-phthalate allyl resins, such as diallyl cycloalkane-based resins.

[0060] Rosin resin derivatives consist of various isomers and different chemical structures, such as derivatives of abietic acid, levopimaric acid, neoabietic acid, palustric acid, dehydroabietic acid, pimaric acid and isopimaric acid. The rosin resin derivatives used in the present invention may be modified with maleic anhydride (i.e., maleic rosin resin) or fumaric acid and esterified with polyols such as glycerol and pentaerythritol. The rosin resin used in the present invention is preferably a phenolic rosin resin.

[0061] 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 resin is soluble / compatible with the acrylic monomers, oligomers, oils, and alkyds. When present, these additional resins may be present in an amount of 1% to 20% by weight, based on the total weight of the ink or coating composition. For example, the additional resins are preferably present in an amount of 1% to 15% by weight; such as 5% to 15% by weight; more preferably 10% to 15% by weight.

[0062] (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 wt% to 45 wt%, such as 1 wt% to 30 wt%, based on the total weight of the ink or coating composition. More preferably, the one or more (meth)acrylate oligomers are present in an amount of 5 wt% to 40 wt%, such as 10 wt% to 40 wt%, even more preferably 15 wt% to 35 wt%, based on the total weight of the ink or coating composition.

[0063] (Meth)acrylate oligomers for use in the present invention have a number average molecular weight of at least 400 Da, for example preferably 400 to 3,000 Daltons or 1000 to 3000 Da. (Meth)acrylate oligomers for use in the present invention preferably have an acrylate functionality >2, more preferably ≧4, even more preferably ≧6.

[0064] Preferably, the (meth)acrylate oligomer has a viscosity of at least 5 Pa.s, measured according to the method described in the examples.

[0065] 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 to impart rheology, pigment wetting, transfer, gloss, chemical resistance and other film properties. Acrylated oils, polyester acrylates such as oil-modified polyester acrylates, acrylated polyurethanes, acrylated polyethers and combinations thereof are preferred.

[0066] The inventors have found that replacing low molecular weight (meth)acrylates (i.e., components having a molecular weight less than 400 Da) with high molecular weight oligomeric (meth)acrylates (i.e., components having a number average molecular weight of at least 400 (e.g., 400-3000 Da)) results in hybrid ink and coating compositions with improved misting. The (meth)acrylate monomers and (meth)acrylate oligomers of part c) preferably have a molecular weight of at least 400 Da.

[0067] (Meth)acrylate Monomers The radiation curable hybrid ink and coating compositions of the present invention may comprise up to 45% by weight, for example 5% to 45% by weight, of one or more multifunctional (meth)acrylate monomers, based on the total weight of the ink or coating composition. The radiation curable hybrid ink and coating compositions of the present invention preferably comprise less than 15% by weight of one or more multifunctional (meth)acrylate monomers.

[0068] 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 is 1,2-ethylene glycol 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, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ethoxylated dipentaerythritol hexaacrylate or mixtures thereof, with ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol triacrylate and propoxylated pentaerythritol tetraacrylate, and combinations thereof being preferred.

[0069] The radiation curable hybrid ink and coating compositions of the present invention may further comprise one or more monofunctional (meth)acrylate monomers. If present, the one or more monofunctional acrylate monomers are typically present in an amount of up to 5% by weight, such as 1% to 5% by weight, preferably up to 4% by weight, more preferably up to 3% by weight, based on the total weight of the ink or coating composition.

[0070] (Meth)acrylate monomers for use in the present invention include monomers derived from vegetable oils and fatty acids, such as soybean acrylates. However, it is preferred that the use of such monomers is limited. For example, the ink or coating of the present invention may contain less than 10% by weight of vegetable oil (meth)acrylates, preferably less than 5% by weight of vegetable oil (meth)acrylates, and even more preferably be substantially free of vegetable oil (meth)acrylates.

[0071] For example, the one or more monofunctional monomers may be present in an amount of from 1% to 3% by weight; or from 1% to 2% by weight; or from 2% to 5% by weight; or from 2% to 3% by weight; or from 3% to 5% by weight.

[0072] Suitable monofunctional acrylate monomers include, but are not limited to, tertiobutylcyclohexanol acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, tetrahydrofurfuryl acrylate, lauryl acrylate, 2-phenoxyethyl acrylate, isodecyl acrylate, ethoxylated phenyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, isooctyl acrylate, octyldecyl acrylate, polycaprolactone acrylate, ethoxylated non-phenyl acrylate, isobornyl acrylate, cyclic trimethylolpropane formal acrylate, stearyl acrylate, behenyl acrylate, alkoxylated lauryl acrylate, combinations thereof, etc. Lauryl acrylate is preferred.

[0073] 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 from 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 from 10% to 30% by weight, and even more preferably in an amount of from 15% to 25% by weight.

[0074] The one or more vegetable oils and vegetable oil esters may preferably be present in an amount of from 0.1% to 20% by weight; or from 0.1% to 15% by weight; or from 0.1% to 10% by weight; or from 0.1% to 5% by weight; or from 0.1% to 1% by weight; or from 0.1% to 0.5% by weight; or from 0.5% to 25% by weight; or from 0.5% to 20% by weight; or from 0.5% to 15% by weight; or from 0.5% to 10% by weight; or from 0.5% to 5% by weight; or from 0.5% to 1% by weight; or from 1% to 25% by weight; or from 1% to 20% by weight; or from 1% to 15% by weight; or from 1% to 10% by weight; or from 1% to 5% by weight; or from 5% to 25% by weight; or from 5% to 20% by weight; or from 5% to 15% by weight; or from 5% to 10% by weight.

[0075] The vegetable oil may be one or more of drying oil, semi-drying oil and non-drying oil.Examples include almond oil, cacao oil, candy nut oil, castor oil, dehydrated castor oil, coconut oil, corn oil, cottonseed oil, grape seed oil, hemp seed oil, linseed oil, olive oil, palm kernel oil, peanut oil, rapeseed oil, rice bran oil, safflower oil, sunflower oil, sesame oil, soybean oil, tall oil, tung oil and walnut oil, including combinations thereof and fatty acid esters, such as fatty acid alkyl esters.

[0076] Alternatively, the oil may be one or more fatty acid alkyl esters, such as rapeseed methyl ester, rapeseed isopropyl ester, caprylic acid methyl ester, capric acid isopropyl ester, lauric acid methyl ester, myristic acid methyl ester, palmitic acid methyl ester, stearic acid methyl ester, oleic acid ethyl ester, erucic acid methyl ester, ricinoleic acid ethyl ester, linoleic acid methyl ester, linolenic acid methyl ester, or palmitic acid isopropyl ester.

[0077] Alkyd Resin 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 from 1 wt% to 15 wt%, based on the total weight of the ink or coating composition. The one or more alkyd resins are preferably present in an amount of from 1 wt% to 12 wt%; for example, from 2 wt% to 10 wt%; more preferably, in an amount of from 3 wt% to 8 wt%; even more preferably, in an amount of from 5 to 8 wt%.

[0078] 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.

[0079] Alkyds are polyesters modified by the addition of vegetable oils, fatty acids and other ingredients, and are therefore partially derived from vegetable oils (or "vegetable alkyds" as used herein). In the inks of the present invention, the alkyds typically have a number average molecular weight of 1,000 to 20,000 Da.

[0080] The alkyd for use in the present invention may be a reaction product of a polyhydric alcohol with an acid or an acid anhydride. The alkyd for use in the present invention is a vegetable alkyd. The alkyd for use in the present invention may be modified with vegetable oils and saturated or unsaturated fatty acids from 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, linoleic acid, linoelaidic acid, eleostearic acid, timnodonic acid, arachidonic acid, clapanodonic 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.

[0081] The alkyds for use in the present invention can be made with vegetable oils transesterified by the addition of polyols. The polyols can be glycerol. The vegetable oils can be tall oil. The alkyds for use in the present invention can include soybean oil, sunflower oil, rapeseed oil, corn oil, tung oil, linseed oil, coconut oil and palm oil. The alkyds for use in the present invention can be any combination of the above alkyds.

[0082] The radiation curable hybrid lithographic ink or coating composition of the present invention preferably comprises the vegetable oil, vegetable oil ester and vegetable alkyd resin in an amount of from 0.1 to 30% by weight, more preferably from 10 to 25% by weight.

[0083] Coloring agent The radiation curable hybrid ink and coating compositions of the present invention may further comprise one or more colorants in the form of a pigment. When present, the one or more colorants are present in an amount of from 1 wt % to 20 wt %, preferably from 5 wt % to 18 wt %, more preferably from 10 wt % to 15 wt %, based on the total weight of the ink or coating composition.

[0084] For example, the one or more colorants may be present in an amount of 1% to 15% by weight; or 1% to 10% by weight; or 1% to 5% by weight; or 1% to 3% by weight; or 1% to 2% by weight; or 2% to 20% by weight; or 2% to 15% by weight; or 2% to 10% by weight; or 2% to 5% by weight; or 2% to 3% by weight; or 5% to 20% by weight; or 5% to 15% by weight; or 5% to 10% by weight; or 10% to 20% by weight; or 10% to 15% by weight; or 15% to 20% by weight.

[0085] Pigments suitable for use in the present invention include conventional organic or inorganic pigments. Representative pigments include 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 116, Pigment Yellow 118, Pigment Yellow 119, Pigment Yellow 120, Pigment Yellow 121, Pigment Yellow 122, Pigment Yellow 123, Pigment Yellow 124, Pigment Yellow 125, Pigment Yellow 126, Pigment Yellow 127, Pigment Yellow 128, Pigment Yellow 129, Pigment Yellow 130, Pigment Yellow 131, Pigment Yellow 132, Pigment Yellow 133, Pigment Yellow 134, Pigment Yellow 135, Pigment Yellow 136, Pigment Yellow 137, Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 140, Pigment Yellow 141, Pigment Yellow 142, Pigment Yellow 143, Pigment Yellow 144, Pigment Yellow 145, Pigment Yellow 146, Pigment Yellow 147, Pigment Yellow 148, Pigment Yellow 149, Pigment Yellow 150, Pigment Yellow 151, Pigment Yellow 152, Pigment Yellow 153, Pigment Yellow 154, Pigment Yellow 155, P 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 62, 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 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, and combinations thereof.

[0086] Photoinitiators The radiation curable hybrid ink and coating compositions of the present invention, when cured by UV light, may further comprise one or more photoinitiators. When present, the one or more photoinitiators may be incorporated in an amount of from 0.1 wt.% to 20 wt.%, 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 from 0.1 wt.% to 15 wt.%, such as from 0.5 wt.% to 15 wt.%, or more preferably from 1 wt.% to 10 wt.%, such as even more preferably from 4 wt.% to 8 wt.%.

[0087] The photoinitiator 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; for example 1% to 3% by weight; or 1% to 2% by weight.

[0088] Examples of suitable photoinitiators include benzophenones, benzil ketals, 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, diethoxy-acetophenone, 2-hydroxy-2-methyl-1-phenylpropane, ... Examples of suitable photoinitiators include, but are not limited to, propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-methyl-1-[4(methoxythio)-phenyl]-2-morpholinopropan-2-one, diphenylacylphenylphosphinoxide, diphenyl(2,4,6-trimethylbenzoyl)phosphinoxide, 2,4,6-trimethylbenzoylethoxyphenylphosphinoxide, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, or mixtures thereof. For EB curable inks, no photoinitiator is required.

[0089] Preferred photoinitiators include Type II photoinitiators thioxanthones such as 2-isopropylthioxanthone and 2,4-diethylthioxanthone, Type II photoinitiators 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-trimethylbenzoyl)-phenyl-phosphinate.

[0090] For inks designed for food packaging, migratory low molecular weight monomeric photoinitiators can be minimized or replaced completely with oligomeric or polymeric photoinitiators. Suitable photoinitiators are, for example, photoinitiators containing oligomeric benzophenone derivatives such as Omnipol BP from IGM Resins, oligomeric amines such as Genopol AB-1 from the Rahn Group, or oligomeric Type I photoinitiators such as Omnipol 910 from IGM.

[0091] Other optional additives Antioxidants can be added to avoid premature polymerization of double bonds in the oil and alkyd resin. Exemplary antioxidants include ascorbic acid, astaxanthin, carotene, chroman (3,4-dihydro-2H-1-benzopyran), hexamethylene bis (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, antioxidants are typically present in an amount of 0.1% to 4% by weight, based on the total weight of the ink or coating composition. For example, one or more antioxidants may be present in an amount of 0.1% to 3% by weight; preferably 0.1% to 2% by weight; or more preferably 0.1% to 1.1% by weight.

[0092] 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.

[0093] To facilitate drying of the 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 these heavy metal salts of organic carboxylic acids include, but are not limited to, manganese linoleate, hexadecanoate or octoate (see, e.g., U.S. Pat. Nos. 5,156,674; 6,899,756; and 7,811,367). The drier can be any of the 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, 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.

[0094] The hybrid inks and coatings of the present invention may further contain conventional additives to modify the flow, surface tension, gloss, pigment wetting and abrasion resistance of the cured coating or printed ink. Such additives contained in the ink or coating are typically surfactants, waxes, shelf-life stabilizers, and the like, and combinations thereof. These additives may function as leveling agents, shelf-life stabilizers, wetting agents, slip agents, flow agents and dispersants. Preferred additives include fluorocarbon surfactants, silicones and organic polymer surfactants. Examples include the Tegorad product line (Tegorad is a trademark and is a commercially available product of Tego Chemie, Essen, Germany) and the Solsperse product line (Solsperse is a trademark and is a commercially available product of the Lubrizol Company). When present, these one or more additives are generally present in an amount of 0.1% 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.

[0095] The synthetic inventive hybrid inks and coatings may contain 1-15% by weight of one or more bio-based waxes. The synthetic inventive hybrid inks and coatings preferably contain 2-10% by weight of one or more bio-based waxes. Bio-sourced waxes for use in the present invention include those based on carnauba, sugar cane, polylactic acid, rice bran, hydrogenated castor oil, and poly-(hydroxybutyrate-co-hydroxyvalerate) PHVB.

[0096] The radiation curable hybrid inks of the present invention may further contain conventional extenders such as clay, talc, calcium carbonate, magnesium carbonate or silica to adjust water uptake, misting and color strength. When present, the one or more extenders or fillers are typically present in an amount of from 1 wt% to 10 wt%, based on the total weight of the ink or coating composition. For example, the one or more extenders or fillers may be present in an amount of from 1 wt% to 8 wt%; or from 1 wt% to 5 wt%; or from 1 wt% to 4.5 wt%; or from 1 wt% to 4 wt%; or from 1 wt% to 3.5 wt%; or from 1 wt% to 3 wt%; or from 1 wt% to 2.5 wt%; or from 1 wt% to 2 wt%; or from 1 wt% to 1.5 wt%; or from 2 wt% to 10 wt%; or from 2 wt% to 8 wt%; or from 2 wt% to 5 wt%; or from 2 wt% to 4.5 wt%. 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.

[0097] The hybrid inks and coatings of the present invention preferably contain less than 5% by weight of synthetic wax, such as PE or PTFE wax. More preferably, the hybrid inks and coatings of the present invention are substantially free of synthetic wax, such as PE wax or PTFE wax.

[0098] Printed Articles 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 polymeric film, glass, ceramic, metal, composites, and the like. Articles also include articles of manufacture such as publications (e.g., brochures), labels, 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.

[0099] The substrate to be printed on may be constructed from any typical substrate material such as paper and carton board. The substrate may be paper printing stock typically used in publications, or it may be packaging material in the form of cardboard sheets or corrugated board.

[0100] Curing of the Hybrid Inks and Coatings of the Present Invention The radiation curable inks and coatings of the present invention can be cured by an actinic radiation source such as UV light provided by high voltage mercury bulbs, medium voltage mercury bulbs, xenon bulbs, carbon arc lamps, metal halide bulbs, UV-LED lamps or sunlight. The applied irradiation wavelength is preferably in the range of 200 nm to 500 nm, more preferably in the range of 250 nm to 350 nm. The UV energy is preferably in the range of 30 to 3,000 mJ / cm. 2 It is preferable that the range is 50 to 500 mJ / cm 2 It is more preferable that the range is within the range of 100 to 200 mm. The bulb can be appropriately selected depending on the absorption spectrum of the radiation-curable composition.

[0101] Alternatively, actinic radiation may also include electron beam radiation (EB). Commercially, EB dryers are available, for example, from Energy Science, Inc., Wilmington, Massachusetts, USA, or from Advanced Electron Beams Inc. (AEB), Wilmington, Massachusetts, USA. The absorbed energy, also known as dose, is measured in units of kilograys (kGy), with 1 kGy equal to 1,000 joules per kilogram. Typically, for complete cure, the electron beam dose should be in the range of 10 kGy to 40 kGy. For radiation curable compositions of the present invention, curing with a radiation dose of 20 to 30 kGy, preferably with an oxygen level of less than 200 ppm, is usually sufficient to obtain a dry, solvent-resistant ink.

[0102] Optionally, an infrared dryer or a heat dryer on a press can be used to accelerate solidification of the oil component.

[0103] Preparation of Radiation Curable Hybrid Inks and Coatings Inks can be made by typical procedures known in the art, usually by dry milling or using flushes, color concentrates, or bases. In a typical dry mill manufacturing procedure for inks, the required amount of dry pigment is mixed with conventional oils solubilized in vegetable oils, alkyd resins, and inert hard resins in a dissolver or mixer for 15-30 minutes to wet all the pigments. The premix is ​​then milled on a three-roll mill (or other grinding mill) at pressures of 1-4 MPa and temperatures of 20-40°C until the desired grinding specifications are met. Photoinitiators can be added before or after milling in the form of a solution or paste.

[0104] The pigment may be introduced as a flush. In the "flush process", the wet pigment presscake is "flashed" 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 eventually flashes into the organic phase, leaving no pigment in the aqueous phase. A significant portion of the water can then be poured off. Heat and vacuum are usually applied to remove the remaining water. The resulting product is called a "flush paste" or pigment concentrate (base). The pigment concentrate is then diluted with acrylate monomer, oligomer, optional photoinitiator and inert hard resin (varnish) solution.

[0105] It is preferred from a versatility standpoint: color concentrates used in coldset, heatset or sheet-fed inks are appreciated by formulators, provided they can also be used in UV hybrid inks.

[0106] example The following examples illustrate certain aspects of the invention and are not intended, nor should they be construed, as limiting its scope in any way.

[0107] Measurement method Molecular weight: The molecular weight of a non-polymeric or oligomeric compound (e.g. a monomer) is defined and calculated according to the molecular structure of the compound. Usually this is given by the technical data sheet of the monomer supplier or can be found on the webpage of the European Chemicals Agency (ECHA).

[0108] The molecular weights of oligomeric and polymeric species are measured by gel permeation chromatography (GPC) performed on a Hewlett-Packard 1050 series HPLC system equipped with two GPC Ultrastyragel columns, 103 Å and 104 Å (5 μm mixed, 300 mm×19 mm, Waters Millipore Corporation, Milford, Massachusetts, USA), with THF as the mobile phase. The column temperature is 40° C. Molecular weights are calculated by comparison with polystyrene standards. Those skilled in the art will understand that this definition of molecular weight typically applies to polymeric materials that have a molecular weight distribution. Unless otherwise stated, the molecular weights reported herein for oligomers and polymers are number average molecular weights.

[0109] Bio-based / bio-renewable content Biobased / bio-renewable carbon content (BRC) is determined using standard methods 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 measure "biobased content" is based on the same concepts as radiocarbon dating, but does not use an age equation. It determines the ratio of the amount of radioactive carbon (14C) in an unknown sample to the amount in a modem reference standard. Fossil carbon does not contain radioactive carbon. The higher the amount of "new" carbon, the higher the 14C. This ratio is reported as the percentage of total carbon that is modem carbon, using the units "pMC" (percent modem carbon), or as BRC (as a percentage). Some suppliers may assess the percentage of bio-based content by weight based on the "recipe" used by the manufacturer (i.e., how much natural material, such as cellulose, is present in the varnish containing cellulose and copolyesters), however, it should be noted that the weight percentage includes the weight contribution not only from carbon but also from other elements in the material.

[0110] For purposes of this invention, BRC content refers to BRC as assessed using ASTM D6866, Method B.

[0111] Carcinogenic, Mutagenic or Reproductively Toxic (CMR) Compounds CMR compounds are classified according to the EU Classification, Labelling and Packaging of substances (CLP) Regulation 1272 / 2008. CMR compounds belong to categories 1A, 1B and 2 of this EU classification.

[0112] Phenolic modified rosin resins can be made from the esterification of glycerol (or pentaerythritol) with a polycondensate of rosin, phenol (or bisphenol A) and formaldehyde.

[0113] viscosity The viscosity was determined using a MCR301 cone-plate rheometer from Anton Paar GmbH at shear rates of D = 2 to 50 1 / s at 23 °C. The viscosity value at D = 50 1 / s was recorded (Pa.s) and the yield value at D = 2 1 / s was recorded.

[0114] tack Inkometer Tack was measured using a calibrated "Inkometer" instrument manufactured by Thwing Albert. 3 of ink was placed on a 32.2°C EPDM rubber dispensing roller and dispensed at a roller speed of 150 rpm for 15 seconds, then 800 rpm for 60 seconds.

[0115] The integrated tack (iTack) was also measured using an Alphatack from Novomatics with 100 μL samples at 30° C. and 800 rpm. The measurement (iTack value) is read after 60 seconds.

[0116] flow Flow was measured using a vertically positioned aluminum plate at 90 degrees onto which 1 ml of ink was placed and the distance (in cm) that the ink had flowed down the plate after 15 minutes was recorded.

[0117] Misting Misting was assessed in two ways. The misting estimate is determined by visual assessment against an internal scale made on real examples. First, a visual assessment (visual confirmation) is used, resulting in values ​​between 0 (perfect), 1 (very good), 2 (good), 3 (acceptable), 4 (poor), and 5 (very poor). Results below 3 are considered acceptable. Then, an "Inkometer" from Thwing Albert is used, with 3.5 g of ink placed on an EPDM rubber distribution roller at 32°C, distributed at a roller speed of 150 rpm for 15 seconds, then at 2000 rpm for 5 minutes. A white sheet of paper is placed behind the roller during the test. The Inkometer measures the optical density (OD) of the ink on the paper.

[0118] Gloss Gloss was measured using a BYK-Gardner Micro Gloss Instrument set at a 60 degree angle and is reported as gloss units.

[0119] Curing evaluation The cure of the prints was assessed by how well the ink from the cured print was transferred (solidified) to another piece of paper under high pressure, simulating the conditions in a large stack of paper or roll of substrate where the freshly cured prints are stored under pressure.

[0120] Ideally, no ink is transferred. Typically, the transfer of an experimental ink to a test paper is compared to the transfer of a control UV ink to a test paper, the control ink being intended for the same application. The amount of set-off ink at a given UV dose is a measure of reactivity and achievable cure speed (productivity).

[0121] The cure of the ink is evaluated by a set-off test used by the following method: The ink was applied to the surface of a cardboard substrate using a print proofing device at the appropriate optical density (OD). The OD is measured by a densitometer. Suitable printed optical densities for lithographic inks are 0.9-1.5 (yellow), 1.0-1.65 (cyan), 1.0-1.5 (magenta), and 1.1-1.9 (black), depending on the substrate. The ink was applied at a line speed of 400 ft / min using a 200 watt Fusion H bulb, with a set-off of 33 mJ / cm. 2 Immediately after UV curing by delivering a UV dose of 10 ... 2 ) was applied to the cured ink sample. Both were introduced in a press and subjected to 1000 bar (10 tons (1000 Kg) / cm 2 ) of pressure was applied. Once pressure was reached the print was released (1 second pressure time). The set off material (transferred ink) on the paperboard substrate was measured with a Techkon Densitometer and compared to the control ink.

[0122] Compared to a control ink, under the same curing conditions and print density, an ink with a lower densitometer number indicates better curing. Densitometer readings of less than 0.50 are usually considered good values.

[0123] Ink Crushing Test The fineness of the ink grind is an important parameter that describes the quality of the dispersion of solid pigment particles in the ink. The fineness of the pigment particles was tested using a grindometer. The grindometer consists of a steel block in which channels of various depths are machined, starting from a depth appropriate for the type of ink being measured and shallowing until they are flush with the surface of the block. The depth of the groove is marked with a scale next to it. The ink to be tested was poured into the deep end of the groove and scraped towards the shallow end with a flat metal scraper. At the 4 μm point on the scale, the ink track was inspected for the number of large irregularities (first number in brackets) and the number of small irregularities (second number in brackets). A score (0 / 0) means that neither large particles nor small irregularities are observed and the ink is rated as passing.

[0124] All inks according to the present invention have acceptable ink grinding properties with particle sizes less than 15 μm.

[0125] stability Two methods were used to test the stability.

[0126] The first method utilizes a Turbiscan static multiple light scattering (SMLS) analyzer to detect particle migration and size variation. The analyzer uses an oven set at 50°C in which samples of the same concentration are placed. Two synchronous detectors are used to analyze both the backscattered (BS) and transmitted (T) signals of the laser light incident on the sample, scanning over the entire length of the sample and taking measurements periodically over a period of 20 hours for up to 9 days. The variation in backscattering over time (ΔBS(%)) indicates the instability of the ink, with larger variations corresponding to greater instability (due to particle settling). The Turbiscan Stability Index (TSI) is determined from the sum of the T and BS variations over the entire height of the sample and plotted as a function of time. A lower TSI indicates increased stability of the sample.

[0127] The second method utilizes the Rheolaser technique based on multi-speckle diffusing wave spectroscopy (MS-DWS) to analyze the rheological properties of a sample without mechanical stress (by passive microrheology). The backscattering (BS) of laser light is measured for the same concentration of the sample during six cycles of temperature. The same temperature ramp rate is used in each of the six cycles that make up one experiment. The response is measured in MicroDynamics (mD) (Hz). Three different temperature ramp rates are used: a) 10-50 °C at 10 °C / min, b) 10-50 °C at 5 °C / min, c) 10-40 °C at 10 °C / min. The resulting Speckle images are mathematically analyzed to obtain the characteristic time as a function of time. The characteristic time is inverted to obtain the mD, and the results are plotted as a function of time. A consistent mD response over multiple cycles indicates stability. In contrast, an increase or decrease in the mD response with increasing number of cycles indicates a lack of stability.

[0128] Examples 1 and 2. Cyan hybrid inks containing 16-22% inert hard resin Cyan hybrid inks of the present invention were made from dry milling on a three-roll mill with three passes at 2 MPa (25° C.) having the composition shown in Table 1 (16%-22% inert hard resin).

[0129] [Table 1]

[0130] The properties of the inks of Examples 1 and 2 were tested as described above, and the results are shown in Table 1A.

[0131] [Table 1A]

[0132] The inks of Examples 1 and 2 exhibit typical values ​​of viscosity (20-60 Pas), flow (1.5-7 cm) and tack (10-40 units on the Incometer and 200-500 units on the Lithotack) for UV lithographic inks, as shown in Table 1A.

[0133] [Table 2]

[0134] The magenta color base was then passed through a three roll mill for one pass at 2 MPa (25° C.).

[0135] Table 3 below shows the composition of the finished ink (13% inert hard resin, 6.2% alkyd and 18% oil and ester components).

[0136] [Table 3]

[0137] The properties of Example 4 were tested as described above, and the results are shown in Table 3A.

[0138] [Table 3A]

[0139] Example 5. Hybrid ink (15% inert hard resin) made from a color base and then UV overcoated Hybrid inks were made from a cyan universal base (color concentrate) that can be used to make sheet-fed inks, heatset inks and coldset inks as well as acrylate letdown varnishes by mixing in a dissolver for 20 minutes at 40° C.-45° C. (50% combined inert hard and alkyd resins and vegetable and mineral oils) and milling on a three-roll mill. The purpose of this experiment is to show that the inks of the present invention can be overprinted with UV overprint varnishes while exhibiting good visual laydown and print properties.

[0140] [Table 4]

[0141] Photoinitiator (PI) compounds and amine synergists include mixtures of phosphine oxides, α-aminoketones, thioxanthones, such as 2,4-diethylthioxanthone, multifunctional aminobenzoate derivatives, and poly(ethylene glycol) bis(p-dimethylaminobenzoate).

[0142] The properties of Example 5 were tested as described above, and the results are shown in Table 4A.

[0143] [Table 4A]

[0144] The inks were printed on a Roland 700 press (Bottcher combi roller and Trelleborg hybrid blanket; 4% Sunfount 480 and 3% IPA front) at 12500 sheets / h on an Invercote G substrate with a target of 1.45 OD.

[0145] The ink was immediately overprinted with UV overprint varnish 44HC150 (Sun Chemical) at 140 lines using an anilox roller and 150 mJ / cm 2 The composition was end cured at 100° C. Gloss was measured as above. Glossback is indicated by a decrease in gloss over time. A decrease of less than 10 gloss units indicates that glossback is within the preferred range.

[0146] [Table 5]

[0147] Table 5 shows that the hybrid inks exhibit no gloss back.

[0148] Example 6. Cyan Hybrid Ink Made from Traditional Sheet-Fed Color Base and Gelled Acrylate Varnish Containing 20% ​​Inactive Resin The hybrid inks shown in Table 6 were made from a cyan conventional sheet-fed ink color base and a gelled acrylate varnish containing 20% ​​inactive resin.

[0149] [Table 6]

[0150] The properties of Example 6 were tested as described above, and the results are shown in Table 6A.

[0151] [Table 6A]

[0152] Stability testing The ink of Example 1 (referred to herein as Agricure) and a comparative ink (Starluxe) that contains only acrylate monomers and oligomers but is not a hybrid ink and therefore does not contain a traditional inactive resin component were tested.

[0153] Turbiscan Turviscan analysis of Example 1 (AgriCure) did not detect any significant variation in ΔBS(%) for Example 1. In contrast, Turviscan analysis of Starluxe, which became opaque / transparent over the course of the experiment, detected an increase in ΔBS(%) variation. Figure 1 shows the TSI for both Example 1 and Starluxe, and how Starluxe evolved further over the course of the experiment, with a higher TSI after 3 days.

[0154] RheoLaser Figure 2 shows the results of the RheoLaser analysis of Starluxe under the same conditions, which showed significantly more variation and noise. Noise is typically an indication of exudation (liquid layer on top). In contrast, Figure 3 shows the results of the RheoLaser analysis of Example 1 (Agricure) for six temperature cycles from 10 to 50 °C using a ramp rate of 10 °C / min. Only slight variations in the mD response were detected.

[0155] Figure 4 shows the overall variation (corresponding to the percentage variation of the first peak normalized to the first peak of the first cycle). The variation of Starluxe starts slowly but increases rapidly after 4 and 6 cycles, with the overall variation percentage being larger than that of Example 1.

[0156] Figure 5 shows how similar results were obtained when the analysis was repeated from 10 to 50 °C at a ramp rate of 5 °C / min.

[0157] Figure 6 shows the results obtained when the analysis was repeated from 10 to 40 °C at a ramp rate of 10 °C / min. Again, significantly more fluctuations and noise were detected for Starluxe compared to Example 1. In this experiment, some initial fluctuations were observed for Example 1 before the sample stabilized after 1 h.

[0158] FIG. 7 shows the results of each of the RheoLaser experiments described above, demonstrating that for each set of experimental conditions, Example 1 had improved stability (after 6 cycles) over Starluxe when tested under the same conditions, indicating that Example 1 has improved stability compared to Starluxe.

[0159] Although the present invention has been described in detail, including preferred embodiments thereof, it will be understood that those skilled in the art, upon consideration of this disclosure, may make modifications and / or improvements therein which fall within the scope and spirit of the invention.

[0160] Numbered embodiments of the invention (forming part of the description) 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) 10-60% non-UV raw materials, which may be inert hard resins, vegetable oils and esters, vegetable alkyd resins, antioxidants; and c) 5% to 45% by weight of one or more multifunctional acrylate monomers and oligomers; d) 0-10% monofunctional acrylate monomers and oligomers; Including, A lithographic radiation curable hybrid ink or coating composition, wherein the ink or coating composition comprises 40% or more BRC.

[0161] 2. A lithographic radiation curable hybrid ink or coating composition as described in embodiment 1, wherein the ink or coating composition comprises 45% or more BRC.

[0162] 3. A lithographic radiation curable hybrid ink or coating composition as described in embodiment 1, wherein the one or more inert hard resins are present in an amount of 10% to 20% by weight.

[0163] 4. A lithographic radiation curable hybrid ink or coating composition as described in embodiment 1, wherein the one or more inert hard resins are present in an amount of 10% to 15% by weight.

[0164] 5. A radiation curable hybrid ink or coating composition for lithographic printing as described in embodiment 1, wherein the one or more inactive hard resins are selected from the group consisting of maleic rosin resins, and combinations thereof.

[0165] 6. A lithographic radiation curable hybrid ink or coating composition as described in embodiment 1, wherein at least one of the inert hard resins is an isodiallyl phthalate resin soluble in acrylate monomers.

[0166] 7. A radiation curable hybrid ink or coating composition for lithographic printing as described in embodiment 1, wherein the one or more inert hard resins are compatible, soluble, or compatible and soluble in the acrylate monomers and oligomers, oils, and alkyd resins.

[0167] 8. The radiation curable hybrid ink or coating composition for lithographic printing according to any one of embodiments 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.

[0168] 9. A lithographic radiation curable hybrid ink or coating composition as described in embodiment 1, wherein the one or more multifunctional acrylate monomers are present in an amount of 5% to 35% by weight.

[0169] 10. A lithographic radiation curable hybrid ink or coating composition as described in embodiment 1, wherein the one or more multifunctional acrylate monomers are present in an amount of 5% to 25% by weight.

[0170] 11. The one or more multifunctional acrylate monomers are selected from the group consisting of 1,2-ethylene glycol 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, and the like. 10. The radiation curable lithographic hybrid ink or coating composition of any one of embodiments 1 to 9, wherein the alkyl group is selected from the group consisting of ethyl acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, propoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ethoxylated dipentaerythritol hexaacrylate, and combinations thereof.

[0171] 12. The radiation curable hybrid ink or coating composition for lithographic printing of any one of the preceding embodiments, further comprising 0.1 to 30% by weight of one or more oils, alkyd resins, or combinations thereof.

[0172] 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% to 15% by weight.

[0173] 14. The radiation curable hybrid ink or coating composition for lithographic printing 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.

[0174] 15. A radiation curable hybrid ink or coating composition for lithographic printing as described in 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.

[0175] 16. The radiation curable hybrid lithographic ink or coating composition of any one of the preceding embodiments, further comprising 0.1% to 20% by weight of one or more acrylate oligomers.

[0176] 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% to 10% by weight.

[0177] 18. The lithographic radiation curable hybrid ink or coating composition of any one 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 of 2 or greater.

[0178] 19. The radiation curable hybrid ink or coating composition for lithography 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.

[0179] 20. The radiation curable hybrid lithographic ink or coating composition of any one of embodiments 1 to 18, further comprising 0.1% to 10% by weight of one or more monofunctional acrylate monomers.

[0180] 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% to 15% by weight.

[0181] 22. The radiation curable hybrid ink or coating composition for lithographic printing of any one of the preceding embodiments, further comprising 0.1% to 40% by weight of one or more colorants.

[0182] 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%.

[0183] 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.

[0184] 25. The radiation curable hybrid lithographic ink or coating composition of any one of embodiments 1 to 23, further comprising 0.1% to 10% by weight of one or more extenders or fillers.

[0185] 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%.

[0186] 27. The radiation curable hybrid ink or coating composition for lithographic printing 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.

[0187] 28. A lithographic radiation curable hybrid ink or coating composition according to any one of the preceding embodiments, further comprising 0.1 to 20% by weight of one or more photoinitiators.

[0188] 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%.

[0189] 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.

[0190] 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.

[0191] 32. The radiation curable hybrid lithographic ink or coating composition of any one of embodiments 1 to 30, further comprising 0.1% to 3% by weight of one or more drying agents.

[0192] 33. The radiation curable hybrid ink or coating composition for lithographic printing 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.

[0193] 34. The radiation curable hybrid ink or coating composition for lithographic printing of any one of embodiments 1 to 32, further comprising 0.1% to 5% by weight of one or more additives.

[0194] 35. The radiation curable hybrid lithographic 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 polymer surfactants, or combinations thereof.

[0195] 36. A printed article comprising a lithographic radiation curable hybrid ink or coating composition according to any one of embodiments 1 to 34.

Claims

1. 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) 10-60% 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 (meth)acrylate monomers and / or oligomers; d) 0-10% of monofunctional (meth)acrylate monomers and / or oligomers; Including, A lithographic radiation curable hybrid ink or coating composition, said ink or coating composition comprising 40% or more bio-renewable content.

2. The lithographic radiation curable hybrid ink or coating composition of claim 1 comprising 0 to 20% by weight of one or more photoinitiators.

3. 3. A lithographic radiation curable hybrid ink or coating composition according to claim 1 or 2, wherein component b) is selected from the group consisting of vegetable oils, vegetable oil esters, alkyd resins, and combinations thereof.

4. 10. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, wherein said ink or coating composition comprises 45% or more bio-renewable content.

5. 10. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, comprising less than 20% by weight, preferably less than 10% by weight, or more preferably less than 5% by weight of compounds classified as carcinogenic, mutagenic, or toxic to reproduction (CMR).

6. 10. A lithographic radiation curable hybrid ink or coating composition according to any preceding claim, which is substantially free of compounds classified as carcinogenic, mutagenic or toxic to reproduction (CMR).

7. 7. A lithographic radiation curable hybrid ink or coating composition according to claim 5 or 6, wherein the CMR compound is selected from the group consisting of trimethylolpropane triacrylate, silicone diacrylate, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and combinations thereof; optionally the CMR compound is trimethylolpropane triacrylate.

8. 10. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, wherein said one or more inactive hard resins of part a) are present in an amount of 10% to 25% by weight, such as 10% to 20% by weight.

9. 10. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, wherein said inactive hard resin of part a) is selected from the group consisting of isodiallyl phthalate resins, non-phthalate allyl resins, rosin resin derivatives, and combinations thereof.

10. 10. A lithographic radiation curable hybrid ink or coating composition according to claim 9, wherein said rosin resin derivative is a phenolic rosin resin.

11. 10. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, wherein said one or more inert hard resins of part a) are compatible, soluble or both compatible and soluble with said (meth)acrylate monomers and oligomers of part c) and said vegetable oil, vegetable oil ester and vegetable alkyd resins of part b).

12. 10. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, further comprising one or more additional 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.

13. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, wherein said (meth)acrylate oligomer of part c) is present in an amount of 0.1% to 45% by weight.

14. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, wherein said (meth)acrylate oligomer of part c) is present in an amount of 15% to 35% by weight.

15. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, wherein said (meth)acrylate oligomer of part c) has a number average molecular weight of at least 400 Daltons, such as from 400 to 3000 Daltons.

16. 10. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, wherein at least 95% by weight of the (meth)acrylate oligomers present in the ink or coating composition have an acrylate functionality of 2 or more, such as 4 or more, or 6 or more.

17. 10. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, wherein said (meth)acrylate oligomer of part c) is selected from the group consisting of acrylated oils, epoxy acrylates, polyester acrylates, acrylated polyurethanes, acrylated polyacrylates, acrylated polyethers, acrylated amines, and combinations thereof.

18. 18. The lithographic radiation curable hybrid ink or coating composition of claim 17, wherein said (meth)acrylate oligomer of part c) is selected from the group consisting of polyester acrylates, acrylated polyurethanes, acrylated polyethers, and combinations thereof.

19. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, wherein said one or more multifunctional (meth)acrylate monomers of part c) are present in an amount up to 35% by weight.

20. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, wherein said one or more multifunctional (meth)acrylate monomers of part c) are present in an amount up to 15% by weight.

21. The one or more multifunctional (meth)acrylate monomers of part c) are selected from the group consisting of 1,2-ethylene glycol 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, tripropylene glycol diacrylate, bisphenol-A diglycidyl ether diacrylate, tripropylene glycol ...

4. The radiation curable lithographic hybrid ink or coating composition of any of the preceding claims, wherein the at least one hydroxypropyl methacrylate is selected from the group consisting of ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, propoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ethoxylated dipentaerythritol hexaacrylate, and combinations thereof.

22. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, wherein said vegetable oils, vegetable oil esters and vegetable alkyd resins of part b) are present in an amount of 0.1 to 30% by weight.

23. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, wherein said vegetable oils, vegetable oil esters and vegetable alkyd resins of part b) are present in an amount of 10% to 25% by weight.

24. 10. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, wherein said vegetable oil ester is a vegetable oil fatty acid alkyl ester.

25. 10. A radiation curable hybrid ink or coating composition for lithographic printing according to any of the preceding claims, wherein the vegetable oil is selected from the group consisting of drying oils, semi-drying oils, non-drying oils, and combinations thereof; optionally, the vegetable oil is linseed oil, soybean oil, and combinations thereof.

26. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims comprising 0.1% to 10% by weight of said monofunctional acrylate monomer of part d).

27. 13. A lithographic radiation curable hybrid ink or coating composition according to any preceding claim, further comprising 0.1% to 40% by weight of one or more colorants, such as 1% to 20% by weight of one or more colorants.

28. 28. The lithographic radiation curable hybrid ink or coating composition of claim 27, wherein the one or more colorants are selected from the group consisting of inorganic pigments, organic pigments, and combinations thereof.

29. 13. A lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, further comprising 0.1% to 10% by weight of one or more extenders and / or fillers, such as 1% to 5% by weight of one or more extenders and / or fillers.

30. 30. The lithographic radiation curable hybrid ink or coating composition of claim 29, 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.

31. A lithographic radiation curable hybrid ink or coating composition according to any preceding claim further comprising from 0.1% to 20% by weight of one or more photoinitiators.

32. A lithographic radiation curable hybrid ink or coating composition according to any preceding claim comprising from 1% to 10% by weight of one or more photoinitiators.

33. 33. A lithographic radiation curable hybrid ink or coating composition according to claim 31 or 32, wherein the one or more photoinitiators are selected from the group consisting of oligomeric photoinitiators, polymeric photoinitiators, and combinations thereof.

34. A lithographic radiation curable hybrid ink or coating composition according to any one of claims 27 to 29, wherein at least one of said photoinitiators is an oligomeric benzophenone derivative.

35. A lithographic radiation curable hybrid ink or coating composition according to any preceding claim further comprising from 0.1% to 3% by weight of one or more driers.

36. 36. The lithographic radiation curable hybrid ink or coating composition of claim 35, 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.

37. A lithographic radiation curable hybrid ink or coating composition according to any preceding claim further comprising from 0.1% to 5% by weight of one or more additives.

38. 38. The lithographic radiation curable hybrid ink or coating composition of claim 37, 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.

39. 13. A lithographic radiation curable hybrid ink or coating according to any preceding claim comprising from 1% to 15% by weight of one or more bio-based waxes, such as from 2% to 10% by weight of one or more bio-based waxes.

40. 40. The lithographic radiation curable hybrid ink or coating of claim 39, wherein the one or more bio-based waxes are selected from the list consisting of carnauba based waxes, sugar cane based waxes, polylactic acid based waxes, rice bran based waxes, hydrogenated castor oil based waxes, poly-(hydroxybutyrate-co-hydroxyvalerate) based waxes, and combinations thereof.

41. 10. A lithographic radiation curable hybrid ink or coating composition according to any preceding claim which is substantially free of mineral oil.

42. 10. A lithographic radiation curable hybrid ink or coating composition according to any preceding claim, comprising less than 5% by weight of synthetic wax, e.g. the ink or coating composition is substantially free of synthetic wax.

43. A printed article comprising the lithographic radiation curable hybrid ink or coating composition of any one of claims 1 to 42 and a substrate.

44. 44. The printed article of claim 43 forming part of a packaging article.

45. A method of making a lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, comprising the steps of: a) Below: i) one or more inactive 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 inert hard resins, vegetable oils, vegetable oil esters, alkyd resins, antioxidants, and combinations thereof; and iii) one or more multifunctional (meth)acrylate monomers and / or oligomers; providing b) mixing said ingredients together to form said hybrid ink or coating; The method includes:

46. A method of printing a lithographic radiation curable hybrid ink or coating composition according to any of the preceding claims, comprising the steps of: a) providing said lithographic radiation curable hybrid ink or coating; b) printing the lithographic ink or coating onto a substrate; and c) curing said lithographic radiation curable hybrid ink or coating; The method includes:

47. 47. The method of claim 46, wherein the curing is performed using UV radiation.

48. 48. The method of claim 46 or 47, wherein the curing is performed using electron beam radiation.

49. Use of the lithographic radiation curable hybrid ink or coating composition according to any of claims 1 to 42 for improving the sustainability of packaging.

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