WO2016187363A1 - Composition d'émulsion pour des compositions d'encre durcissable par énergie, processus d'impression et procédé associés - Google Patents

Composition d'émulsion pour des compositions d'encre durcissable par énergie, processus d'impression et procédé associés Download PDF

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WO2016187363A1
WO2016187363A1 PCT/US2016/033162 US2016033162W WO2016187363A1 WO 2016187363 A1 WO2016187363 A1 WO 2016187363A1 US 2016033162 W US2016033162 W US 2016033162W WO 2016187363 A1 WO2016187363 A1 WO 2016187363A1
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water
alkoxylated
coating
ink
energy curable
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PCT/US2016/033162
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English (en)
Inventor
Joshua M. Rosenheck
John H. Larsen
Thomas J. STEWART
Leander H. Bauer
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Lubrizol Advanced Materials, Inc.
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Publication of WO2016187363A1 publication Critical patent/WO2016187363A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/023—Emulsion inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents

Definitions

  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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)).
  • an emulsion composition comprises
  • 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.
  • HLB hydrophilic lipophilic balance
  • an energy curable ink or coating composition comprising;
  • water-in-organic phase emulsion composition delivers 5 to 35% by weight water to the ink composition.
  • 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.
  • 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.
  • 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.
  • 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.
  • hydrocarbylene will refer to divalent hydrocarbon groups that may optionally include other heteroatoms such as O and N as defined for hydrocarbyl.
  • 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.
  • the present invention comprises an emulsion composition comprising:
  • 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
  • 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.
  • 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%.
  • 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.
  • 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.
  • emulsifier package comprising one or more and desirably two or more different emulsion stabilizing surfactants.
  • 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.
  • 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.
  • low molecular weight polyols such as a polyol of less than 300g/mole molecular weight, such as sorbitan
  • fatty acids 10 to 25 carbon atoms.
  • One such emulsifier is sorbitan mono-oleate.
  • 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.
  • 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.
  • 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.
  • 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.
  • mono-unsaturated monomer such as (meth)acrylate
  • hydrophobic groups e.g. C10-C20 alkyl groups
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 alkoxyl
  • 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.
  • 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 al
  • 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.
  • 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.
  • 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.
  • a promoter such as chlorine.
  • One or sometimes more than one maleic group succinic anhydride group after grafting
  • 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.
  • the amine is an alkanolamine, and in another embodiment the alkanolamine is a ⁇ , ⁇ -dialkylalkanolamine.
  • Useful amines include for example ethanolamine, diethanolamine, triethanolamine, and ⁇ , ⁇ -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.
  • 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.
  • 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-C 6 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the saccharide is first alkoxylated and then carboxylated.
  • the saccharide is first carboxylated then alkoxylated.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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%.
  • 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.
  • 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.
  • the water phase 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.
  • 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.
  • 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.
  • 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.
  • polymerizable 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • "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.
  • 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.
  • 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.
  • 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.
  • the term "cured ink” or “cured coating” refers to a curable ink or coating that has been polymerized.
  • the curable components of a curable ink or curable coating react upon curing to form a polymerized or cross-linked network.
  • the liquid or fluid curable ink or coating cross-links, polymerizes and/or hardens to form a film of cured ink or cured coating.
  • 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.
  • radiation 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.
  • 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.
  • 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.
  • resins including grinding resins and adhesion promoting resins
  • monomers such as by passing over a 3-roll mill, until a desired grind gauge specification 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.
  • let down varnishes that include a mixture of resins and optionally photo initiators
  • the letdown material can be mixed until homogenous.
  • 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.
  • 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
  • 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.
  • Other mono-ethylenically unsaturated monomers include C 8 -Ci5 styrene and substituted styrene, vinyl esters of vinyl alcohol with C 2 to Ci 8 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 C 8 -C 2 o alpha-beta unsaturated olefins.
  • 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,
  • 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.
  • 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.
  • 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
  • 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.
  • the formulations of the present invention may also include a hybrid component containing both vinyl ether and acrylate functionality.
  • 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-(
  • 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).
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • the ink optionally comprises a urethane acrylate oligomer.
  • a 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
  • 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.
  • 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.
  • epoxide based oligomers made from ring opening epoxide functionalized compounds with carboxylic acids, amine functional reactants, or polyols
  • 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.
  • 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.
  • EBECRYL series e.g. EBECRY L770, IRR467, 81, 84, 83, 80, 675, 800, 810, 812, 1657, 1810, IRR302, 450, 670, 830, 870, 1830, 1870
  • epoxy (meth)acrylates examples 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.
  • EBECRYL series e.g. EBECRYL 600, 860, 2958, 3411, 3600, 3605, 3700, 3701, 3703, 3702, 3708, RDX63182, 6040, etc.
  • 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.
  • the UV activated initiator belongs to the group of alpha-amino ketone based UV activated initiators.
  • the UV activated initiator comprises 2-methyl-l-[4- (methylthio)phenyl]-2-(4-mo holinyl)-l-propanone (IrgacureTM 907) or 2-benzyl-2- dimethylamino-l-(4-mo holinophenyl)-butanone-l (IrgacureTM 369) or mixtures thereof.
  • the UV activated initiator comprises an acylphosphine oxide, benzophenone, benzoates, and/or thioxanthone (preferably said UV activated initiator comprises (IrgacureTM 819) phenyl bis(2,4,6-trimethylbenzoyl)-phosphine oxide; (GenocureTM PBZ) 4-phenylbenzophenone; (GenocureTM BDMM) 2-benzyl-2- dimethylamino-4'mo holinobutyrophenone; (GenocureTM MBF) methylbenzoylformate; (GenocureTM ITX) thioxanthone; or (GenocureTM EPD) ethyl-4-
  • said UV activated initiator comprises an alpha-hydroxyketone (preferably said UV activated initiator comprises (IrgacureTM 184) (hydroxy cyclohexyl)(phenyl)keton; (IrgacureTM 1173) 2-hydroxy-2- methylpropiophenone; (IrgacureTM 2959) l-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2- methyl-1 -propane- 1 -one) or mixtures thereof.
  • said UV activated initiator comprises (IrgacureTM 184) (hydroxy cyclohexyl)(phenyl)keton; (IrgacureTM 1173) 2-hydroxy-2- methylpropiophenone; (IrgacureTM 2959) l-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2- methyl-1 -propane- 1 -one) or mixtures thereof.
  • GenocureTM is a trademark of Rahn AG in Zurich Switzerland while IrgacureTM is a trademark of BASF in Germany.
  • 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-
  • 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.
  • 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.
  • 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
  • defoamer component other additives, or a
  • the ink composition in one embodiment of the invention is a lithographic printing ink composition.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition d'émulsion comprenant de l'eau, une phase organique de monomère polymérisable, et un ensemble émulsifiant possédant un indice d'équilibre hydrophile-lipophile inférieur ou égal à 10, qui est utile en tant qu'additif pour revêtement ou encre durcissable par énergie. Un revêtement ou une encre (polymérisable) durcissable par énergie comprenant une émulsion de gouttelettes d'eau et une multitude de monomères polymérisables est utile en tant que revêtement ou encre. L'invention concerne également un processus de fabrication d'un revêtement ou d'une encre durcissable par énergie, consistant tout d'abord à fabriquer une émulsion d'eau dans au moins un monomère, puis à additionner cette émulsion (peu importe l'ordre) aux autres constituants de l'encre durcissable par énergie.
PCT/US2016/033162 2015-05-21 2016-05-19 Composition d'émulsion pour des compositions d'encre durcissable par énergie, processus d'impression et procédé associés WO2016187363A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109456500A (zh) * 2017-10-20 2019-03-12 山东大学 一种羧酸季铵盐型羟丙基磷酸酯钠沥青乳化剂及其制备方法
CN109594950A (zh) * 2019-01-08 2019-04-09 中国石油天然气股份有限公司 乳化沥青法水淹火驱油藏可燃封堵工艺

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4981517A (en) 1989-06-12 1991-01-01 Desanto Jr Ronald F Printing ink emulsion
US5378739A (en) 1991-11-01 1995-01-03 Ricoh Company, Ltd. Emulsion ink for use in stencil printing
US5389130A (en) 1993-06-25 1995-02-14 Milliken Research Corporation Printing ink emulsion having reduced VOC
US5876468A (en) 1996-09-05 1999-03-02 Lubrizol Adibis Holdings (Uk) Limited Detergents for hydrocarbon fuels
US6140392A (en) 1998-11-30 2000-10-31 Flint Ink Corporation Printing inks
US6348519B1 (en) 1995-05-02 2002-02-19 Ricoh Company, Ltd. Emulsion ink and printing method using emulsion ink
US6444716B1 (en) 2000-01-24 2002-09-03 The Procter & Gamble Company Foam materials and high internal phase emulsions made using oxidatively stable emulsifiers
US6797735B2 (en) 2000-07-05 2004-09-28 Nippon Shokubai Co., Ltd. Process for producing porous polymer
WO2005041987A1 (fr) * 2003-10-29 2005-05-12 Gentis, Inc. Emulsions polymerisables pour le genie tissulaire
US20060162237A1 (en) * 2002-12-13 2006-07-27 Mullay John J Fuel composition having a fuel, water, a high molecular weight emulsifier, and a surfactant including natural fats, non-ionic and ionic surfactants, co-surfactants, fatty acids and their amine salts, or combinations thereof
US7857899B2 (en) 2004-05-21 2010-12-28 The Lubrizol Corporation Emulsion composition and vehicle and ink compositions and printing process and method thereof
WO2013188746A2 (fr) * 2012-06-15 2013-12-19 Sun Chemical Corporation Encres offset lithographiques à teneur en eau et en charges

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4981517A (en) 1989-06-12 1991-01-01 Desanto Jr Ronald F Printing ink emulsion
US5378739A (en) 1991-11-01 1995-01-03 Ricoh Company, Ltd. Emulsion ink for use in stencil printing
US5389130A (en) 1993-06-25 1995-02-14 Milliken Research Corporation Printing ink emulsion having reduced VOC
US6348519B1 (en) 1995-05-02 2002-02-19 Ricoh Company, Ltd. Emulsion ink and printing method using emulsion ink
US5876468A (en) 1996-09-05 1999-03-02 Lubrizol Adibis Holdings (Uk) Limited Detergents for hydrocarbon fuels
US6140392A (en) 1998-11-30 2000-10-31 Flint Ink Corporation Printing inks
US6444716B1 (en) 2000-01-24 2002-09-03 The Procter & Gamble Company Foam materials and high internal phase emulsions made using oxidatively stable emulsifiers
US6797735B2 (en) 2000-07-05 2004-09-28 Nippon Shokubai Co., Ltd. Process for producing porous polymer
US20060162237A1 (en) * 2002-12-13 2006-07-27 Mullay John J Fuel composition having a fuel, water, a high molecular weight emulsifier, and a surfactant including natural fats, non-ionic and ionic surfactants, co-surfactants, fatty acids and their amine salts, or combinations thereof
WO2005041987A1 (fr) * 2003-10-29 2005-05-12 Gentis, Inc. Emulsions polymerisables pour le genie tissulaire
US7857899B2 (en) 2004-05-21 2010-12-28 The Lubrizol Corporation Emulsion composition and vehicle and ink compositions and printing process and method thereof
WO2013188746A2 (fr) * 2012-06-15 2013-12-19 Sun Chemical Corporation Encres offset lithographiques à teneur en eau et en charges

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109456500A (zh) * 2017-10-20 2019-03-12 山东大学 一种羧酸季铵盐型羟丙基磷酸酯钠沥青乳化剂及其制备方法
CN109456500B (zh) * 2017-10-20 2020-03-10 山东大学 一种羧酸季铵盐型羟丙基磷酸酯钠沥青乳化剂及其制备方法
CN109594950A (zh) * 2019-01-08 2019-04-09 中国石油天然气股份有限公司 乳化沥青法水淹火驱油藏可燃封堵工艺

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