Water-based inks for shrink and non-shrink polymer films

Abstract

To provide a water-based ink or the like suitable for printing on a shrinkable polymer film used for packaging and exhibiting improved resistance characteristics.SOLUTION: The present invention provides a process for making a printed shrinkable polymeric film substrate by applying an ink or overprint varnish comprising a self-crosslinking acrylic emulsion. The inks and overprint varnishes are resistant to abrasion, scratching, chemicals, moisture / water, and heat, and are also resistant to repeated bending and folding.SELECTED DRAWING: None

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 62 / 410,437, filed October 20, 2016, which is incorporated herein in its entirety.

[0002] FIELD OF THE INVENTION The present invention relates to water-based ink and coating compositions, including overprint varnishes. The compositions are particularly suitable for printing on shrinkable polymeric films, such as those used for shrink-wrap labels on food and pharmaceutical packaging. In some cases, the compositions can also be printed on non-shrinkable polymeric films. [Background technology]

[0003] Inks and coatings for shrinkable polymer films are typically solvent-based. However, there are problems associated with solvent-based inks and coatings. For example, solvents are generally volatile, and volatile solvents are falling out of favor for safety and environmental reasons. Furthermore, residual volatile solvents in the dried ink or coating often migrate from the ink or coating, causing product contamination when the substrate is used for packaging food, pharmaceuticals, or other products.

[0004] Currently available water-based inks for printing on shrinkable and other polymeric films generally contain polyurethane, acrylic, cellulose, and / or epoxy ester resins. Many of the currently available inks contain bisphenol-A (BPA), which is known to be toxic.

[0005] WO 2016 / 028850 discloses water-based inks and coatings containing self-crosslinking acrylic polymers suitable for printing on coated or uncoated paper and paperboard substrates, such as those used in food packaging.

[0006] EP 1493762 discloses polyurethane resins useful as binders in inks for printing on shrink sleeves. Inks containing the polyurethane resins, as well as methods for preparing and using the polyurethane resins, are also disclosed.

[0007] JP 2004-238578 describes an ink containing a polyurethane resin and a cellulose resin, which ink is suitable for printing on shrink label olefin-based films.

[0008] JP 2011-148302 discloses a shrink label printed on at least one surface with an ink or coating containing a urethane acrylic resin and an acrylic resin, or containing a urethane acrylic resin, an acrylic resin and a cellulose-based resin.

[0009] JP 2011-153172 describes a printing ink for labels, which contains a cellulose resin, an acrylic resin and an energy-curable monomer.

[0010] US 2006 / 0246243 and WO 2005 / 005507 disclose polyurethane resins and inks containing the resins suitable for printing on shrink sleeves.

[0011] US 2010 / 0212830 discloses a solventless thermosetting composition comprising at least one (iso)cyanate, a nitrogen-based latent curing agent, and optionally an epoxy resin and a modifier. The composition is used for bonding, casting, sealing, and coating substrates, particularly electronic components.

[0012] US 2009 / 0297796 discloses water-based screen printing inks that may be suitable for other printing methods, primarily containing specialized pigments and crosslinkers.

[0013] US 7,807,739 discloses an aqueous composition for coating a substrate, the composition comprising a crosslinkable polymer, an acrylic polymer, and an epoxy silane.

[0014] US 2013 / 0309516 relates to a coating composition having an acrylic polymer with a low glass transition temperature, which contains crosslinkable functional groups and a crosslinking agent.

[0015] JP 3301267 relates to a water-based ink containing a resin for use on corrugated board.

[0016] CN 101812255 relates to inks containing acrylic resins for use on high temperature resistant cartons.

[0017] JP H04-225081 discloses an aqueous printing ink composition containing a resin acid salt, water, a colorant, and an organometallic chelate compound. The ink is useful for printing on paper cartons.

[0018] There remains a need for water-based inks, coatings, and varnishes that are suitable for printing on shrinkable polymeric films used in packaging and that exhibit improved resistance properties. Summary of the Invention

[0019] The present invention provides ink and coating compositions and overprint varnishes containing a self-crosslinking acrylic polymer, a coalescing agent, and at least one silicone emulsion. The ink and coating compositions are particularly suitable for printing on shrinkable polymer films, such as those used in shrink-wrap labels. The compositions may also be used on non-shrinkable polymer films. The printed ink and coating compositions exhibit good adhesion and resistance properties.

[0020] In certain aspects, the present invention provides a process for printing on a polymeric substrate, comprising: a) i. at least one self-crosslinking acrylic polymer; ii. at least one coalescing agent; iii. at least one silicone emulsion, and iv.Water Including, v. The self-crosslinking acrylic polymer has a glass transition temperature above 0°C; Providing an ink or coating composition; b) applying the ink or coating composition of a) to a polymeric substrate; and c) drying the ink or coating composition on the polymer substrate; and The present invention provides a process including:

[0021] In another aspect, the present invention provides a printed polymeric substrate made by the process of the present invention.

[0022] In one embodiment, the printed polymer substrate is a shrinkable polymer film.

[0023] In one embodiment, the present invention provides an article comprising a printed polymeric substrate made by the process of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0024] It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the subject matter claimed.

[0025] The headings are used for organizational purposes only and are not intended to limit the invention in any way.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the inventor belongs. All patents, patent applications, published applications and publications, websites, and other publications mentioned throughout this disclosure are incorporated by reference in their entirety for all purposes unless otherwise stated.

[0027] It has been found that an ink or overprint varnish containing a self-crosslinked acrylic polymer, a coalescing agent, and at least one silicone emulsion can exhibit good adhesion on a shrinkable polymer film along with the required resistance properties if the self-crosslinked acrylic polymer has a glass transition temperature (Tg) above 0° C. Advantageously, the self-crosslinked acrylic polymer has a Tg of about 20° C. to about 70° C.

[0028] definition In this application, the use of the singular includes the plural unless specifically stated otherwise. As used herein, the singular forms "a," "an," and "the" are intended to include the plural as well, unless the context clearly dictates otherwise.

[0029] In this application, the use of "or" means "and / or" unless stated otherwise.

[0030] As used herein, the terms "comprises" and / or "comprising" specify the presence of stated features, integers, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. Furthermore, to the extent that the terms "includes," "having," "has," "with," "composed," "comprised," or variations thereof are used in either the detailed description or the claims, such terms are intended to include in a manner similar to the term "comprising."

[0031] As used herein, ranges and amounts may be expressed as "about" a particular value or range. "About" is intended to include the exact amount. Thus, "about 5 percent" also means "about 5 percent" and "5 percent." "About" means within typical experimental error for the intended use or purpose.

[0032] As used herein, the terms "ink and coating composition(s)", "ink(s) and overprint varnish(s)", "overprint varnish(s)", "ink(s)", "varnish(s)", "coating composition(s)", "coating(s)", and the like, when referring to the present invention, all refer to components of the present invention.

[0033] As used herein, the term "article(s)" refers to a substrate or an article of manufacture. Examples of articles include, but are not limited to, substrates such as paper, plastic, plastic or polymer film, glass, ceramic, metal, composite material, publications (e.g., booklets), labels, and articles of manufacture such as packaging materials (e.g., flexible shrinkable and non-shrinkable polymeric films, and cardboard sheets or corrugated cardboard), containers (e.g., bottles, cans), polyolefins (e.g., polyethylene or polypropylene), polyesters (e.g., polyethylene terephthalate), metallized foils (e.g., laminated aluminum foil), metallized polyesters, metal containers, etc.

[0034] Throughout this disclosure, all parts and percentages are by weight (wt% or mass% based on total weight) and all temperatures are in °C unless otherwise indicated.

[0035] Inks and overprint varnishes and processes for printing on flexible polymeric films Self-crosslinking polymers contain self-reactive functionality and therefore do not inherently require the use of a separate co-reactant. Self-crosslinking polymers are usually in the form of aqueous dispersions or emulsions and are typically the product of at least two monomers reacting with each other. For example, such polymers may contain both carbonyl and amine functional groups.

[0036] There are several mechanisms by which polymers can self-crosslink. One mechanism is through the use of phase-separated polymers, such as core-shell polymers. The shell polymer is hydrophilic, while the core polymer is hydrophobic. The hydrophilic shell maintains the dispersion, while the hydrophobic core provides reactive sites for crosslinking.

[0037] Typically, in self-crosslinking acrylic polymer chemistry, polymers containing ketone groups crosslink at room temperature when combined with carbonyl-reactive di- or polyfunctional compounds. One example of these reactive compounds is a bishydrazide. Such self-crosslinking acrylic emulsions are provided as one-component products.

[0038] Depending on the type of acrylic, the self-crosslinking reaction may be initiated by evaporation of water during drying, a change in the pH of the vehicle, or curing at elevated temperatures where the self-crosslinking reaction occurs more quickly or the reactive groups are unblocked.

[0039] An example of self-crosslinking is given in GB-A-2045768, which describes a dispersion based on the emulsion polymerization product of a monomer mixture containing primarily lower alkyl (meth)acrylate monomers, small amounts of (meth)acrylic acid, and glycidyl (meth)acrylate.

[0040] More recently, polymer particles with a continuous gradient morphology have been developed. In this mechanism, ketone groups are concentrated in the low Tg region of the polymer particle. Self-crosslinked polymers are prepared by emulsion polymerization. The use of gradient morphology requires little or no coalescing solvent and allows for minimum film formation temperatures of less than 5°C while maintaining the desired resistivity properties.

[0041] Another method for preparing self-crosslinking acrylic dispersions is to not only perform emulsion polymerization but also include in the mixture an acrylic oligomer containing reactive and / or co-reactive groups, in which the reactive oligomer is grafted onto the gradient morphology core particles.

[0042] The self-crosslinking acrylic polymer may, for example, comprise a binder selected from the group consisting of styrene / acrylic acid ester copolymers, styrene / acrylic acid ester copolymers containing acrylamide groups, and copolymers preferably based on acrylonitrile, methacrylamide and acrylic acid esters.

[0043] Preferably, the self-crosslinking acrylic polymer is formed from reactive monomers comprising at least one monomer selected from methyl acrylic acid (MAA), methyl methacrylate (MMA), butyl acrylate, butyl methacrylate, styrene, and methylstyrene. Advantageously, the self-crosslinking polymer is a styrene / acrylic ester copolymer.

[0044] In a preferred embodiment of the present invention, self-crosslinking polymers are produced via carbonyl / amine reaction.Advantageously, acrylates with pendant N-methylol groups are used, such as N-isobutoxymethylol acrylamide (NiBMA).Commercially available acrylates formed from such monomers include, but are not limited to, Alberdingk AC2714VP, Synthomer AM00035, Organikkimyan Orgal PO86V, and DSM Neocryl XK12 and XK14.

[0045] The Tg of an acrylic polymer is relative to the acrylic polymer before self-crosslinking. A higher Tg prevents premature gelation of the acrylic polymer. Typically, a self-crosslinked acrylic polymer has a Tg above 0°C. Preferably, the self-crosslinked acrylic polymer may have a Tg of about 20 to 70°C. For example, the self-crosslinked acrylic polymer may have a Tg of about 20 to about 65°C; or about 20 to about 60°C; or about 20 to about 55°C; or about 20 to about 50°C; or about 20 to about 45°C; or about 20 to about 40°C; or about 20 to about 35°C; or about 20 to about 30°C; or about 20 to about 25°C; or about 25 to about 70°C; or about 25°C to about 65°C; or about 25°C to about 60°C; or about 25°C to about 55°C; or about 25°C to about 50°C; or about 25°C to about 45°C; or about 25°C to about 40°C; or about 25°C to about 35°C; or about 25°C to about 30°C; or about 30°C to about 70°C; or about 30°C to about 65°C; or about 30°C to about 60°C; or about 30°C to about 5 5°C; or about 30°C to about 50°C; or about 30°C to about 45°C; or about 30°C to about 40°C; or about 30°C to about 35°C; or about 35°C to about 70°C; or about 35°C to about 65°C; or about 35°C to about 60°C; or about 35°C to about 55°C; or about 35°C to about 50°C; or about 35°C to about 45°C; or about 35°C to about 40°C; or It may have a Tg of about 40°C to about 70°C, or about 40°C to about 65°C, or about 40°C to about 60°C, or about 40°C to about 55°C, or about 40°C to about 50°C, or about 40°C to about 45°C, or about 45°C to about 70°C, or about 45°C to about 65°C, or about 45°C to about 60°C, or about 45°C to about 55°C, or about 45°C to about 50°C. Advantageously, the self-crosslinking acrylic polymer has a Tg of about 40°C to 60°C.

[0046] Typically, the inks and overprint varnishes of the present invention comprise about 15 wt% to 70 wt% acrylic polymer (self-crosslinking acrylic polymer plus non-self-crosslinking acrylic polymer), based on the total weight of the ink or overprint varnish composition. For example, the inks and overprint varnishes of the present invention may contain, based on the total weight of the ink or overprint varnish composition, from about 15 wt% to about 65 wt%; or from about 15 wt% to about 60 wt%; or from about 15 wt% to about 55 wt%; or from about 15 wt% to about 50 wt%; or from about 15 wt% to about 45 wt%; or from about 15 wt% to about 40 wt%; or from about 15 wt% to about 30 wt%; or from about 15 wt% to about 25 wt%; or from about 15 wt% to about 20 wt%; or from about 20 wt% to about 70 wt%; or from about 20 wt% to about 65 wt%; or from about 20 wt% to about 60 wt%; or from about 20 wt% to about 55 wt% %; or about 20 wt% to about 50 wt%; or about 20 wt% to about 45 wt%; or about 20 wt% to about 40 wt%; or about 20 wt% to about 35 wt%; or about 20 wt% to about 30 wt%; or about 20 wt% to about 25 wt%; or about 25 wt% to about 70 wt%; or about 25 wt% to about 65 wt%; or about 25 wt% to about 60 wt%; or about 25 wt% to about 55 wt%; or about 25 wt% to about 50 wt%; or about 25 wt% to about 45 wt%; or about 25 wt% to about 40 wt%; or about 25 wt% to about 35 wt%; or about 25 wt% to about 30 wt% acrylic polymer.

[0047] Based on the total weight of the acrylic polymer (i.e., based on the total weight of [self-crosslinking] + [non-self-crosslinking]), about 50 wt% to 85 wt% of the acrylic polymer is self-crosslinking. For example, the self-crosslinking acrylic polymer may be 50 wt% to about 80 wt%, or about 50 wt% to about 75 wt%, or about 50 wt% to about 70 wt%, or about 50 wt% to about 65 wt%, or about 50 wt% to about 60 wt%, or about 50 wt% to about 55 wt%, or about 55 wt% to about 85 wt%, or about 55 wt% to about 80 wt%, based on the total weight of the acrylic polymer. t%; or about 55 wt% to about 75 wt%; or about 55 wt% to about 70 wt%; or about 55 wt% to about 65 wt%; or about 55 wt% to about 60 wt%; or about 60 wt% to about 85 wt%; or about 60 wt% to about 80 wt%; or about 60 wt% to about 75 wt%; or about 60 wt% to about 70 wt%; or about 60 wt% to about 65 wt%.

[0048] The inks and overprint varnishes of the present invention typically contain about 5 wt% to 60 wt% of the self-crosslinking acrylic polymer, based on the total weight of the ink or varnish composition. For example, the ink or varnish may contain about 5 wt% to about 55 wt%, or about 5 wt% to about 50 wt%, or about 5 wt% to about 45 wt%, or about 5 wt% to about 40 wt%, or about 5 wt% to about 35 wt%, or about 5 wt% to about 30 wt%, or about 5 wt% to about 25 wt%, or about 5 wt% to about 20 wt%, or about 5 wt% to about 15 wt%, or about 5 wt% to about 10 wt%, or about 10 ... about 60wt%; or about 10wt% to about 55wt%; or about 10wt% to about 50wt%; or about 10wt% to about 45wt%; or about 10wt% to about 40wt%; or about 10wt% to about 35wt%; or about 10wt% to about 30wt%; or about 10wt% to about 25wt%; or about 10wt% to about 20wt%; or about 10wt% to about 15wt%; or about 15wt% to about 60wt%; or about 15wt% to about 55wt%; or about 15wt % to about 50wt%; or about 15wt% to about 45wt%; or about 15wt% to about 40wt%; or about 15wt% to about 35wt%; or about 15wt% to about 30wt%; or about 15wt% to about 25wt%; or about 15wt% to about 20wt%; or about 20wt% to about 60wt%; or about 20wt% to about 55wt%; or about 20wt% to about 50wt%; or about 20wt% to about 45wt%; or about 20wt% to about 40wt%; or about 2 or about 25 wt% to about 45 wt%; or about 25 wt% to about 40 wt%; or about 25 wt% to about 35 wt%; or about 25 wt% to about 30 wt%; or about 20 wt% to about 25 wt%; or about 25 wt% to about 60 wt%; or about 25 wt% to about 55 wt%; or about 25 wt% to about 50 wt%; or about 25 wt% to about 45 wt%; or about 25 wt% to about 40 wt%; or about 25 wt% to about 35 wt%; or about 25 wt% to about 30 wt%; or about 25 wt% to about 20 wt% of the self-crosslinking acrylic polymer.

[0049] The inks and overprint varnishes of the present invention contain a coalescing agent (coalescing aid). The coalescing agent optimizes film formation. The coalescing agent functions as a temporary plasticizer for the polymer particles and lowers the minimum film formation temperature (MFFT) of the polymer emulsion. Common coalescing agents include solvents such as ester alcohols, esters, and glycol ethers. Examples of such solvent coalescing agents include, but are not limited to, Eastman Texanol ester alcohols, Eastman EEH solvent, and Eastman DB solvent. Low Tg acrylic emulsions may also be used as coalescing agents. Advantageously, the coalescing agents used in the present invention are acrylic emulsions typically having a Tg below 20°C, preferably below 0°C. Suitable coalescing agents include, but are not limited to, Dow Lucidene 605, DSM NeoCryl A-1125, NeoCryl A-2095, BASF Joncryl 8052, and BASF Joncryl ECO 2124.

[0050] Typically, the inks and overprint varnishes of the present invention contain from about 2 wt% to about 20 wt%, preferably from about 5 wt% to about 15 wt%, of coalescent, based on the total weight of the ink or varnish composition. For example, the inks and overprint varnishes may contain from about 2 wt% to about 15 wt%, or from about 2 wt% to about 10 wt%, or from about 2 wt% to about 5 wt%, or from about 5 wt% to about 20 wt%, or from about 5 wt% to about 15 wt%, or from about 5 wt% to about 10 wt% of coalescent.

[0051] The inks and overprint varnishes of the present invention also contain a silicone emulsion. The addition of a silicone emulsion to the formulation helps improve the overall resistance properties. Examples of suitable silicone emulsions include, but are not limited to, DC 84, DC 51, and DC 209S, available from Dow Corning, as well as Worleeadd 350. These silicones are high molecular weight polydimethylsiloxane emulsions and contain reactive silanol groups. Alternatively, a blocked reactive silicone emulsion may be used.

[0052] Typically, the inks and overprint varnishes of the present invention contain from about 0.2 wt % to about 3 wt %, and preferably from about 1 wt % to about 2 wt %, of the silicone emulsion, based on the total weight of the ink or varnish composition. For example, the inks and overprint varnishes may contain the silicone emulsion in an amount of from about 0.2 wt% to about 2.5 wt%; or from about 0.2 wt% to about 2 wt%; or from about 0.2 wt% to about 1.5 wt%; or from about 0.2 wt% to about 1 wt%; or from about 0.2 wt% to about 0.5 wt%; or from about 0.5 wt% to about 3 wt%; or from about 0.5 wt% to about 2.5 wt%; or from about 0.5 wt% to about 1.5 wt%; or from about 0.5 wt% to about 1 wt%; or from about 1 wt% to about 3 wt%; or from about 1 wt% to about 2.5 wt%; or from about 1 wt% to about 2 wt%; or from about 1 wt% to about 1.5 wt%.

[0053] The inks and overprint varnishes of the present invention contain water. The water may be added directly or may be included in the composition as part of an acrylic or silicone emulsion. Typically, the inks and overprint varnishes of the present invention contain about 25 wt % to about 50 wt % water, based on the total weight of the ink or overprint varnish. For example, the inks and overprint varnishes of the present invention may contain water in an amount of from about 25 wt% to about 45 wt%; or from about 25 wt% to about 40 wt%; or from about 25 wt% to about 35 wt%; or from about 25 wt% to about 30 wt%; or from about 30 wt% to about 50 wt%; or from about 30 wt% to about 45 wt%; or from about 30 wt% to about 40 wt%; or from about 30 wt% to about 35 wt%; or from about 35 wt% to about 50 wt%; or from about 35 wt% to about 45 wt%; or from about 35 wt% to about 40 wt%; or from about 40 wt% to about 50 wt%; or from about 40 wt% to about 45 wt%; or from about 45 wt% to about 50 wt%.

[0054] The inks and overprint varnishes of the present invention optionally further comprise one or more colorants. Such colorants include pigments and / or dyes. Examples of suitable organic or inorganic pigments include carbon black, zinc oxide, titanium dioxide, phthalocyanines, anthraquinones, perylenes, carbazoles, monoazos and diazobenzimidazoles, rhodamines, indigoids, quinacridones, diazopyranthrones, dinitranilines, pyrazoles, diazopyranthrones, dinityanilines, pyrazoles, dianisidines, pyranthrones, tetrachloroisoindolines, dioxazines, monoazoacrylides, and anthrapyrimidines. Dyes include, but are not limited to, azo dyes, anthraquinone dyes, xanthene dyes, azine dyes, combinations thereof, and the like.

[0055] When present, organic pigments and dyes are typically present in an amount of about 0.1% to about 7% (w / w) based on the total weight of the ink or overprint varnish. For example, organic pigments and dyes may be present in an amount of 0.1% to 6.5%, or 0.1% to 6%, or 0.1% to 5.5%, or 0.1% to 5%, or 0.1% to 4.5%, or 0.1% to 4%, or 0.1% to 3.5%, or 0.1% to 3%, or 0.1% to 2.5%, or 0.1% to 2%, or 0.1% to 1.5%, or 0.1% to 1%, or 0.1% to 0.5%, or 0.5% to 7%, or 0.5% to 6.5%, or 0.5% to 6%, or 0.5% to 5.5%, or 0.5% to 5%. or 0.5% to 4.5%; or 0.5% to 4%; or 0.5% to 3.5%; or 0.5% to 3%; or 0.5% to 2.5%; or 0.5% to 2%; or 0.5% to 1.5%; or 0.5% to 1%; or 1% to 7%; or 1% to 6.5%; or 1% to 6%; or 1% to 5.5%; or 1% to 5%; or 1% to 4.5%; or 1% to 4%; or 1% to 3.5%; or 1% to 3%; or 1% to 2.5%; or 1% to 2%; or 1% to 1.5%.

[0056] When present, inorganic pigments are typically present in an amount of 1% to 40% (w / w) based on the total weight of the ink or overprint varnish. For example, the inorganic pigment may be present in an amount of 1% to 35%, or 1% to 30%, or 1% to 25%, or 1% to 20%, or 1% to 15%, or about 1% to about 10%, or about 1% to about 5%, or 5% to 40%, or 5% to 35%, or 5% to 30%, or 5% to 25%, or 5% to 20%, or 5% to 15%, or about 5% to about 10%, or about 10% to about 40%. or 10% to 35%; or 10% to 30%; or 10% to 25%; or 10% to 20%; or 10% to 15%; or 15% to 40%; or 15% to 35%; or 15% to 30%; or 15% to 25%; or 15% to 20%; or 20% to 40%; or 20% to 35%; or 20% to 30%; or 20% to 25%.

[0057] The inks and overprint varnishes of the present invention may optionally contain one or more other additives, including, but not limited to, humectants, alcohols, polyethylene wax emulsions, wax dispersions, antifoaming agents, ammonia, defoamers, dispersants, stabilizers, silicones, rheology modifiers, plasticizers, and the like.

[0058] Examples of such additives include isopropanol and n-propanol, polyethylene wax emulsions such as Munzing Lubraprint 2036 and Byk Aquacer 531, wax dispersions such as Munzing Lubraprint 499, Keim Ultralube D816 and Crayvallac WW1001, antifoaming agents such as Byk 023 and Evonik Tegofoamex 1488, wetting agents such as Evonik TegoWet 500, Byk Dynwet 800 and Air Products Surfynol AD01, biocides such as WR-0268 available from Thor Chemicals, and dispersing agents such as Byk Disperbyk 190.

[0059] When present, such additives are typically present in an amount of about 0.1 wt% to about 5 wt%, based on the total weight of the ink or overprint varnish composition. For example, the additive may be present in an amount of about 0.1 wt% to about 4.5 wt%, or about 0.1 wt% to about 4 wt%, or about 0.1 wt% to about 3.5 wt%, or about 0.1 wt% to about 3 wt%, or about 0.1 wt% to about 2.5 wt%, or about 0.1 wt% to about 2 wt%, or about 0.1 wt% to about 1.5 wt%, or about 0.1 wt% to about 1 wt%, or about 0.1 wt% to about 0.5 wt%. Or it may be present in an amount of about 0.5 wt% to about 5 wt%; or about 0.5 wt% to about 4.5 wt%; or about 0.5 wt% to about 4 wt%; or about 0.5 wt% to about 3.5 wt%; or about 0.5 wt% to about 3 wt%; or about 0.5 wt% to about 2.5 wt%; or about 0.5 wt% to about 2 wt%; or about 0.5 wt% to about 1.5 wt%; or about 0.5 wt% to about 1 wt%.

[0060] The inks and overprint varnishes of the present invention are preferably substantially free of bisphenol-A (BPA) and, advantageously, are preferably free of epoxy esters. BPA and epoxy esters have been associated with toxicity. Furthermore, when the ink or overprint varnish is applied to food or pharmaceutical packaging, any BPA and / or epoxy esters present may migrate into the product and cause contamination.

[0061] When present, the inks and overprint varnishes of the present invention contain 300 ppm or less of BPA. BPA may be present in amounts less than 250 ppm; or less than 200 ppm; or less than 150 ppm; or less than 100 ppm. Advantageously, the inks and overprint varnishes of the present invention are BPA-free.

[0062] When present, the inks and overprint varnishes of the present invention contain 30 wt% or less of BPA, based on the total weight of the ink or overprint varnish composition. For example, the inks and overprint varnishes of the present invention may contain less than 25 wt%, or less than 20 wt%, or less than 15 wt%, or less than 10 wt%, or less than 5 wt%, or less than 1 wt% of epoxy esters. Advantageously, the inks and overprint varnishes of the present invention are free of epoxy esters.

[0063] The inks and overprint varnishes of the present invention may be used for any type of printing, but are advantageously gravure or flexographic printing inks or coating compositions. The inks and overprint varnishes of the present invention are preferably formulated for use with shrinkable polymeric film substrates, but may also be used with non-shrinkable polymeric film substrates. While the most common substrate used in heat-shrinking processes is polyethylene terephthalate (PET), the inks and overprint varnishes of the present invention are equally suitable for other flexible polymeric films. Examples of other polymeric films include oriented polypropylene (OPP), polyvinyl chloride (PVC), oriented polystyrene (OPS), and polylactic acid film (PLA). Polymeric films can be used, for example, for a wide range of shrinkable sleeve products. These shrink-grade films typically activate at temperatures between 55°C and 65°C and may shrink up to 75% in the machine direction. It should be noted that the inks and overprint varnishes of the present invention are also suitable for use with films that activate outside the 55°C to 65°C range, or that are not heat-activated at all.

[0064] The inks and overprint varnishes of the present invention are preferably approved by regulatory agencies for indirect food contact situations. All materials used in the inks and overprint varnishes are preferably successfully tested for migration potential and approved by the Toxic Substances Control Act (TSCA) and the Food and Drug Administration (FDA).

[0065] In one embodiment, the present invention relates to a water-based acrylic ink for printing onto heat-shrinkable polymer films that can be shrunk by hot water / steam, in contrast to prior art water-based inks that can only be shrunk by infrared radiation. The water-based ink of the present invention is preferably printed by flexography or gravure printing, but is not limited to these two printing methods. The ink is similar to that described in WO 2016 / 028850, but is specially formulated for flexography or gravure printing, especially onto shrinkable polymer films.

[0066] In another embodiment, the inks and overprint varnishes of the present invention can be used on milk / juice sachets made from clear, non-shrinking polymeric film. Most often, the film is polypropylene, but other films can also be used, including, but not limited to, polyethylene film (PE), PET, and aluminum foil and various flexible laminate structures.

[0067] When the composition is used as an overprint varnish, it is usually transparent and uncolored. The overprint varnish is used to protect the previously printed ink, providing enhanced abrasion resistance and chemical resistance. That is, the previously printed ink itself tends to be rubbed off, removed by chemicals, or damaged by heat. The overprint varnish is abrasion-resistant, chemical-resistant, and provides a protective layer that is resistant to heat, so that the print remains intact.

[0068] The present invention is further illustrated by the following examples.

[0069] Example The following examples illustrate certain embodiments of the present invention and are not intended to, and should not be construed as, limiting its scope in any way.

[0070] Test Method printing Print samples were made using a wire-wound K-bar (9 μm) on various shrink film substrates, typically available from Gunze, Klockner, and Pentaplast. The shrink film substrates used were PVC, polyester, PET, glycol-modified polyester, PETG, OPS, and polypropylene. Prints were allowed to dry under ambient conditions (25°C and 50% relative humidity (RH)).

[0071] Hot water test The ink was applied to a shrink film substrate (approximately 300 mm long by 150 mm wide) and the film was confirmed to shrink transversely to the printing direction. The print was half-immersed in a water bath set at 95°C for 15 minutes. The shrunken print was removed from the water, flattened, and dried on a paper cloth. The test prints were evaluated for adhesion, scratch resistance, and wrinkle resistance.

[0072] Tape Adhesion Test Scotch 610 adhesive tape was applied to the print sample. The tape was manually removed by pulling slowly, followed by a fast pull, perpendicular to the surface of the print. The tape was removed immediately after application. Adhesion was rated on a scale of 1 to 5 or 1 to 10, as shown in each results table.

[0073] Adhesion was scored on a scale of 1 to 5 as follows: 1 = Over 80% ink removal 2 = 60% to 80% ink removal 3 = 40% to 60% ink peeling 4 = 10% to 40% ink peeling 5 = Less than 10% ink peeling

[0074] Adhesion was scored on a scale of 1 to 10 as follows: 1 = 90% or more ink removal 2 = 80% ink removal 3 = 70% ink removal 4 = 60% ink removal 5 = 50% ink removal 6 = 40% ink removal 7 = 30% ink removal 8 = 20% ink removal 9=10% ink removal 10 = No ink peeling

[0075] Scratch resistance The print samples were placed printed side up on a hard surface and scratched with the back of the index fingernail. The prints were rated for the level of ink removal using a scale of 1 to 5 as described above in the Adhesion Test.

[0076] Wrinkle test The print sample was gripped with a thumb and index finger on either side of the print, held approximately 1 inch apart, and vigorously rotated for 50 cycles by twisting the edges in opposite directions so that the printed sides faced each other, simulating repeated flexing of the print. The level of ink removal and / or damage to the print surface was assessed on a scale of 1 to 5 as described above in the adhesion test.

[0077] Curl test Using a sharp knife, cross cuts were made into the prints, approximately 5 cm across, and the amount of curl was assessed. Curl was rated on a scale of 1 to 5 as follows: 1 = Severe curl 2 = Moderate to severe curl 3 = Medium curl 4 = Light to medium curl 5 = Mild curl

[0078] Environmental Product Drop Test A drop of liquid product (glucose or cola) was placed on the print and left at room temperature for 24 hours, after which the product was wiped off with a damp paper cloth and the print damage was rated on a scale of 1 to 5 as described above in the adhesion test.

[0079] 30℃ product drop test A drop of liquid product (glucose or cola) was placed on the print surface. The print was placed in an oven set at 30°C for 24 hours. The product was then wiped off with a damp paper cloth and the print damage was rated on a scale of 1 to 5 as described above in the adhesion test.

[0080] Product immersion test A piece of printed sample was immersed in a jar of liquid product (glucose or cola) for 24 hours. The printed sample was then removed from the jar and rinsed with water to remove the product. The sample was rated for damage on a scale of 1 to 5 as described above for tape adhesion.

[0081] blocking Printed samples were placed face-to-face (AA) or face-to-back (AB) in a Specac Blocking Tester and subjected to 10 MPa of pressure for 10 minutes at room temperature. Samples were visually inspected for the absence of blocking and scored on a scale of 1 to 5 or 1 to 10, as shown in each results table. Blocking is the transfer of ink from one substrate to another. Severe blocking means that 90% or more of the ink has transferred from one substrate to the other, while mild blocking means that 10% or less of the ink has transferred from one substrate to the other, preferably no ink has transferred.

[0082] Scoring on a scale of 1 to 5, blocking scores were as follows: 1 = severe blocking 2 = moderate to severe blocking 3 = Moderate blocking 4 = mild to moderate blocking 5 = mild blocking

[0083] Scoring on a scale of 1 to 10, blocking scores were as follows: 1 = 90% or more ink transfer 2 = 80% ink transfer 3 = 70% ink transfer 4 = 60% ink transfer 5 = 50% ink transfer 6 = 40% ink transfer 7=30% ink transfer 8=20% ink transfer 9=10% ink transfer 10 = No ink transfer

[0084] Folding test The print sample was folded and the fold was rubbed repeatedly between the fingers for 20 seconds. The folded print was rated for print damage on a scale of 1 to 5 as described above for the Adhesion Test.

[0085] Wet friction resistance The prints were allowed to air dry for 7 days. Using a Satra Rub Tester (Model STM 461), a felt pad (25 mm OD) was saturated with the specified reagents (water, milk, juice, Saniglide line lubricant, hydrogen peroxide (H2O2)) and rolled over the surface of the print with a 1.8 kg load. Results were reported as the number of rubs required for complete ink removal, with higher numbers indicating better rub resistance. When testing line lubricant and hydrogen peroxide, the liquid was allowed to sit on the printed substrate for 3 minutes, followed by the rub test as described above.

[0086] Cooling wet friction resistance The dried prints were placed in a bucket of water and allowed to cool for 16-24 hours, after which they were tested using the Satra rub test with water as the test reagent.

[0087] Wet and wet friction test The dried prints were stored at 50°C and 30% relative humidity for 16-24 hours, after which they were tested using the Satra rub test with water as the reagent.

[0088] Hand wet rub test The dried print was grasped with a thumb and index finger on either side of the print, held approximately 1 inch apart, printed sides facing each other, and vigorously rotated under running water for 50 cycles to simulate repeated flexing of the print. The level of ink / varnish peeling was rated on a scale of 1 to 10, with 10 being excellent and 1 being poor, as follows: 1 = 90% or more ink removal 2 = 80% ink removal 3 = 70% ink removal 4 = 60% ink removal 5 = 50% ink removal 6 = 40% ink removal 7 = 30% ink removal 8 = 20% ink removal 9=10% ink removal 10 = No ink peeling

[0089] Sliding test Davenport friction coefficient The static and kinetic coefficient of friction (CoF) was evaluated according to ASTM D1894 using a Davenport CoF tester.

[0090] Ink and / or overprint varnish were printed onto PE / OPP / PET / PVC or OPS film substrates. Print samples measuring at least 254 cm long and 8 cm wide were prepared. One sample was attached to the test bench with adhesive tape, ensuring it was flat, smooth, and held without stretching. Another sample was attached to the back of the sled with adhesive tape, ensuring it was not touching the printed surface. A string was attached to the sled and gently placed on the left edge of the print on the test bench so that it was centered between the two L-shaped marks and its leading edge was aligned with the right edge of the marks. A small amount of slack was left in the string. The machine was started and the sled was pulled along the test bench at a speed of 15 cm / min. When measuring static CoF, the digital display was immediately reset upon start-up to ensure no erroneous readings were registered. CoF was measured on face-to-face (AA) or face-to-back (AB) samples.

[0091] Static friction is the force that holds a stationary object back until the point at which it begins to move. Thus, static CoF relates to the force that restricts the movement of a stationary object on a relatively smooth, flat surface. Static CoF is recorded as the final (maximum) reading on a digital display, or as the highest force recorded early in the recording device's tracking.

[0092] Kinetic friction is the force that resists regular motion of an object over a surface. Therefore, kinetic CoF is the average force required to keep a sled moving along the test platform. The reading from a CoF tester is the average of the measurements taken to keep the sled moving (either averaging the highest and lowest readings, or taking a tracking average if using a digital recording device).

[0093] The static and kinetic coefficients of friction (CoF) are calculated as follows: CoF = (force in grams) / (weight of sled in grams) Where: Force in grams = Measurement x 10 if sensitivity is set to X1, or Force in grams = Measurement x 2 if sensitivity is set to X5.

[0094] Printability (flexographic printing) Printability was evaluated in the production of prints. Prints were judged for defects in either solid or toned areas. Evaluation was on a gray scale, with 10 = excellent and 1 = poor. Only prints that passed as commercially acceptable were considered suitable for the process of the present invention. The portion of ink coverage that was not printed on the substrate was evaluated (percent ink not taken). The scoring scale was as follows: 1 = Poor - 90% or more of the ink does not adhere 2 = 80% of the ink does not adhere 3 = 70% of the ink does not adhere 4 = 60% of the ink does not adhere 5 = 50% of the ink does not adhere 6 = Less than 10% ink loss - commercially acceptable 7 = Commercially acceptable - some imperfections may occur 8=Slight imperfections 9 = Very slight imperfections 10 = Excellent - No defects

[0095] Cleanability Cleanability is a measure of how easily the ink can be removed from equipment after a print run on a commercial press. Cleanability is evaluated by press operators and rated as either acceptable or unacceptable. Only inks that do not cause any excessive downtime to normal production are considered acceptable.

[0096] resolubilability Redissolvability is a measure of how easily the ink remains redissolvable in itself during a press run. If the ink is not sufficiently redissolvable in itself, printing problems will occur due to residual ink drying on the press. Only inks that are sufficiently redissolvable so as not to cause excessive printing problems were considered acceptable.

[0097] Examples 1 and 2. Water-based white ink and water-based cyan ink A water-based white ink, Example 1, was prepared for use in the process of the present invention. The formulation of Example 1 is shown in Table 1 below. [Table 1] Neocryl XK14 acrylic emulsion is a self-crosslinking acrylic emulsion with a Tg of approximately 50°C. Neocryl A1125 is a water-based self-crosslinking acrylic copolymer emulsion with a MFFT below 0°C. Joncryl 8052 is an acrylic emulsion with a Tg of -35°C. Disperbyk 190 is a styrene block copolymer wetting agent. Tego Foamex is a polyether siloxane copolymer emulsion defoamer. Aquacer 531 is a modified PE wax emulsion in water. Surfynol AD01 is a non-ionic surfactant based on Gemini technology. DC209S is a silicone emulsion in water.

[0098] A water-based cyan ink, Example 2, was prepared for use in the process of the present invention. The formulation for Example 2 is shown below in Table 2. Note that although water is not listed as a separate component, the composition contains water because the acrylic emulsion, wax emulsion, and silicone emulsion contain water. [Table 2] Joncryl ECO2124 is a glycol ether-free acrylic emulsion with a Tg of -35°C. Crayvallac WW1001 is a PE wax dispersion in water.

[0099] Comparative Example 1A (white) and Comparative Example 2A (cyan) were prepared similarly to Examples 1 and 2, except that NeoCryl XK14 self-crosslinking acrylic emulsion (having a Tg above 0° C.) was replaced with Wallpol 01B self-crosslinking acrylic emulsion (having a Tg below 0° C.) Comparative Example 1B (white) and Comparative Example 2B (cyan) are solvent-based Sleeve Flex inks commercially available from Sun Chemical.

[0100] Test ink samples were reduced to printing viscosity (19 seconds Zahn #2 cup) with water. Examples 1 and 2, and Comparative Examples 1A and 2A were printed onto 50 μm PET shrink film and tested as described above. Results are shown in Tables 3-8. Basic initial test, product drip test, product test, curl test, and blocking test were performed before shrinkage. Hot water test results are after shrinkage in hot water. [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8]

[0101] Example 3. Water-based overprint varnish Overprint varnishes of the present invention were prepared according to the formulations in Table 9. [Table 9]

[0102] A commercially available comparative ink, Aquathene CB Red / Blue Carrier Bag Ink (Sun Chemical), was printed on various substrates: PE, PET, and PP. An overprint varnish of the present invention was then applied over the comparative ink. Separate prints of the comparative ink on PE without the overprint varnish were also made. As noted above, the present invention is a surprising discovery: inks prepared as in WO 2016 / 028850 are suitable for printing on shrinkable polymer flexible film substrates. These inks were previously thought to be suitable only for polyethylene-coated board substrates. Ink 1 (red) and Ink 2 (blue) (from Table 1 of WO 2016 / 028850) were printed on PE substrates, and the results surprisingly show that the Satra rub resistance is comparable to the overprint varnish of the present invention. The Satra rub resistance results for the prints are shown in Table 10. Results are reported as the number of rubs required for complete ink removal, with a higher number of rubs indicating better rub resistance. Note that the results are an average of the red and blue ink samples. [Table 10]

[0103] 1Separate prints of both Aquathene CB red and blue (comparative inks) were made, and the results in Table 10 are the average of the two prints.

[0104] 2 Because this is a visual test and OPV is transparent (colorless), to obtain accurate results, red and blue inks with poor resistance properties were first printed onto the substrate and then OPV was applied. The poorly resistant red and blue inks used were Aquathene CB (Sun Chemical), commercially available for use on polyethylene carrier bags. First, separate prints of both the Aquathene CB red and blue inks were made on the polymer substrates specified in Table 10, and then subsequently overprinted with the OPV of Example 3. The results in Table 10 demonstrate that the OPV of the present invention provides superior resistance properties to an ink that has relatively poor resistance properties without the OPV of Example 3. The OPV results in Table 10 are the average of the red and blue inks. For comparison purposes, the rub of the Aquathene CB carrier bag red / blue ink (without OPV) is also shown in Table 10. These results demonstrate that the resistance properties are derived from the OPV.

[0105] 3 Red and blue inks were prepared using the formulations from Table 1 of WO 2016 / 028850, then printed and dried separately and tested for rub resistance. The results show that inks based on these formulations and printed according to the present inventive process onto shrinkable polymer substrates far outperform Aquathene inks that were not overprinted.

[0106] The physical properties of the OPV of Example 3 and the Sun ink exemplified in WO 2016 / 028850 were tested. Results are based on the average of two prints (one red and one blue) printed on a PE substrate. The results are shown in Table 11. [Table 11]

[0107] These results confirm that the OPV of the present invention achieves similar durability improvements as the inks of the present invention and WO 2016 / 028850.

[0108] Overall, the results show that the inks and overprint varnishes of the present invention are suitable for shrinkable flexible polymeric film substrates (as well as non-shrinkable polymeric film substrates). The inks and overprint varnishes of the present invention exhibit superior properties compared to commercially available inks.

[0109] Although the present invention has been described in detail, including preferred embodiments thereof, it will be appreciated that those skilled in the art, upon consideration of this disclosure, may make modifications and / or improvements thereto which are within the scope and spirit of the invention.

Claims

1. 1. A process for printing on a polymer substrate, comprising: a) i) at least one self-crosslinking acrylic polymer; ii) at least one coalescing agent; iii) at least one silicone emulsion, and iv) water wherein the self-crosslinking acrylic polymer has a glass transition temperature above 0°C; b) applying the ink or coating composition of a) to a polymer substrate; and c) drying the ink or coating composition on the polymeric substrate; and The process includes:

2. 2. The process of claim 1, wherein the polymer substrate is selected from the group consisting of oriented polypropylene (OPP), polyvinyl chloride (PVC), oriented polystyrene (OPS), polyethylene terephthalate (PET), and polylactic acid film (PLA).

3. 3. The process of claim 1, wherein the polymer substrate is a shrinkable polymer substrate.

4. The process of any one of claims 1 to 3, wherein the self-crosslinking acrylic polymer of the ink or coating composition has a glass transition temperature of from 20°C to 70°C.

5. The process of any one of claims 1 to 4, wherein the self-crosslinking acrylic polymer of the ink or coating composition has a glass transition temperature of from 40°C to 60°C.

6. 6. The process of any one of claims 1 to 5, wherein the self-crosslinking acrylic polymer of the ink or coating composition is formed from monomers selected from methyl acrylic acid (MAA), methyl methacrylate (MMA), butyl acrylate, butyl methacrylate, styrene, and methylstyrene.

7. The process of any one of claims 1 to 6, wherein the self-crosslinking acrylic polymer of the ink or coating composition is a styrene / acrylic acid ester copolymer.

8. The process of any one of claims 1 to 7, wherein the self-crosslinking acrylic polymer of the ink or coating composition is formed from a carbonyl / amine reaction.

9. The process of any one of claims 1 to 8, wherein the self-crosslinking acrylic polymer of the ink or coating composition is an acrylic emulsion.

10. The process of any one of claims 1 to 9, wherein the coalescing agent has a glass transition temperature of 20°C or less.

11. The process of any one of claims 1 to 10, wherein the coalescing agent has a glass transition temperature of 0°C or less.

12. The process of any one of claims 1 to 11, wherein the coalescing agent for the self-crosslinking acrylic polymer is an acrylic emulsion.

13. The process of any one of claims 1 to 12, wherein the silicone emulsion of the ink or coating composition comprises a high molecular weight polydimethylsiloxane having reactive silanol groups.

14. The process of any one of claims 1 to 13, wherein the ink or coating composition comprises from 5 wt% to 60 wt% of the self-crosslinking emulsion, based on the total weight of the ink or coating composition.

15. The process of any one of claims 1 to 14, wherein the ink or coating composition comprises 20 wt% to 60 wt% of the self-crosslinking acrylic emulsion, based on the total weight of the ink or coating composition.

16. The process of any one of claims 1 to 15, wherein the ink or coating composition comprises 30 wt% to 50 wt% of the self-crosslinking acrylic polymer, based on the total weight of the ink or coating composition.

17. The process of any one of claims 1 to 16, wherein the ink or coating composition comprises from 2 wt% to 20 wt% of a coalescing agent, based on the total weight of the ink or coating composition.

18. The process of any one of claims 1 to 17, wherein the ink or coating composition comprises from 5 wt% to 15 wt% of a coalescing agent, based on the total weight of the ink or coating composition.

19. The process of any one of claims 1 to 18, wherein the ink or coating composition comprises 0.2 wt% to 3 wt% of silicone emulsion, based on the total weight of the ink or coating composition.

20. The process of any one of claims 1 to 19, wherein the ink or coating composition comprises 1 wt% to 2 wt% of silicone emulsion, based on the total weight of the ink or coating composition.

21. The process of any one of claims 1 to 20, wherein the ink or coating composition further comprises a colorant.

22. 22. The process of claim 21, wherein the colorant is a pigment dispersion.

23. The process of any one of claims 21 to 22, wherein the ink or coating composition comprises from 5 wt% to 50 wt% of the pigment dispersion, based on the total weight of the ink or coating composition.

24. The process of claims 21 to 23, wherein the ink or coating composition comprises 20 wt% to 45 wt% of the pigment dispersion, based on the total weight of the ink or coating composition.

25. The process of any one of claims 21 to 24, wherein the ink or coating composition comprises 30 wt% to 40 wt% of the pigment dispersion, based on the total weight of the ink or coating composition.

26. 26. The process of any one of claims 1 to 25, wherein the ink or coating composition further comprises one or more additives selected from the group consisting of humectants, alcohols, polyethylene wax emulsions, wax dispersions, antifoaming agents, waxes, ammonia, defoamers, dispersants, stabilizers, silicones, rheology modifiers, and plasticizers.

27. The process of any one of claims 1 to 26, wherein the ink or coating composition contains no more than 300 ppm bisphenol-A (BPA).

28. The process of any one of claims 1 to 27, wherein the ink or coating composition does not contain bisphenol-A.

29. The process of any one of claims 1 to 28, wherein the ink or coating composition contains up to 30 wt% of an epoxy ester.

30. The process of any one of claims 1 to 29, wherein the ink or coating composition does not contain an epoxy ester.

31. The process of any one of claims 1 to 30, wherein the ink or coating composition is an overprint varnish.

32. 32. The process of claim 31 , wherein the overprint varnish is applied directly onto the substrate.

33. 32. The process of claim 31 , wherein the overprint varnish is applied over one or more first-down inks and / or coatings.

34. 34. The process of claim 33, wherein the first down ink and / or coating does not comprise an ink or coating composition according to the process of claim 1.

35. A printed substrate made by the process of any one of claims 1 to 34.

36. 36. The printed substrate of claim 35, wherein the substrate is selected from the group consisting of oriented polypropylene, polyvinyl chloride, oriented polystyrene, polyethylene terephthalate, and polylactic acid films.

37. The substrate to be printed according to any one of claims 35 to 36, wherein the substrate to be printed is a shrinkable polymer film.

38. An article comprising the printed substrate according to any one of claims 35 to 37.

39. The process of any one of claims 1 to 34, wherein the ink or coating composition is a gravure or flexographic ink or coating composition.

40. The process of any one of claims 1 to 34 or 39, wherein the ink or coating composition is water-based.

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