WO2016187363A1

WO2016187363A1 - Emulsion composition for energy curable ink compositions and a printing process and method thereof

Info

Publication number: WO2016187363A1
Application number: PCT/US2016/033162
Authority: WO
Inventors: Joshua M. Rosenheck; John H. Larsen; Thomas J. STEWART; Leander H. Bauer
Original assignee: Lubrizol Advanced Materials Inc
Current assignee: Lubrizol Advanced Materials Inc
Priority date: 2015-05-21
Filing date: 2016-05-19
Publication date: 2016-11-24
Anticipated expiration: 2017-11-21
Also published as: TW201707778A

Abstract

An emulsion composition comprises water, an organic phase of polymerizable monomer, and an emulsifier package having a hydrophilic lipophilic balance number of 10 or less is useful as an additive to energy curable ink or coating. An energy curable (polymerizable) ink or coating comprising an emulsion of water droplets and a variety of polymerizable monomers is useful as an ink or coating. A process of making an energy curable ink or coating is also described by first making an emulsion of water in at least one monomer and then adding that emulsion (in any order) to the other components of the energy curable ink.

Description

EMULSION COMPOSITION FOR ENERGY CURABLE INK COMPOSITIONS AND A PRINTING PROCESS AND METHOD THEREOF

FIELD OF INVENTION

[0001] The present invention involves a stable water-in-organic phase emulsion composition of water, one or more unsaturated polymerizable monomers, and a surfactant capable of forming a water-in-organic phase emulsion from the other two components. The water-in-organic phase emulsion is useful in an energy curable ink compositions containing the water-in-organic phase emulsion composition. An energy polymerized printing process can be improved, in certain aspects, when it includes the water-in-organic phase emulsion composition within the energy curable ink composition.

BACKGROUND OF THE INVENTION

[0002] One way to get very fluid coatings with almost no organic solvents volatilized to the environment is to use energy cured inks and coatings such as electron beam polymerized or UV initiated polymerized inks and coatings. These compositions often include oligomers to increase viscosity and coating thickness, if increased viscosity is desired. These inks and coatings were developed to eliminate solvents and carriers, so these inks and coatings are generally considered solvent free.

[0003] In solvent based inks and coatings, techniques have developed to emulsify water into the solvent to partially replace a portion of the solvent with water, thereby reducing the volatile organic solvents released to the environment when such solvent based inks were dried.

[0004] DeSanto, Jr. et al. in US Patent No. 4,981,517 disclose a printing ink emulsion system containing an oil-based phase and water-mi scible phase and exhibiting a high degree of stability against phase separation in use.

[0005] Koike et al. in US Patent No. 5,378,739 disclose a W/O emulsion ink for use in stencil printing which is composed of an oil phase and a water phase with the respective ratios by wt. % thereof being (20 to 40):(80 to 60).

[0006] Batlaw et al., in US Patent No. 5,389, 130, disclose an ink composition for Gravure printing wherein the vehicle is a water-in-oil emulsion of a water immiscible organic phase and an aqueous phase in the range of 9: 1 to 1 : 1 thereby significantly reducing VOC emissions with no detrimental effect on print quality. [0007] Kingman et al., in US Patent No. 6, 140,392, disclose single fluid lithographic printing inks that include a continuous phase and a discontinuous polyol phase.

[0008] Ohshima et al., in US Patent No. 6,348,519, disclose an emulsion ink, by which clear images are produced, having excellent drying and fixing properties and preservation stability and does not bleed, strike through or leak.

[0009] US Patent 6,444,716 B l discloses a microporous open-celled polymeric foam material derived from a high internal phase water-in-monomer emulsion.

[0010] US Patent No. 6,797,735 B2 describes a process for producing porous polymer by starting with emulsifying water in a monomer component, polymerizing the monomer, etc.

[0011] US Patent No. 7,857,899 describes a water-in-oil emulsion of water, a hydrocarbon distillate having a boiling point range of 215 to 325 °C, and an emulsion stabilizing surfactant that functioned in a lithographic heat set ink to reduce the amount of volatile organic solvent in the ink.

SUMMARY OF THE INVENTION

[0012] An object of the present invention is to modify the properties (such as increased viscosity, modified cure time, modified set time, reduced water pick-up, lower material cost, etc.) of an energy curable ink or coating containing emulsified water droplets. It was desired to be able to vary the amount of water added to an energy curable (polymerizable) ink or coating, so a water containing masterbatch type of water-in-organic phase emulsion (water, emulsifier package, and an organic phase comprising at least one monomer (free radically polymerizable unsaturated compound)) was developed. This was considered more desirable than trying to emulsify water into a partially or fully formulated ink or coating. It was found that it is easier to make water-in-monomer emulsions when the monomer(s) are relatively hydrophobic and have low solubility in the water phase (and the water phase has low solubility in the monomer(s)).

[0013] To achieve the foregoing objects in accordance with the present invention as described and claimed herein, an emulsion composition comprises

(a) 10 to 80, 85, 90, 95, 96, or 97 wt.% of a water phase;

(b) 0.1 or 0.2 to 10 or 20 wt.% of an emulsifier package having a HLB (hydrophilic lipophilic balance) value of 0 to 60, and more preferably a range from 0, 2, 4, or 6 to 10 which can be a blend of one or more or two or more emulsifiers; and (c) from 3, 4, 5, 6, 7, 8, 9, or 10 to about 89 or 90 wt.% of organic phase based on the weight of the emulsion composition and desirably comprising at least 50, 60, 70, 80, or 90 wt.% of one or more mono-unsaturated polymerizable monomer(s) based on the weight of the organic phase.

[0014] In a further embodiment of this invention, an energy curable ink or coating composition comprising;

(a) a water-in-organic phase emulsion composition as described hereinabove and throughout this application;

(b) optionally one or more polyunsaturated (e.g. polyethylenically unsaturated) polymerizable monomers; and

(c) optionally one or more colorants in the form of a pigment or dye;

wherein the water-in-organic phase emulsion composition delivers 5 to 35% by weight water to the ink composition.

[0015] In a further embodiment, a method/process of forming a radiation curable ink or coating comprising dissolving the emulsifier package in an organic phase comprising at least 50, 60, 70, 80 or 90 wt.% of one or more Cio-20-alkyl esters of (meth)acrylic acid forming a solution, emulsifying water in said solution of emulsifier package forming a water-in-monomer emulsion, formulating an energy curable ink or coating formulation by combining the additional components to the ink and said water-in-monomer emulsion, optionally adding colorant in the form of one or more dyes or pigments, optionally adding co-polymerizable oligomers of polyester, polyepoxide, or polyurethane, optionally adding polymerizable co-monomers having two or more reactive (polymerizable) unsaturated groups, and blending said components.

[0016] In an additional embodiment of the invention, a printing process comprising employing in the printing process an energy curable ink composition comprising an emulsion composition as described hereinabove and throughout this application.

A still further embodiment of the invention is a method to improve a printing process, comprising employing in the printing process an energy curable ink or coating composition comprising a water-in-organic phase emulsion composition as described herein. In lithographic inks the emulsified water can increase the gloss of the coating, increase the viscosity of the ink (facilitating quicker development (requiring less coats) of a sufficiently thick coating), and lowering of the water pick-up of the lithographic ink (facilitating reaching equilibrium water absorption during a lithographic press set-up and reducing waste print substrate generation while trying to get the lithographic ink to equilibrium water absorption and viscosity.

DETAILED DESCRIPTION OF THE INVENTION

[0017] Definitions. To simplify things we will use parentheses around "meth" to indicate that a named molecule can optionally include a methyl substituent such as (meth)acrylic acid will refer to methacrylic acid and/or acrylic acid and methyl (meth)acrylate will refer to methacrylate and/or acrylate. The term hydrocarbyl will refer to monovalent hydrocarbon groups that may optionally include other heteroatoms (such as O and N) in conventional or specified amounts such as one oxygen and/or nitrogen for every four carbon atoms in the group, but preferably just carbon and nitrogen. The term hydrocarbylene will refer to divalent hydrocarbon groups that may optionally include other heteroatoms such as O and N as defined for hydrocarbyl. The term organic phase will refer to hydrocarbon compounds primarily of carbon and hydrogen but including up to 30 wt.% of nitrogen and oxygen and up to 10 wt.% of other heteroatoms (such as sulfur, phosphorus, and silicone) based on the weight of the organic phase.

[0018] The present invention comprises an emulsion composition comprising:

(a) water;

(b) at least one emulsifier package having a HLB value of 10 or less; and

(c) an organic phase comprising one or more mono-unsaturated polymerizable monomer(s);

wherein the water is present at 10 to 90, 95, 96 or 97% by weight, the organic phase comprising one or more mono-unsaturated polymerizable monomers is present from 3, 4, 5 or 6 to 60, 70, 80, 85, or 90% by weight, and the surfactant is present at 0.1 or 0.2 to 10 or 20 % by weight, wherein said weight percent is based on the weight of the water-inorganic phase emulsion.

[0019] The water component (a) of the water-in-organic phase emulsion composition can comprise water from any source that allows formation of the emulsion and that can be used in a printing ink composition to include sanitized water, tap water, softened water, deionized water, distilled water, filtered water, membrane osmosis water, etc. The water can be present in the emulsion composition on a weight basis at 10 to 80, 85, 90, 95, 96 or 97%), and in other embodiments preferably from 20, 30, or 40 to 97%, and desirably from 50 or 70 to 95 or 97%. In one embodiment said water or water phase optionally comprises 0.1 to 10 wt.% ammonium nitrate dissolved therein, which adds some iconicity to the water phase, and in some embodiments creates a more stable emulsion.

[0020] Component (b) of the water-in-organic phase emulsion composition can be an emulsifier package comprising one or more and desirably two or more different emulsion stabilizing surfactants. In one embodiment, it is preferred that at least 10, 20, 30, 40, or 50 wt.%) of the emulsifier package is polymeric emulsifiers having a number average molecular weight at least 500, 800, or 1000 g/mole and desirably less than 5000 or 10,000 g/mole. These polymeric emulsifiers tend to enhance the stability of the water droplets formed preventing them from aggregating into larger droplets or becoming broken down into smaller droplets. Thus, these preserve the emulsified water droplets formed during further processing and formulation into inks or coatings. In one embodiment, it is preferred that at least 10, 20, 30, 40 or 50 wt.%> of the emulsifier package is one or more fatty acid esters of low molecular weight polyols (such as a polyol of less than 300g/mole molecular weight, such as sorbitan) with fatty acids of 10 to 25 carbon atoms. One such emulsifier is sorbitan mono-oleate. These low molecular weight emulsifiers (due to their ability to quickly move through the continuous phase to new interfaces between the water and organic phase) help to form the initial small particle size emulsion of water in the organic phase.

[0021] The surfactant can be a compound or composition or a mixture of compounds and/or compositions that is capable of forming an emulsion with water and the one or more unsaturated polymerizable monomer(s) of the present invention which can comprise one or more (meth)acrylate monomers and that is compatible with the energy curable ink compositions of the present invention. The surfactant can be an organic compound. The organic compound can be a cationic compound such as a quaternary ammonium salt, an anionic compound such as an alkali or alkaline earth metal salt of an alkylaryl sulfonate, an amphoteric compound such as a betaine inner salt that can contain a quaternary ammonium group and an anionic acid group such as a carboxylate or sulfonate or phosphate group, a nonionic compound such as an alkoxylated alcohol, or a mixture thereof. The surfactant can also be referred to as a detergent, an emulsifier or a wetting agent. The individual surfactants can have a hydrophilic lipophilic balance (HLB) number ranging from 0 to 60, 0 to 30, or 0 to 20. The emulsifier package has an HLB calculated from the HLB of the individual surfactants and their respective weight percent in the final composition. The emulsifier package desirably has an HLB of 0 to 20, more desirably 0 to 10 and preferably from 2, 4, or 6 to about 10. The HLB number is the relative attraction of the surfactant for the phases of an emulsion which are normally a polar aqueous phase and a nonpolar oil phase.

[0022] Component (c) of the emulsion composition is an organic phase comprised generally of one or more mono-unsaturated polymerizable monomers and optionally other hydrophobic liquid (or materials soluble in the organic phase) use in the ink or coating compositions. In one embodiment, the mono-unsaturated polymerizable monomers are at least 50, 60, 70, 80, or 90 wt.% of the organic phase of the emulsion. In one embodiment, at least 50, 60, 70, 80, or 90 wt.% of the organic phase is mono-unsaturated monomers as opposed to polyunsaturated monomers. Generally, we like low molecular weight (low viscosity) monomers as opposed to polymerizable oligomers of polyester, polyurethane or epoxy based oligomers for the emulsion; although a few oligomers or a small percentage of oligomers would be acceptable under most circumstances. We like mono-unsaturated monomer (such as (meth)acrylate) with larger hydrophobic groups (e.g. C10-C20 alkyl groups) as they are less compatible with the water phase than lower alkyl (meth)acrylates. The polyunsaturated esters of mono or polyhydric lower alcohols are polar enough due to their multiple ester linkages to be more difficult to use in an emulsion.

[0023] A surfactant having a low HLB number will have more of an attraction for the nonpolar organic or oil phase which favors the formation of a water-in-oil emulsion. A surfactant having a high HLB number will have more of an attraction for the polar aqueous phase which favors the formation of an oil-in-water emulsion. In an embodiment of the invention, the emulsion stabilizing surfactant can have a HLB number of 10 or less, and in other instances of 9 or less, or 8 or less. In another embodiment of the invention, the surfactant can have a HLB number of 0 to 10, and in other instances from 0, 2, 4, or 6 to 8, 9, or 10. The emulsion composition of the present invention can be a water-in-organic phase emulsion. The water phase of the water-in-organic phase emulsion of the present invention can comprise droplets having a number average diameter from 0.05 or 0.1 to 10 micrometers, and in other instances from 0.3 to 8 micrometers, or 0.5 to 6 micrometers.

[0024] The surfactant of the present invention can comprise a reaction product of a hydrocarbyl-substituted acylating agent with an amine, an alcohol, or a mixture thereof; a Mannich reaction product of hydrocarbyl- substituted hydroxy-containing aromatic compound, an aldehyde, with an amine containing at least one primary or secondary amino group; a hydrocarbyl -substituted carboxylic acid, an alkoxylated alcohol, a carboxylate ester of an alkoxylated alcohol, or a mixture thereof; an alkoxylated alkylphenol, a carboxylate ester of an alkoxylated alkylphenol, or a mixture thereof; an alkoxylated fatty carboxylic acid, a carboxylate ester of an alkoxylated fatty carboxylic acid, or a mixture thereof; a fatty carboxylic acid ester; a polymer, copolymer or block copolymer of one or more alkylene oxides; an alkoxylated and/or carboxylated monosaccharide or disaccharide; an alkoxylated fatty carboxylic acid ester or vegetable oil or animal oil or mixture thereof; an amine; an alkoxylated amine; an amide; an alkoxylated amide; an alkanolamide; an alcohol to include for example fatty alcohols having 4 to 22 carbon atoms; a sulfonate to include sulfonated amines, sulfonated amides, olefin sulfonates, sulfonated oils, petroleum sulfonates, sulfonated fatty acids, sulfonates of alkoxylated alkylphenols, sulfonates of aromatic compounds and alkylated aromatic compounds such as for example sulfonates of benzene and naphthalene and toluene and dodecylbenzene and alkylated diphenyl ether, and mixtures thereof; an amine oxide; a betaine compound to include lecithin or a lecithin derivative; an imidazoline to include fatty acid based imidazolines and derivatives thereof; a phosphate ester to include derivatives thereof; lignin or a derivative thereof; a quaternary ammonium salt; a sulfate to include sulfates of alcohols, sulfates of alkoxylated alcohols, sulfates of alkoxylated alkylphenols, sulfates of oils, sulfates of fatty acids, sulfates of fatty esters, and mixtures thereof; a sulfosuccinate or a derivative thereof to include sulfosuccinamates; a soap such as a metal or ammonium salt of a carboxylic acid; a copolymer of a poly(oxyalkylene glycol) and a poly(12- hydroxystearic acid); or a mixture thereof.

[0025] The emulsifier package can be two or more surfactants of the same type, such as for example a mixture of two or more alkoxylated alcohols or a mixture of one higher molecular weight/polymeric emulsifier and one lower molecular weight fatty acid ester of a polyol. The mixture of surfactants can be two or more surfactants of two or more different types, such as for example, a mixture of two alkoxylated alcohols and one alkoxylated alkylphenol or a mixture of one alkoxylated alcohol, one alkoxylated alkylphenol and one fatty carboxylic acid ester. The surfactants of this invention are available commercially and/or can be prepared by well-known methods. The surfactants of this invention can include for example the commercially available emulsifiers and detergents that are described in McCutcheon's Emulsifiers & Detergents, North American and International Edition, 1993 Annuals, MC Publishing Company. This publication includes most of the surfactant types listed hereinabove.

[0026] In an embodiment of this invention, the surfactant comprises a reaction product of a hydrocarbyl -substituted acylating agent and an amine, an alcohol, or a mixture thereof; a Mannich reaction product of hydrocarbyl -substituted hydroxy-containing aromatic compound, an aldehyde, and an amine containing at least one primary or secondary amino group; a hydrocarbyl -substituted carboxylic acid; an alkoxylated alcohol, a carboxylate ester of an alkoxylated alcohol, or a mixture thereof; an alkoxylated alkylphenol, a carboxylate ester of an alkoxylated alkylphenol, or a mixture thereof; an alkoxylated fatty carboxylic acid, a carboxylate ester of an alkoxylated fatty carboxylic acid, or a mixture thereof; a fatty carboxylic acid ester; a polymer, copolymer or block copolymer of one or more alkylene oxides; an alkoxylated and/or carboxylated monosaccharide or disaccharide; an alkoxylated fatty carboxylic acid ester or vegetable oil or animal oil or mixture; or a mixture thereof.

[0027] The surfactant can be a reaction product of a hydrocarbyl-substituted acylating agent and an amine and/or alcohol. The hydrocarbyl substituent of the reaction product of the hydrocarbyl-substituted acylating agent and amine, alcohol or mixture thereof can have a number average molecular weight of 110 to 5000, and in other instances of 140 to 3500, or 160 to 2500 or 500 to 1500. The hydrocarbyl substituent can be derived from an olefin or polyolefin. The polyolefin can be a homopolymer of a single C2-C10 olefin such as for example isobutylene or a copolymer of two or more C2-C10 olefins such as for example ethylene and propylene and optionally butadiene. In an embodiment of the invention the hydrocarbyl substituent is derived from a polyisobutylene which can have a vinylidene content of terminal double bonds that is low at 30% or less or that is high at 50% or more. The acylating agent can be derived from an alpha, beta-unsaturated monocarboxylic or polycarboxylic acid or reactive equivalent thereof to include an anhydride or an ester or an acid halide. Useful alpha, beta-unsaturated carboxylic acids or reactive equivalents thereof include for example methyl acrylate, fumaric acid and maleic anhydride. In an embodiment of the invention the alpha, beta-unsaturated carboxylic acid or reactive equivalent thereof is maleic anhydride. Methods to prepare a hydrocarbyl-substituted acylating agent are well known and generally involve for example heating a polyisobutylene or chlorinated polyisobutylene and maleic anhydride at 150 to 250 °C optionally in the presence of a promoter such as chlorine. One or sometimes more than one maleic group (succinic anhydride group after grafting) can be added to each polyisobutylene molecule. The amine can be a monoamine, a polyamine or a mixture thereof. The amine can have primary amino groups, secondary amino groups, tertiary amino groups, or a mixture thereof. The amine can be an alkanolamine that contains one or more hydroxy groups. In an embodiment of the invention the amine is an alkanolamine, and in another embodiment the alkanolamine is a Ν,Ν-dialkylalkanolamine. Useful amines include for example ethanolamine, diethanolamine, triethanolamine, and Ν,Ν-diethylethanolamine. The alcohol can be a monohydric or polyhydric alcohol. The hydrocarbyl-substituted acylating agent and amine and/or alcohol can be reacted in a ratio based on acyl equivalents to equivalents of reactive amino groups and/or hydroxy groups that is respectively 1 :0.3-5, and in other instances is 1 :0.5-4.5, or 1 : 1.5-4.5 or 1 :0.5-2.5. The reactive amino and/or hydroxy groups on an equivalent basis for example in N,N-di ethyl ethanolamine are 2 and in ethanolamine can be 2 or 3. The reaction product of a hydrocarbyl-substituted acylating agent and amine and/or alcohol can be prepared by heating the reactants at 50 to 200 °C and as described in US Patent No. 5,334,318.

[0028] The surfactant can be a Mannich reaction product. The hydrocarbyl substituent of the hydrocarbyl-substituted hydroxy-containing aromatic compound of the Mannich reaction product can have a number average molecular weight of 50 to 5000, 80 to 3000, or 110 to 800 or 750 to 2300. The hydrocarbyl substituent can be derived from a polyolefin as described hereinabove for the reaction product of the hydrocarbyl-substituted acylating agent and amine and/or alcohol. In an embodiment of the invention, the hydrocarbyl substituent of the hydrocarbyl-substituted hydroxy-containing aromatic compound is derived from a polyisobutylene, and in other embodiments the polyisobutylene has a terminal double bond or vinylidene content that is 30% or less, or 50% or more. The hydroxy-containing aromatic compound can be derived from a phenolic compound containing one or more hydroxy groups such as for example phenol or catechol and can contain a C1-C3 alkyl group such as for example o-cresol. The aldehyde of the Mannich reaction product can be a Ci-C₆ aldehyde such as for example formaldehyde and reactive equivalents thereof. The amine of the Mannich reaction product can be an amine that contains at least one primary or secondary amino group that is capable of undergoing a Mannich reaction. The amine can be ammonia, a monoamine, a polyamine, or a mixture thereof. The amine can be an alkanolamine that contains one or more hydroxy groups. Useful amines include for example di-methylamine, ethylenediamine, ethanolamine and diethanolamine. The hydrocarbyl-substituted hydroxy-containing aromatic compound, aldehyde and amine can be reacted in a mole ratio that is respectively 1 :0.5-1.5:0.5-1.5. In an embodiment of the invention, the Mannich reaction product is prepared from a hydrocarbyl-substituted phenol, formaldehyde and diethanolamine where the hydrocarbyl substituent is derived from a polyisobutylene. Methods to prepare a Mannich reaction product are well known and generally involve an acid catalyzed alkylation of a hydroxy- containing aromatic compound with a polyolefin followed by reaction of the alkylation product with an aldehyde and an amine as described in US Patent No. 5,876,468.

[0029] The surfactant can be a hydrocarbyl-substituted carboxylic acid which can comprise a carboxylic acid as described in detail above for a carboxylic acid of the hydrocarbyl-substituted acylating agent, a C4-C30 fatty carboxylic acid, a dimer and/or trimer of an unsaturated fatty carboxylic acid, or a mixture thereof. In an embodiment of the invention, the hydrocarbyl-substituted carboxylic acid is a hydrocarbyl-substituted acylating agent which is an alkenylsuccinic acid where the alkenyl substituent is derived from a polyisobutylene. The fatty carboxylic acid can have 4 to 30 carbon atoms, 6 to 25 carbon atoms or 8 to 22 carbon atoms. The fatty carboxylic acid can be linear, branched or a mixture thereof. The fatty carboxylic acid can be saturated, unsaturated or a mixture thereof. The fatty carboxylic acid can be a single acid or a mixture of 2 or more acids that differ in carbon number, branching and/or saturation. The dimer and/or trimer of an unsaturated fatty carboxylic acid can be derived from dimerization or trimerization of an unsaturated fatty carboxylic acid having 4 to 30 carbon atoms, 6 to 25 carbon atoms, or 8 to 22 carbon atoms. Useful fatty carboxylic acids and dimer and trimer acids thereof include for example oleic acid, stearic acid, tall oil fatty acid, and dimers and/or trimers of Ci8 unsaturated fatty carboxylic acids. Fatty carboxylic acids and dimers and/or timers of unsaturated fatty carboxylic acids are available commercially from several manufacturers.

[0030] The surfactant can be an alkoxylated alcohol, a carboxylate ester of an alkoxylated alcohol, or a mixture thereof. The alcohol can be a monohydric alcohol, a polyhydric alcohol containing 2 or more hydroxy groups such as for example a glycol or glycerol, or a mixture thereof. The alcohol can have 1 to 30 carbon atoms, 4 to 25 carbon atoms, or 6 to 22 carbon atoms. The alcohol can be linear, branched or a mixture thereof. The alcohol can be saturated, unsaturated or a mixture thereof. The alcohol can be a single alcohol or a mixture of two or more alcohols that differ in carbon number, saturation and/or branching. The alkoxylated alcohol can be monoalkoxylated with a single alkylene oxide unit or polyalkoxylated with 2 or more alkylene oxide units. The alkoxylated alcohol can have 1 to 50 alkylene oxide units, 1 to 10 alkylene oxide units or 1 to 5 alkylene oxide units. The alkylene oxide can have 2 to 16 carbon atoms, 2 to 10 carbon atoms or 2 to 6 carbon atoms. The polyalkoxylated alcohol can be derived from a single alkylene oxide or from 2 or more alkylene oxides that differ in carbon number where the 2 or more alkylene oxides can be reacted as a mixture or sequentially with the alcohol. The carboxylate ester of an alkoxylated alcohol can be obtained by reacting an alkoxylated alcohol with a carboxylic acid or reactive equivalent thereof such as an anhydride or ester or acid halide where the carboxylic acid can be a mono- or polycarboxylic acid having per mole of the mono- or polycarboxylic acid 1 to 220 carbon atoms, 1 to 180 carbon atoms, or 1 to 110 carbon atoms. The alkoxylated alcohol and carboxylate ester thereof are commercially available such as for example ethoxylated and/or propoxylated alcohols and/or can be prepared by well-known methods.

[0031] The surfactant can be an alkoxylated alkylphenol, a carboxylate ester of an alkoxylated alkylphenol, or a mixture thereof. The alkyl substituent of the alkylphenol can be linear, branched or a mixture thereof. The alkyl substituent can be saturated, unsaturated or mixture thereof. The alkyl substituent can have 1 to 180 carbon atoms, 4 to 110 carbon atoms or 7 to 85 carbon atoms. The alkylphenol can be a single alkylphenol or a mixture of 2 or more alkylphenols that differ in carbon number, saturation and/or branching. The alkylphenol can be monoalkoxylated or can be polyalkoxylated with a single alkylene oxide or with 2 or more alkylene oxides. The carboxylate ester of an alkoxylated alkylphenol can be obtained by reacting an alkoxylated alkylphenol with a carboxylic acid or reactive equivalent thereof. The alkoxylated alkylphenol and carboxylate ester thereof are commercially available and/or can be prepared by well-known methods.

[0032] The surfactant can be an alkoxylated fatty carboxylic acid, a carboxylate ester of an alkoxylated fatty carboxylic acid, or a mixture thereof. The fatty carboxylic acid can have 4 to 30 carbon atoms, and in other instances can have 6 to 25 carbon atoms, or 8 to 22 carbon atoms. The fatty carboxylic acid can be linear, branched or a mixture thereof. The fatty carboxylic acid can be saturated, unsaturated or a mixture thereof. The fatty carboxylic acid can be a single acid or a mixture of 2 or more acids that differ in carbon number, branching and/or saturation. The fatty carboxylic acid can be monoalkoxylated or can be polyalkoxylated with a single alkylene oxide or with 2 or more alkylene oxides as described in detail above for the alkoxylated alcohol. The carboxylate ester of an alkoxylated fatty carboxylic acid can be obtained by reacting an alkoxylated fatty carboxylic acid with a carboxylic acid or reactive equivalent thereof as described in detail above for the carboxylate ester of an alkoxylated alcohol. The alkoxylated fatty carboxylic acid and carboxylate ester thereof are commercially available and/or can be prepared by well-known methods.

[0033] The surfactant can be a fatty carboxylic acid ester. The fatty carboxylic acid or reactive equivalent thereof, to include an anhydride, an ester or an acid halide, can have in the acid portion of the compound 4 to 30 carbon atoms, and in other instances can have 6 to 25 or 8 to 22 carbon atoms. The fatty carboxylic acid can be a single acid or a mixture of 2 or more acids that differ in carbon number, branching and/or saturation for the alkoxylated fatty carboxylic acid. The fatty carboxylic acid ester can be obtained by esterifying or reacting the acid or a reactive equivalent thereof with an alcohol or a reactive equivalent thereof to include an alkene. The alcohol can be a monohydric alcohol, a polyhydric alcohol having 2 or more hydroxy groups, or a mixture thereof. The monohydric alcohol can have 1 to 30 carbon atoms, can be linear or branched or a mixture thereof, and can be saturated or unsaturated or a mixture thereof. The monohydric alcohol can be a single alcohol or a mixture of 2 or more alcohols that differ in carbon number, branching and/or saturation. The polyhydric alcohol can be a glycol, a polyhydroxy alcohol having 3 or more hydroxy groups, or a mixture thereof. The glycol can include for example ethylene glycol, propylene glycol, neopentyl glycol, or mixtures thereof. The polyhydroxy alcohol containing 3 or more hydroxy groups can include for example glycerol and oligomers of glycerol such as a glycerol dimer and trimer, mono- and dipentaerythritol, l, l, l-tris(hydroxymethyl)alkanes such as 1, 1, 1- tris(hydroxymethyl)propane, polyhydroxy alcohols derived from monosaccharides such as sorbitol and its cyclic anhydride sorbitan, or mixtures thereof. The polyhydroxy alcohol containing 3 or more hydroxy groups can be alkoxylated as described in detail above for the alkoxylated alcohol. In embodiments of the invention the polyhydroxy alcohol containing 3 or more hydroxy groups can be alkoxylated prior to or following esterification of the fatty carboxylic acid with the polyhydroxy alcohol. Useful fatty carboxylic acid esters can include for example methyl oleate; glycerol mono- or di- or trioleate or mixtures thereof; ethylene glycol mono- or distearate or mixtures thereof; sorbitan mono- or trioleate or mixtures thereof; poly(oxyalkylene) sorbitan esters; triglycerol diisostearate; poly(ethylene glycol) dilaurate where the polyglycol has a 200 molecular weight; or mixtures thereof. The fatty carboxylic acid esters are commercially available and/or can be prepared by well-known methods.

[0034] The surfactant can be a polymer, copolymer or block copolymer of one or more alkylene oxides. The polymer can be obtained by polymerizing a single alkylene oxide while the copolymer and block copolymer can be obtained by polymerizing 2 or more alkylene oxides that differ in carbon number respectively as a mixture or sequentially. The alkylene oxide can have 2 to 16 carbon atoms, and in other instances can have 2 to 10 or 2 to 6 carbon atoms. The polymer or copolymer or block copolymer can comprise 2 to 50, 2 to 25 or 2 to 10 alkylene oxide units. Useful polymers, copolymers and block copolymers include for example polymers, copolymers and block copolymers from ethylene oxide, propylene oxide, or mixtures thereof. The polymers, copolymers and block copolymers are available commercially and/or can be prepared by well-known methods.

[0035] The surfactant can be an alkoxylated and/or carboxylated saccharide. The saccharide can comprise a monosaccharide and/or derivative thereof, a disaccharide, or a mixture thereof. The monosaccharide can comprise an aldose, ketose, or mixture thereof. The monosaccharide derivative can comprise a hemiacetal of an aldose, a hemiketal of a ketose, or a mixture thereof. The disaccharide can comprise a dimer of an aldose and/or ketose. Useful saccharides include for example glucose, sucrose, methyl glucoside, or mixtures thereof. The saccharide can be monoalkoxylated or can be polyalkoxylated with a single alkylene oxide or with 2 or more alkylene oxides that differ in carbon number for the alkoxylated alcohol. The saccharide can be carboxylated with one or more fatty carboxylic acid units or a reactive equivalent thereof for the fatty carboxylic acid ester. The saccharide can be both alkoxylated and carboxylated as described above in this paragraph. In an embodiment of the invention, the saccharide is first alkoxylated and then carboxylated. In another embodiment of the invention, the saccharide is first carboxylated then alkoxylated. Useful alkoxylated and/or carboxylated saccharides include for example methyl glucoside dioleate, methyl glucoside sesquistearate, or mixtures thereof. The alkoxylated and/or carboxylated saccharides are commercially available and/or can be prepared by well-known methods.

[0036] The surfactant can be an alkoxylated fatty carboxylic acid ester or vegetable oil or animal oil or mixture thereof. The fatty carboxylic acid ester or vegetable oil or animal oil will generally contain one or more reactive hydroxy groups that can be alkoxylated. Useful fatty esters, vegetable oils and animal oils can include for example esters of 12-hydroxystearic acid, esters of polyols containing 1 or more reactive hydroxy groups such a mono- or diglyceride, castor oil, hydrogenated castor oil, or mixtures thereof. The fatty ester or vegetable or animal oil can be monoalkoxylated with a single alkylene oxide unit or polyalkoxylated with 2 or more alkylene oxide units. The alkoxylated fatty ester or vegetable oil or animal oil can have 1 to 50 alkylene oxide units, and in other instances can have 1 to 35 or 1 to 20 alkylene oxide units. The alkylene oxide can have 2 to 16 carbon atoms, and in other instances can have 2 to 10 or 2 to 6 carbon atoms. The polyalkoxylated fatty ester or vegetable oil or animal oil can be derived from a single alkylene oxide or from 2 or more alkylene oxides that differ in carbon number where the 2 or more alkylene oxides can be reacted as a mixture or sequentially with the fatty ester or vegetable oil or animal oil. Useful alkoxylated fatty esters or vegetable oils or animal oils can include for example ethoxylated mono- and diglycerides and mixtures thereof; ethoxylated castor oil; ethoxylated, hydrogenated castor oil; or a mixture thereof. The alkoxylated fatty carboxylic acid esters, vegetable oils and animal oils are commercially available and/or can be prepared by well-known methods.

[0037] The surfactant in an embodiment of the present invention can be a reaction product of a hydrocarbyl-substituted acylating agent and an amine, an alcohol, or a mixture thereof; a fatty carboxylic acid ester; or a mixture thereof. In another embodiment of the invention, the surfactant can be a reaction product of an alkenyl succinic anhydride and an amine; a fatty carboxylic acid ester of a polyhydric alcohol; or a mixture thereof. The surfactant in a further embodiment of this invention can be a reaction product of an alkenylsuccinic anhydride and an alkanolamine wherein the alkenyl substituent is derived from a polyisobutylene; a sorbitan fatty carboxylic acid ester; or a mixture thereof. [0038] The surfactant can be present in the emulsion composition of the invention in an amount that is sufficient to stabilize the water-in-organic phase emulsion composition from phase separation after preparation of the emulsion composition and prior to and during its use in an ink or coating composition of this invention. The amount of the surfactant present in the water-in-organic phase emulsion composition can desirably be on a weight basis from 0.1 or 0.2 to 10 or 20 %, and in another embodiments of the invention can desirably be from 0.3 or 0.5 to 5 or 7.5%.

[0039] The water-in-organic phase emulsion composition of the present invention can be prepared at ambient or room temperatures, and in other instances can be prepared at 1 or 2 to 100 °C; 5, 10 or 20 to 90 °C; or 10 or 20 to 80 °C. The emulsion composition can be prepared by simply combining the components of the emulsion in any order of addition. The preferred surfactants of the emulsifier package are more soluble in the hydrocarbon phase than the water phase so they are dissolved in the hydrocarbon (monomer) phase in the examples. To make the process for the preparation of the emulsion more efficient, the surfactant can initially be dissolved in the continuous phase (one or more unsaturated polymerizable monomers) and then the inner or water phase can gradually be metered into the solution of the surfactants and outer phase. Generally, it may be desirable to heat the water phase to a higher temperature than the monomer phase to make the water phase even lower in viscosity relative to the continuous phase.

[0040] To prepare a more stable emulsion, the components can be stirred or mixed as they are combined using a stirrer which can be a moderate to high speed stirrer. The stirring rate of the stirrer on a revolutions per minute basis can be at 100 to 500,000, and in other instances can be at 100 or 200 to 10,000 or 20,000 rpm (revolutions per minute). Any type of stirrer can be used such as a propeller, turbine (optionally pitched), anchor, and dispersing homogenizing blades. The stirrer tip speed may be a better indicator of the shear force utilized. Generally, a tip speed of from 0.2 or 1 to 3 m/sec will be sufficient to form such an emulsion. There may be a benefit to adding the water phase (phase to be dispersed) to the monomer phase (the continuous phase). The length of time needed for stirring the components to form a stable emulsion will generally be until the inner phase comprises droplets having a mean diameter of 0.1 to 10 micrometers (microns). [0041] The water-in-organic phase emulsion composition of the present invention can comprise one or more additional components as described herein below for the components of the energy curable ink or coating composition.

[0042] Energy curable ink and coating compositions are well known to the art and the various initiators and energy sources are well known to the art. We use the term polymerizable to also describe these systems as they go from monomers to polymers over a short curing time such as less than one second to several seconds to a minute or two. While we mention free radical mechanism, these monomers and emulsions would work as well with cationic or anionic polymerization systems if the particular ionic polymerization system is tolerant of water. A preferred composition is UV energy activated free radical polymerizations where a UV source activates a compound in the energy curable system that initiates polymerization. Another preferred composition is electron beam cured. If the polymerization system is using free radicals it will often have a mechanism or additive to reduce the probability that oxygen in the atmosphere will inhibit polymerization.

[0043] The water-in-organic phase emulsion composition can be present in the energy curable ink or coating composition on a weight basis at 1 to 40 wt.%, and in other instances at 2 to 25 wt.%, or at 7 or 8 to 20 or 25 wt.% based on the weight of the energy curable ink or coating composition. The surfactant can be present in the ink composition on a weight basis at 0.006 to 9.9%, and in other instances at 0.006 to 8.5%, or at 0.008 to 7.5% or at 0.008 to 5% or at 0.008 to 3%>. The water can be present in the energy curable ink composition from 1 to 30 wt.%, more desirably 2 or 3 to 20 wt.% and preferably 6 to 15 wt.%) based on the weight of the energy curable ink or coating compositions. The mono- unsaturated monomer and optional polyunsaturated polymerizable monomer carried forward from the water-in-monomer emulsion can be present in the ink or coating composition from 0.4, 0.5, or 0.6 to about 3, 4, or 5 wt.%> of the coating. But additional monomers of the same type can be added during formulation of the energy curable ink, so there is no upper limit on the amount of monofunctional monomer in the energy curable ink or coating.

[0044] The water-in-organic phase emulsions are useful in energy cured inks and coatings. The emulsions can be added to the other components to the ink or coating formulation and the dispersed water phase will be transferred into the ink or coating with very little change in droplet size. The additional components to an energy cured ink or coating are generally polymerizable monomers (mono or poly(ethylenically unsaturated) and optional components selected from viscosity control agents, energy activated initiators, wetting agents, gloss control agent, defoamer, plasticizer, colorants, dispersant for the colorant (if the colorant is not soluble or self-dispersable in the formulation), polymerization inhibitor, etc. Generally, energy curable inks and coatings use a percentage of multifunctional monomers to crosslink the ink or coating during polymerization. This increases the resistance of the coatings or inks to wear, temperature, solvents, water, etc. If the coating or ink is to be applied to a flexible substrate the amount of crosslinking may be less, as the coating will need some flexibility to deform when the substrate deforms. If the coating or ink is to be applied to a rigid substrate, there is an option to heavily crosslink the ink or coating.

[0045] The coating or ink can be applied to the substrate by a variety of methods. These include gravure printer or coater, lithographic printing, roll coater, comma coater, blade coater, air knife coating, curtain coater, kiss roll coater, spray coater, wheel coater, spin coater, dip coater, cascade coater, flexographic coater, digital (e.g. inkjet) printer, slot coater, wire bound bar coater, screen printing, spray applicator, bar coater, etc. The substrate can be a synthetic or natural paper, various natural fiber and synthetic polymer boards, wood, wall paper, vinyl wall paper, home appliances, mobile phones, woven or nonwoven sheets, toys, furniture, cabinets, molding, handrails, flooring, vehicles, sports equipment, safety equipment, etc.

[0046] The energy curable ink or coating can be cured using any appropriate energy source. Exemplary energy sources include actinic radiation, such as radiation having a wavelength in the ultraviolet or visible or infrared region of the spectrum; accelerated particles, such as electron beam radiation; or thermal, such as heat. Examples of suitable sources of actinic radiation include, but are not limited to, mercury lamps, xenon lamps, carbon arc lamps, tungsten filament lamps, lasers, light emitting diodes, sunlight, and electron beam emitters and combinations thereof. Energy sources include mercury lamps, xenon lamps, carbon arc lamps, tungsten filament lamps, lasers, light emitting diodes, sunlight, and electron beam emitters or combinations thereof. In some methods, the ink or coating is curable by any one of UV, LED, H-UV and EB radiation or a combination thereof, particularly by using UV radiation. The methods result in a printed article that includes the cured ink or coating provided herein. [0047] As used herein, "monomer" refers to a material having a viscosity less than that of an oligomer and a relatively low molecular weight (i.e., having a molecular weight less than about 500 g/mole) and containing one or more polymerizable groups, which are capable of polymerizing and combining with other monomers or oligomers to form other oligomers or polymers. A monomer can have a viscosity of 150 cP or less measured at 25°C at a shear rate of about 4 to 20 sec^"1 with a Brookfield viscometer. A monomer can be used to modulate the viscosity of an oligomer or of an ink or coating composition.

[0048] As used herein, "oligomer" refers to a material having a viscosity greater than that of a monomer and a relatively intermediate molecular weight (i.e., having a molecular weight greater than about 500 g/mole but generally less than 100,000 g/mole) having one or more radiation polymerizable groups, which are capable of polymerizing and combining with monomers or oligomers to form other oligomers or polymers. The number average molecular weight of the oligomer is not particularly limited and can be, for example, between about 500-10,000 g/mole. Oligomer molecular weight and its distribution can be determined by gel permeation chromatography. An oligomer can be used to modulate the viscosity of an ink or coating composition.

[0049] As used herein, "cure" or "curing" refers to a process that leads to polymerizing, hardening and/or cross-linking of monomer and/or oligomer units to form a polymer. Curing can occur via any polymerization mechanism, including, e.g., free radical routes, and/or in which polymerization is photo initiated, and can include the use of a radiation sensitive photo initiator. As used herein, the terms "curable ink" and "curable coating" refer to an ability of an ink or coating to polymerize, harden, and/or cross-link in response to suitable curing stimulus. As used herein, the term "cured ink" or "cured coating" refers to a curable ink or coating that has been polymerized. In a cured ink or coating, the curable components of a curable ink or curable coating react upon curing to form a polymerized or cross-linked network. On curing, the liquid or fluid curable ink or coating cross-links, polymerizes and/or hardens to form a film of cured ink or cured coating. When the curable ink or curable coating cures from a liquid state to a solid state, the curable monomers and/or oligomers form (1) chemical bonds, (2) mechanical bonds, or (3) a combination of a chemical and mechanical bonds.

[0050] As used herein, "radiation curable" or "energy curable" refers to curing in response to exposure to suitable radiation. The term "radiation curable" or "energy curable" is intended to cover all forms of curing upon exposure to a radiation source. The energy source used to initiate crosslinking of the radiation-curable components of the composition can be actinic, such as radiation having a wavelength in the ultraviolet or visible region of the spectrum; accelerated particles, such as electron beam radiation; or thermal, such as heat or infrared radiation. Examples of suitable sources of actinic radiation include mercury lamps, xenon lamps, carbon arc lamps, tungsten filament lamps, lasers, light emitting diodes, sunlight, and electron beam emitters. The curing light can be shuttered, filtered or focused.

[0051] The inventive inks and coatings provided herein can be prepared using any technique known in the art for preparation of inks and coatings. For example, ink bases can be prepared by mixing a pigment with a liquid mixture of resins (including grinding resins and adhesion promoting resins), monomers, water-in-organic phase emulsion, oligomers or a combination thereof. Each base can be milled, such as by passing over a 3-roll mill, until a desired grind gauge specification is achieved. Once the desired grind is achieved, the base composition can be let down using let down varnishes that include a mixture of resins and optionally photo initiators, and the letdown material can be mixed until homogenous. In the case of the white inks, and generally for coatings, milling may not be necessary. The components of these inks and coatings generally are mixed using a high speed stirrer to obtain the final composition.

[0052] The formulations of the present invention can include a mono-acrylate component. Suitable mono-acrylates or their mono(meth) acrylates components include monofunctional ethylenically unsaturated monomers such as, for example, monofunctional acrylate ester (CD277), monofunctional acrylate ester (CD278), acrylic ester (CD587), acrylic ester (CD585), acrylic monomer (CD420), 2-phenoxy ethyl acrylate (SR 339), cyclic trimethylolpropane formal acrylate (SR 531), isodecyl acrylate (SR 395), lauryl acrylate (SR 335), tridecyl acrylate (SR 489), stearyl acrylate (SR 257), 2(2-ethoxyethoxy) ethyl acrylate (SR 256), isooctyl acrylate (SR 440), tetrahydrofurfuryl acrylate (SR 285) (available from Sartomer, Exton, Pennsylvania), methyl acrylate, ethyl acrylate, isopropyl acrylate, n-hexyl acrylate, allyl acrylate, 2-(2'-vinyloxy ethoxy)ethyl acrylate (VEEA) (available from Nippon Shokubai Co., Inc, Tokyo, Japan), and acrylates or their (meth)acrylates of straight chain, branched chain, or cyclic alkyl alcohols of from 1 to 30 carbon atoms, including polyether alcohols. [0053] Specific examples include acrylates of alcohols having more than four carbon atoms with acrylic or methacrylic acid, for example lauryl acrylate and stearyl acrylate; (meth)acrylates of polyether alcohols, such as 2-(2-ethoxyethoxy)ethyl acrylate; (meth)acrylates, of cyclic alcohols, optionally containing an aliphatic linking group between the (meth)acrylate and the cyclic group, such as tetrahydrofuran acrylate (SR 285), oxetane acrylate, isobornyl acrylate (SR 506), cyclopentadiene acrylate, and the like and any subset thereof. Any combinations or subset of the foregoing may be utilized.

[0054] Other mono-ethylenically unsaturated monomers include C₈-Ci5 styrene and substituted styrene, vinyl esters of vinyl alcohol with C₂ to Ci₈ carboxylic acids, acrylonitrile (optionally methyl, ethyl or propyl substituted), acrylamide monomers of 3 to 30 carbon atoms, vinyl chloride, vinyl pyridine, vinyl pyrrolidone, maleic anhydride, mono C1-C15 alkyl substituted fumarate monomers, di C1-C15 dialkyl substituted fumarate monomers, and C₈-C₂o alpha-beta unsaturated olefins.

[0055] Preferred diacrylates include, but are not limited to: ethylene glycol diacrylate, propylene glycol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, tertraethylene glycol diacrylate, tetrapropylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, bisphenol A diglycidyl ether diacrylate, resorcinol diglycidyl ether diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, cyclohexane dimethanol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated cyclohexanedimethanol diacrylate, propoxylated cyclohexanedimethanol diacrylate, epoxy diacrylate, aryl urethane diacrylate, aliphatic urethane diacrylate, polyester diacrylate, vinyl ester diacrylate and mixtures thereof.

[0056] Preferred triacrylates include, but are not limited to: trimethylol propane triacrylate, glycerol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, aryl urethane triacrylates, aliphatic urethane triacrylates, melamine triacrylates, epoxy novolac triacrylates, aliphatic epoxy triacrylate, polyester triacrylate, and mixtures thereof. [0057] Preferred tetraacrylates include, but are not limited to: di- trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, ethoxylated dipentaerythritol tetraacrylate, propoxylated dipentaerythritol tetraacrylate, aryl urethane tetraacrylates, aliphatic urethane tetraacrylates, polyester tetraacrylates, melamine tetraacrylates, epoxy novolac tetraacrylates, and mixtures thereof. Higher functionality acrylates, e.g. pentaacrylates, hexaacrylates, etc. are also available and may be used.

[0058] The ink or coating formulations of the present invention can include a vinyl ether component as a free radically polymerizable compound(s). Suitable vinyl ether components include vinyl ethers such as, for example, ethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, triethylene glycol monobutyl vinyl ether, cyclohexanedimethanol divinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, propenyl ether propylene carbonate, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, diethylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexyl vinyl ether, 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, 2,2- bis(4- vinyloxyethoxyphenyl)propane, and 1 ,4-bis(2-vinyloxyethoxy)benzene, specifically triethyleneglycol divinylether (Rapi-Cure® DVE-3), cyclo hexane dimethyl divinyl ether (Rapi-Cure® CHVE), 4-hydroxybutylvinylether (Rapi-Cure® 4-HBVE), polyether cyclic polyols (Rapi-Cure® PECP), and dodecyl vinyl ether (Rapi-Cure® DDVE) (available from ISP Performance Chemicals, Wayne, New Jersey), ethyleneglycol monovinyl ether (EGM-VE), ethyl vinyl ether (E-VE), propyl vinyl ether (P-VE), isobutyl vinyl ether (iB-VE), 1,6-hexanediol divinyl ether (HD-DVE), aminopropyl vinyl ether (APVE), tert-amyl vinyl ether (TAVE), butanediol divinyl ether (BDDVE), n-butyl vinyl ether (NBVE), tert- butyl vinyl ether (TBVE), cyclohexanedimethanol divinyl ether (CHDVE), cyclohexanedimethanol monovinyl ether (CHMVE), cyclohexyl vinyl ether (CVE), diethylaminoethyl vinyl ether (DEAVE), diethyleneglycol divinyl ether (DVE-2), diethyleneglycol monovinyl ether (MVE-2), dodecyl vinyl ether (DDVE), ethyleneglycol butyl vinyl ether (EGBVE), ethyleneglycol divinyl ether (EGDVE), ethylhexyl vinyl ether (EHVE), hexanediol divinyl ether (HDMVE), 4-hydroxybutyl vinyl ether (4-HBVE), isopropyl vinyl ether (IPVE), octadecyl vinyl ether (ODVE), polyethyleneglycol-520 methyl vinyl ether (MPEG500-VE), polytetrahydrofuran divinyl ether (PTHF290-DVE), plurio-E200 divinyl ether (PEG200-DVE), n-propyl vinyl ether ( PVE), tetraethyleneglycol divinyl ether (DVE-4), triethyleneglycol divinyl ether (DVE-3), triethyleneglycol methyl vinyl ether (MTGVE), and trimethylolpropane trivinyl ether (TMPTVE) (available from BASF Aktiengesellschaft, Ludwigshafen, Germany), and hydroxyl ethyl vinyl ether (F£EVE), diethylene glycol divinyl ether (DEG-DVE), (available from Nisso Maruzen Chemical, Tokyo, Japan) and any combination or subset thereof.

[0059] Alternately, vinyl ether based oligomers may be utilized in the formulations of the invention. An example of a vinyl ether based oligomer is VEctomer® 1312, a mixture of vinyl ether terminated aromatic ester oligomers (available from Morflex Inc., Greensboro, North Carolina). Any combinations or subset of the foregoing may be utilized.

[0060] The formulations of the present invention may also include a hybrid component containing both vinyl ether and acrylate functionality. These difunctional monomers are especially useful for decreasing the viscosity of curable compositions. Exemplary difunctional monomers include but are not limited to 2-(2-vinylethoxy)ethyl (meth)acrylate, 2-(2 -vinyl ethoxy)-2-propyl (meth)acrylate, 2-(2 vinylethoxy)-3 -propyl (meth)acrylate, 2-(2-vinylethoxy)-2-butyl(meth)acrylate, 2-(2-vinylethoxy)-4-butyl (meth)acrylate, 2-(2-allylethoxy) ethyl (meth)acrylate, 2-(2-allylethoxy)-2-propyl (meth)acrylate, 2-(2-allylethoxy)-3 -propyl (meth)acrylate, 2-(2-allylethoxy)-2 -butyl (meth)acrylate, 2-(2-allylethoxy)-4-butyl (meth)acrylate, 2-(2-vinylpropoxy)ethyl (meth)acrylate, 2-(2-vinylpropoxy)2-propyl (meth)acrylate, 2-(2-vinylpropoxy)-3 -propyl (meth)acrylate, 2-(3-vinylpropoxy)ethyl (meth)acrylate, 2-(3-vinylpropoxy)-2-propyl (meth)acrylate, 2-(3-vinylpropoxy)-3 -propyl (meth)acrylate, and sub-sets and combinations comprising at least one of the foregoing. The compound 2-(2- vinylethoxy)ethyl acrylate (VEEA) is commercially available from Nippon Shokubai Co., Inc, Tokyo, Japan. Any combinations or subset of the foregoing may be utilized.

[0061] The free-radically polymerizable compound(s) characterized by having one or more ethylenically unsaturated group(s) per compound may be commercially available polyesters, polyethers epoxide oligomers, or urethanes functionalized with ethylenically unsaturated groups. These could be any aliphatic or aromatic polyester, polyether, epoxide oligomers, or urethane. Aromatic polyesters and urethanes tend to have higher potential use temperatures than aliphatic urethane and polyesters (but that can be varied by the choice of the other components in the polyester or polyurethane such as the polyol used in the polyester and the macromolecular diol or diamine reactant). It is desirable that both the polyester, polyether, epoxide oligomers, and polyurethane be functionalized with one or more ethylenically unsaturated group so they can be co-polymerized during the energy cured, e.g. UV activated free radical, reaction.

[0062] When the free-radically polymerizable compound(s) characterized by having one or more ethylenically unsaturated group(s) per compound are oligomeric polyepoxide, oligomeric polyester, oligomeric polyether or oligomeric polyurethane, desirably they have a number average molecular weight from about 200, 300, or 500 to about 5000 or 10,000 g/mole and said one or more ethylenically unsaturated groups (more desirably two or more ethylenically unsaturated groups and preferably 2 to 5 ethylenically unsaturated groups. More desirably, the number average molecular weight is from about 300, 500, 800, or 1000 to about 2000 or 3000 g/mole.

[0063] The oligomer having an ethylenically unsaturated group in the present invention may be any oligomer, and examples thereof include an olefin-based oligomer (an ethylene oligomer, a propylene oligomer, a butene oligomer, etc.), a vinyl-based oligomer (a styrene oligomer, a vinyl alcohol oligomer, a vinylpyrrolidone oligomer, an acrylate oligomer, a methacrylate oligomer, etc.), a diene-based oligomer (a butadiene oligomer, a chloroprene rubber, a pentadiene oligomer, etc.), a ring-opening polymerization type oligomer (di-, tri-, tetra-ethylene glycol, polyethylene glycol, poly ethyl eneimine, etc.), an addition-polymerization type oligomer (an oligoester acrylate, a polyamide oligomer, a polyisocyanate oligomer), and an addition-condensation oligomer (a phenolic resin, an amino resin, a xylene resin, a ketone resin, etc.), having an ethylenically unsaturated group. Among them an oligoester (meth)acrylate is preferable, and among them a urethane (meth)acrylate, a polyester (meth)acrylate, and an epoxy (meth)acrylate are preferable, and a urethane (meth)acrylate is more preferable.

[0064] As the urethane (meth)acrylate, an aliphatic urethane (meth)acrylate and an aromatic urethane (meth)acrylate may preferably be cited, and an aliphatic urethane (meth)acrylate may more preferably be cited. As oligomer commercial products, examples of urethane (meth)acrylates include R1204, R1211, R1213, R1217, R1218, R1301, R1302, R1303, R1304, R1306, R1308, R1901, and R1150 manufactured by Dai-lchi Kogyo Seiyaku Co., Ltd., the EBECRYL series (e.g. EBECRYL 230, 270, 4858, 8402, 8804, 8807, 8803, 9260, 1290, 1290K, 5129, 4842, 8210, 210, 4827, 6700, 4450, and 220) manufactured by Daicel-Cytec Company Ltd., NK Oligo U-4HA, U-6HA, U-15HA, U-108A, and U200AX manufactured by Shin-Nakamura Chemical Co., Ltd., and Aronix M-1100, M-1200, M-1210, M-1310, M-1600, and M- 1960 manufactured by Toagosei Co., Ltd., CN964 and A85 manufactured by Sartomer. The ink optionally comprises a urethane acrylate oligomer. Where such a monomer contains one or more than one ethylenically unsaturated groups it is part of component (a) or (b) respectively. The urethane acrylate oligomer is preferably an aliphatic urethane oligomer Examples of commercially available aliphatic urethane oligomers include: CN 934 CN 934X50, CN 944B85, CN 945A60, CN 945B85, CN 953B70, CN 961 E75, CN 961 H81, CN 962, CN 963 A80, CN 963B80, CN 963E75, CN 963E80, CN 963J85, CN 964, CN 964A85, CN 964B85, CN 964H90, CN 964E75, CN 965, CN 965 A80, CN 966A80, CN 966B85, CN 966H90, CN 966180, CN 966J75, CN 966R60, CN 968, CN 982E75, CN 982P90, CN 983, CN 983B88, CN 984 and CN 985B88, all available from Sartomer, and mixtures comprising two or more thereof. Examples of commercially available aromatic urethane oligomers include CN 970A60, CN 970E60, CN 970H75, CN 971 A80, CN 972, CN 973 A80, CN 973H85, CN 973 J75, CN 975, CN 977C70, CN 978, CN 980, CN 980M50, CN 981, CN 981 A75, CN 981 B88, ON 982A75 and CN 982B88, all from Sartomer, and mixtures comprising two or more thereof.

[0065] The free-radically polymerizable compound(s) characterized by having one or more ethylenically unsaturated group(s) per compound may be commercially available epoxide based oligomers (made from ring opening epoxide functionalized compounds with carboxylic acids, amine functional reactants, or polyols) and reacting on one or more ethylenically unsaturated group per compound. These are well known commercially to formulators of UV curable coatings. They can have a variety of glass transition temperatures and good resistance to thermal degradation, hydrolysis, solvent swelling, fracture, etc. The epoxide based oligomers can be derived from aromatic epoxides like the diglycidyl ethers of bisphenol A or they can be derived from aliphatic epoxides. Epoxides can be formed from the olefin peroxidation and thus can have a variety of structures.

[0066] Examples of polyester (meth)acrylates include the EBECRYL series (e.g. EBECRY L770, IRR467, 81, 84, 83, 80, 675, 800, 810, 812, 1657, 1810, IRR302, 450, 670, 830, 870, 1830, 1870, 2870, IRR267, 813, IRR483, 811, etc.) manufactured by Daicel-Cytec Company Ltd. and Aronix M-6100, M-6200, M-6250, M-6500, M-7100, M-8030, M-8060, M-8100, M-8530, M-8560, and M-9050 manufactured by Toagosei Co., Ltd. Examples of epoxy (meth)acrylates include the EBECRYL series (e.g. EBECRYL 600, 860, 2958, 3411, 3600, 3605, 3700, 3701, 3703, 3702, 3708, RDX63182, 6040, etc.) manufactured by Daicel-Cytec Company Ltd.

[0067] The energy curable inks and coatings provided herein can contain one or more photo initiators. The amount of the UV activated free radical initiator (if used) in the ink or coating composition is desirably from about 0.5 to about 30 parts by weight, more desirably from about 0.5 or 1 to 20 parts by weight, and preferably from about 0.5 or 1 to about 10 or 15 parts by weight per 100 parts total of the ink or coating. In one embodiment, the UV activated initiator belongs to the group of alpha-amino ketone based UV activated initiators. In one embodiment, the UV activated initiator comprises 2-methyl-l-[4- (methylthio)phenyl]-2-(4-mo holinyl)-l-propanone (Irgacure™ 907) or 2-benzyl-2- dimethylamino-l-(4-mo holinophenyl)-butanone-l (Irgacure™ 369) or mixtures thereof. In one embodiment, the UV activated initiator comprises an acylphosphine oxide, benzophenone, benzoates, and/or thioxanthone (preferably said UV activated initiator comprises (Irgacure™ 819) phenyl bis(2,4,6-trimethylbenzoyl)-phosphine oxide; (Genocure™ PBZ) 4-phenylbenzophenone; (Genocure™ BDMM) 2-benzyl-2- dimethylamino-4'mo holinobutyrophenone; (Genocure™ MBF) methylbenzoylformate; (Genocure™ ITX) thioxanthone; or (Genocure™ EPD) ethyl-4-

(dimethylamino)benzoate; or mixtures thereof). Genocure™ EPD and ITX are often considered synergists to be used with other UV initiators that benefit from synergists. In one embodiment, said UV activated initiator comprises an alpha-hydroxyketone (preferably said UV activated initiator comprises (Irgacure™ 184) (hydroxy cyclohexyl)(phenyl)keton; (Irgacure™ 1173) 2-hydroxy-2- methylpropiophenone; (Irgacure™ 2959) l-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2- methyl-1 -propane- 1 -one) or mixtures thereof. Genocure™ is a trademark of Rahn AG in Zurich Switzerland while Irgacure™ is a trademark of BASF in Germany. Examples of photo initiators that can be included in the ink and coating compositions include, but are not limited to, benzoin ethers, such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; alkylbenzoins, such as methylbenzoin, ethylbenzoin, propylbenzoin, butylbenzoin and pentylbenzoin; benzyl derivatives, such as benzyl-dimethylketal; 2,4,5- triaryl-imidazole dimers, such as 2-(o-chlorophenyl)-4,5- diphenylimidazole dimer, 2-(o- chloro-phenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5- phenyl-imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl- imidazole dimer, 2-(2,4- dimethoxyphenyl)-4,5-diphenyl-imidazole dimer; acridine derivatives such as 9-phenylacridine and l,7-bis(9,9'-aridinyl)heptane; N- phenylglycine; benzophenones, anthraquinones, thioxanthones and derivatives thereof, including chloro-benzophenone, 4-phenylbenzophenone, trimethyl-benzophenone, 3,3'- dimethyl-4- methoxybenzophenone, 4,4'-dimethylamino-benzophenone, 4,4 ' -bis(diethyl- amino)- benzophenone, acrylated benzophenone, methyl-o-benzoyl benzoate, isopropyl- thioxanthone, 2-chloro and 2-ethyl-thioxanthone, 2-benzyl-2-(dimethyl-amino)-4'- morpholino-butyrophenone and hydroxy benzophenone; acetophenone derivatives including 2,2-dimethoxy-2-phenyl-acetophenone, 2,2-diethoxyacetophenone, 2, 2- dimethoxy-2-phenylacetophene and 1 -hydroxy cyclohexylacetophenone; 2-hydroxy-2- methyl-l-phenylpropanone; 4-benzoyl-4'-methyl-diphenyl sulfide; ethyl 4-dimethyl- amino-benzoate; 2-ethyl-hydroquinone; (2,4,6-trimethylbenzoyl)diphenyl phosphine oxide (Lucerin TPO, available from BASF, Munich, Germany); ethyl(2,4,6-trimethyl- benzoyl- phenyl phosphinate; a-hydroxy ketone photo initiators, such as 1 -hydroxy - cyclohexyl- phenyl ketone (e.g., Irgacure® 184 available from Ciba Specialty Chemical (Hawthorne, NY), 2-hydroxy-2-methyl- 1 -phenylpropanone, 2-hydroxy-2-methyl- 1 -(4- isopropyl- phenyl)propanone, 2-hydroxy-2 -methyl- 1 -(4-dodecylphenyl)propanone, 2-hydroxy-2- methyl- 1 -phenylpropanone and 2-hydroxy-2-methyl- 1 -[(2- hydroxyethoxy)-phenyl]- propanone; (2,6-dimethoxy-benzoyl)-2,4,4-trimethylpentyl phosphine oxide (e.g., commercial blends Irgacure® 1800, 1850, and 1700 available from Ciba Specialty Chemical); 2,2-dimethoxyl -2 -phenyl acetophenone (e.g., Irgacure® 651, available from Ciba Specialty Chemical); bisacylphosphine oxide photoinitiators, such as bis(2,4,6- trimethylbenzoyl)phenyl-phosphine oxide (e.g., Irgacure® 819 from Ciba Specialty Chemical), bis(2,6-dimethoxybenzoyl)-isooctyl-phosphine oxide and ethoxy (2,4,6- trimethyl-benzoyl) phenyl phosphine oxide (Lucerin® TPO-L from BASF), and combinations thereof.

[0068] A colorant is component added to generate color. It may be a finely ground solid organic or inorganic material that is usually insoluble in an ink and that imparts color to the ink. A colorant can comprise a pigment, a dye, a toner, or a mixture thereof. In an embodiment of the invention the colorant is a pigment, a dye, or a mixture thereof. A pigment or toner is generally insoluble in the ink or coating. The colorant can further comprise an extender, for example kaolin clay, calcium carbonate, silica, talc, or a mixture thereof where the extender is a white pigment used to reduce the strength or improve the properties of a colorant. In an embodiment of the invention the colorant is a pigment. The pigment can comprise an inorganic pigment, an organic pigment, or a mixture thereof. The inorganic pigment can comprise a white pigment to include titanium dioxide; a colored pigment to include iron blue and ultramarine blue; or a mixture thereof. The organic pigment can comprise a black pigment to include furnace blacks; a colored pigment to include diarylide yellow, hansa yellow, phthalocyanine blue, reflex blue, rubine, rhodamine, red lake C, or a mixture thereof; or a mixture thereof.

[0069] The ink or coating composition can further comprise a wax such as for example beeswax, carnauba, paraffin, polyethylene, polytetrafluoroethylene, or mixtures thereof which can improve slip and scuff/rub resistance; a wetting agent to improve dispersion of a colorant; a matting agent to reduce the gloss, a surfactant to improve wetting of the substrate, a humectant to modify the moisture content, a defoamer component, other additives, or a mixture thereof.

[0070] The ink composition in one embodiment of the invention is a lithographic printing ink composition.

[0071] Furthermore, from the viewpoint of retention of formulation properties during storage and prevention of premature polymerizations, the coating or ink composition preferably comprises a polymerization inhibitor. The polymerization inhibitor is preferably added at 200 to 20,000 ppm relative to the total amount of the coating or ink composition. Examples of the polymerization inhibitor include a nitroso-based polymerization inhibitor, a hindered amine-based polymerization inhibitor, hydroquinone, benzoquinone, p-methoxyphenol, butylated hydroxyl toluene (BHT), TEMPO, TEMPOL, and AI cupferron.

[0072] The present invention further comprises use of an energy cured ink in a lithographic printing process comprising employing in the printing process an ink composition comprising as described in detail throughout this application a) an emulsion composition, and a colorant. [0073] The following examples provide illustrations of the invention. These examples are non-exhaustive and are not intended to limit the scope of the invention.

EXAMPLES

[0074] Several water-in-organic phase emulsions were made from three different monofunctional monomers using a blend of sorbitan mono-oleate and a polyisobutylene succan of about 1000 g/mole number average molecular weight salted with diethyl ethanolamine. In each example, the monomer and the emulsifiers were mixed together at room temperature (22-25 °C) placed in appropriate sized metal beaker, stirred with a G-blade (a dispersion disc blade 3 to 10 cm in diameter, similar to a Cowles blade with slightly less shear). Water was added at a fixed rate (20-25 g/min) to the vortex formed by the G-blade. As we were adding 80-85% water to a 15-20% organic phase the vertical position of the G-blade in the organic phase was occasionally readjusted to keep the G-blade near the vortex of the stirred organic phase. After the addition of all of the water, the stirrer speed was increased for about 5 to 15 minutes to finish forming the emulsion. The emulsion was then allowed to stand overnight and the viscosity was measured the next day with a TA Rheometer (such as a R1000) using shear raters of 1 sec^"1 and 10 sec^"1.

Table 1 Emulsion 1

Components of Example 1 Wt.% in final formulation Grams added

SR395 (isodecyl acrylate) 12.3 87.75

Sorbitan mono-oleate 2.0 14.3

Polyisobutylene succan 2.1 14.95

diethylethanolamine salt

Water 83.4 598

Total 99.9 715 Table 2 Emulsion 1 Mixing Process

[0075] Water feed rate was about 21 g/min. After 29.5 minutes, the rotation speed was increased to 484 rpm and the emulsion was stirred an additional 5-15 minutes. The viscosity the next day and at room temperature was 43 cps at 1 sec^"1 and 13 cps at 10 sec^"1. The water droplet diameter size was less than 5.5 micrometer.

Table 3 Emulsion 2

Components of Example 2 Wt.% in final formulation Grams added

EM70 (isobornyl acrylate) 12.5 75.0

Sorbitan mono-oleate 2.2 13.2

Polyisobutylene succan 2.3 13.8

diethylethanolamine salt

Water 83.0 498

Total 100 600 Table 4 Emulsion 2 Mixing Process

[0076] Water feed rate was about 23 g/min. After 21 minutes the rotation speed was increased to 550 rpm and the emulsion was stirred an additional 10 minutes. The viscosity the next day and at room temperature was 241 cps at 1 sec^"1 and 49 cps at 10 sec^"1. The water droplet diameter size was less than 5.5 micrometer.

Table 5 Emulsion 3

Components for Example 3 Wt.% in final formulation Grams added

EM215 (lauryl acrylate) 1 1.1 78

Sorbitan mono-oleate 1.8 12.7

Polyisobutylene succan 1.9 13.3

diethylethanolamine salt

water 85.1 596

Total 99.9 700

Table 6 Emulsion 3 Mixing Process

[0077] Water feed rate was about 23 g/min. After 26 minutes 40 seconds the rotation speed was increased to 516 rpm and the emulsion was stirred an additional 10 minutes. The viscosity the next day and at room temperature was 92 cps at 1 sec^"1 and 21 cps at 10 sec^"1. The water droplet diameter size was < 5.5 micrometer.

[0078] The above emulsions can be formulated into an energy curable ink with enhanced properties, such as increased or varied viscosity, reduced tendency to absorb water, revised gloss values, etc.

[0079] A millbase was prepared from a pigment, dispersants, and energy curable monomers. The millbase would be mixed with other components, including optional energy activated free radical initiators, additional monomer, etc. to make an ink.

Table 7 Millbase Formulation

[0080] The millbase was initially mixed for 5 minutes at a slow speed with a mixing blade having two propeller type blades with three blades on each propeller. Then 200 g of 2.4-2.8 mm beads were added and the rpm was increased to 1200 using the same two propeller blades. The pigment was ground for 120 minutes at 50 °C to a diameter size of 9 um. Then it was ground for 150 minutes at 48 °C until the particles size was reduced to 7-8 um. The dispersion filtered and flowed acceptably, but the next day it wouldn't flow but easily sheared back into a fluid composition. The millbase was remade several times. A 60 minute milling at 46 °C, 120 minutes at 47 °C and 150 minutes at 46 °C in the second preparation. A 60 minute milling at 47 °C, 120 minutes at 43 °C, and 150 minutes at 45 °C was used for the third preparation.

[0081] The following table 8 illustrates how the emulsions 1, 2, and 3 can be formulated into energy cured inks using the millbase 1 of table 7. The ink formulations were mixed with stirring and then with a DAK mixer before testing. DAK mixers are available from Synergy Devices Limited/Speedmixer in the UK. Ink 5 does not include any water, and uses a lauryl acrylate monomer of Ink 6. Ink 6 contains an emulsion of water in lauryl acrylate. Ink 7 is similar to Inks 5 and 6 but contains no water and replaces lauryl acrylate with at isodecyl acrylate. Ink 8 uses Emulsion 1 (water emulsified in isodecyl acrylate) and can be compared to Ink 7 that lacks the water phase.

Table 8 Energy Curable Ink Formulations

EM621- 100 is a modified epoxy acrylate (possibly based on Bisphenol A) with 100% active sold by Eternal Chemical Co., Ltd. in China used as a reactive monomer with some low profile (anti-shrinkage) effect.

Table 9 Properties of Ink Formulations in Table 8

[0082] The data in Table 9 illustrates that the emulsion of water produces an energy curable lithographic ink with desirable higher gloss values, higher viscosity, and lower water pick up than similar formulations without the emulsified water. The water pick up reported above was determined an automated water balance device for lithographic inks called Lithotronic IV available from Novomatics GmbH in Germany under their Labtech Solutions brand. The Lithotronic IV is designed to measure the water balance performance of offset inks and fount solutions with 1% accuracy with the temperature, shear-rate, and fountain solution content all separately variable. A drop in torque is associated with the emulsion being saturated with water. It was also noted that the energy curable inks of Table 9 with emulsified water concentrates added set quicker during the curing process than similar inks with only the same monofunctional monomer present.

While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications, thereof, will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims

What is claimed is:

1. An emulsion composition comprising of water droplets dispersed in an organic phase, wherein said water droplets are colloidally stabilized with an emulsifier package having a calculated HLB of 0-60 (more preferably a HLB of 10 or less) and said emulsifier package comprises at least one emulsifier, wherein said water droplets are at least 10wt.% of said emulsion, and wherein at least 50 wt.% of said organic phase is esters of (meth)acrylic acid with C8-C30 (more desirably C10-C20) monohydric or polyhydric alcohols (preferably the alcohols are predominantly monohydric); and

wherein the water is present at 10 to 97% by weight and wherein said water optionally comprises 0.1 to 10 wt.% ammonium nitrate dissolved therein, the one or more unsaturated polymerizable monomer(s) is present at 3 to 90% by weight, and the emulsifier package is present at 0.1 to 10% by weight.

2. The emulsion composition of claim 1, wherein at least 20 wt.% of said emulsifier package is an emulsifier(s) having a number average molecular weight between 500 and 2500 g/mole.

3. The emulsion composition of claim 1 or 2, wherein at least 20 wt.% of said emulsifier package comprises a polyisobutylene based emulsifier having a number average molecular weight between 500 and 2500 g/mole.

4. The emulsion composition of claims 1, 2, or 3, wherein at least 20 wt.% of said emulsifier package comprises a sorbitan monoalk(en)ylate, wherein said alk(en)ylate has from 12 to about 24 carbon atoms.

5. The emulsion composition of any of claims 1-4, wherein said water droplets are from 30 to 90 wt.% of said emulsion.

6. The emulsion composition of any of claims 1-5, wherein the one or more unsaturated monomers is suitable for use in an energy curable printing ink or energy curable coating composition.

7. The emulsion composition of any of claims 1-6, wherein the water phase comprises droplets having a mean diameter of 0.1 to 10 microns.

8. The emulsion composition of any of claims 1-7, wherein the water is present at 40 to 95% by weight, and wherein the organic phase comprises one or more mono-unsaturated polymerizable monomer(s) in an amount of at least 60 wt.% of said organic phase.

9. The emulsion composition of any of claims 1-8, wherein the emulsifier package comprises one or more emulsifiers from the group comprising a reaction product of a hydrocarbyl-substituted acylating agent and an amine, an alcohol, or a mixture thereof; a Mannich reaction product of hydrocarbyl-substituted hydroxy-containing aromatic compound, an aldehyde, and an amine containing at least one primary or secondary amino group; a hydrocarbyl-substituted carboxylic acid; an alkoxylated alcohol, a carboxylate ester of an alkoxylated alcohol, or a mixture thereof; an alkoxylated alkylphenol, a carboxylate ester of an alkoxylated alkylphenol, or a mixture thereof; an alkoxylated fatty carboxylic acid, a carboxylate ester of an alkoxylated fatty carboxylic acid, or a mixture thereof; a fatty carboxylic acid ester; a polymer, copolymer or block copolymer of one or more alkylene oxides; an alkoxylated and/or carboxylated saccharide; an alkoxylated fatty carboxylic acid ester or vegetable oil or animal oil or mixture thereof; an amine; an alkoxylated amine; an amide; an alkoxylated amide; an alkanolamide; an alcohol; a sulfonate; an amine oxide; a betaine compound; an imidazoline; a phosphate ester; lignin or a derivative thereof; a quaternary ammonium salt; a sulfate; a sulfosuccinate or derivative thereof; a soap; and a copolymer of a poly(oxyalkylene glycol) and a poly(12- hydroxystearic acid).

10. The emulsion composition of any of claims 1-9, wherein the emulsifier package comprises a reaction product of an alkenyl succinic anhydride and an alkanolamine wherein the alkenyl substituent is derived from a polyisobutylene; a sorbitan fatty carboxylic acid ester; or a mixture thereof.

11. The emulsion composition according to any of claims 1-10, wherein said at emulsifier package has a HLB number of 10 or less;

wherein the water is present at 10 to 90% by weight, the organic phase is present at less than 88%) by weight, and the emulsifier package is present at 2 to 10%> by weight based on the weight of said emulsion composition.

12. An energy curable ink or coating composition, comprising:

the water-in-organic phase emulsion composition of claim 1;

either 2 wt.% or more of one or more polyunsaturated polymerizable monomers; or 2 wt.% or more of one or more ethylenically functional copolymerizable oligomers selected from the group comprising polyester, polyether, epoxide or polyurethane, wherein the emulsion composition is present at 6 to 99% by weight of the ink composition, and the energy curable ink composition is suitable for use in printing or coating a substrate.

13. The energy curable composition of claim 12, wherein the water-in-organic phase emulsion delivers 5 to 35 wt% of water to the energy curable ink composition.

14. The energy curable composition (coating or ink) according to claim 12 or 13, wherein said coating or ink compositions is curable with electron beam radiation.

15. The energy curable coating or ink composition according to claim 12 or 13, wherein said coating or ink composition further comprises a UV activated initiator system and is curable by UV radiation.

16. The energy curable coating or ink composition according to any of claims 12-15, wherein said coating or ink composition is a coating for application on cellulosic substrates (preferably paper or wood), masonry, plastic, or metal.

17. The energy curable coating or ink composition according to any of claims 12-16, wherein said coating or ink composition further comprises a pigment or dye and is an ink composition for creating images and/or text.

18. The energy curable coating or ink composition according to claim 12-17, wherein said ink composition is a lithographic energy curable ink.

19. The energy curable coating or ink composition of any of claims 12-18, wherein the surfactant comprises a reaction product of an alkenylsuccinic anhydride and an alkanolamine wherein the alkenyl substituent is derived from a polyisobutylene and a sorbitan fatty carboxylic acid ester.

20. The energy curable coating or ink composition of any of claims 12-18, wherein said composition applied as a protective or decorative coating on a substrate.

21. The energy curable coating or ink composition of any of claims 12-18, wherein the surfactant comprises a surfactant selected from the group comprising a reaction product of a hydrocarbyl -substituted acylating agent and an amine, an alcohol, or a mixture thereof; a Mannich reaction product of hydrocarbyl -substituted hydroxy-containing aromatic compound, an aldehyde, and an amine containing at least one primary or secondary amino group; a hydrocarbyl -substituted carboxylic acid; an alkoxylated alcohol, a carboxylate ester of an alkoxylated alcohol, or a mixture thereof; an alkoxylated alkylphenol, a carboxylate ester of an alkoxylated alkylphenol, or a mixture thereof; an alkoxylated fatty carboxylic acid, a carboxylate ester of an alkoxylated fatty carboxylic acid, or a mixture thereof; a fatty carboxylic acid ester; a polymer, copolymer or block copolymer of one or more alkylene oxides; an alkoxylated and/or carboxylated saccharide; an alkoxylated fatty carboxylic acid ester or vegetable oil or animal oil or mixture thereof; an amine; an alkoxylated amine; an amide; an alkoxylated amide; an alkanolamide; an alcohol; a sulfonate; an amine oxide; a betaine compound; an imidazoline; a phosphate ester; lignin or a derivative thereof; a quaternary ammonium salt; a sulfate; and a sulfosuccinate or derivative thereof; a soap; a copolymer of a poly(oxyalkylene glycol) and a poly(12- hydroxystearic acid).

22. A process for forming an energy (e.g. radiation) curable coating or ink compositions comprising the steps of;

a) dissolving an emulsifier package having an HLB value of 10 or less in at least one ester of (meth)acrylic acid with C8-C30 (more desirably C10-C20) monohydric alcohols forming a solution of emulsifier package in (meth)acrylic ester;

b) emulsifying water in said solution of emulsifier package in acrylic ester forming an emulsified water phase in (meth)acrylic ester, wherein said water phase is from 10 to 95 wt.% of the combined weight of said emulsified water, (meth)acrylic ester, and emulsifier package and wherein said water phase optionally comprises 0.1 to 10 wt.% ammonium nitrate dissolved therein; formulating an energy curable coating or ink composition by combining al) at least one polyethylenically unsaturated monomer or oligomer capable of polymerization with energy curing with bl) said emulsified water phase in (meth)acrylic ester;

optionally adding pigment(s) and/or dye(s) to said energy curable coating or ink composition; and

optionally adding a UV initiator package to said energy curable coating or ink composition.