Kit for improved oxygen barrier coating and product comprising an improved oxygen barrier coating

The present invention is related to a kit for making an improved oxygen barrier coating and a product comprising said improved oxygen barrier coating.

Articles made of plastic (i.e. synthetic polymers such as poly ethylene (PE), polypropylene (PP) or polyethylene terephthalate (PET)) are extremely efficient for the purposes of flexible packaging. However, this advantage has led to an extreme use of plastic materials, and without efficient recycling the environ mental pollution that can already be observed (e.g. pollution of the oceans) will increase.

Flexible packaging materials that are intended for food applica tions (or pharmaceutical applications or other materials which need protection) furthermore comprise functional coating layers in addition to layers made from the above plastic materials. Plastic materials do not satisfactorily prevent permeation of oxygen and moisture. As a consequence, food provided within said flexible packaging may suffer from detrimental effects such as oxidation or hydration/dehydration. To address this problem, ox ygen barrier coating layers have been provided in flexible pack aging materials. Conventionally, coatings consisting of metals and chlorinated polymers, such as poly(vinyl chloride) (PVC) and poly (vinylidene chloride) (PVDC), have been used for this pur pose. Aluminum oxide with an oxygen transmission rate (OTR) of approximately 1 mL/m ² day has been most commonly used these days (Thuy et al., Green Chem., 2021, 23, 2658).

However, flexible packaging materials comprising such an oxygen barrier coating layer often give rise to health and environmen- PSIEG032WO /04.07.2022 2 PSIEG032WO-2022090238 tal issues, due to the characteristics of the used materials (presence of metals, chlorinated polymers). If one wants to re cycle flexible packaging materials comprising such an oxygen barrier coating layer, one would have first to delaminate said oxygen barrier coating layer. However, this is not an easy pro cess and furthermore expensive. Accordingly, today still many food packaging wastes are disposed of through landfills or in cineration. Upon burning, PVDC and PVC release hazardous gases. Moreover, incineration of plastic materials is detrimental with respect to the amount of CO2 released therewith and its contribu tion to global warming.

In some regions (e.g. the EU) regulations have been implemented requiring a certain recycling rate to be obtained until a cer tain point in time. Furthermore and independent from regula tions, all major brand owners made commitments to increase the amount of recycled material in their products.

In order to address the problems that are associated with oxygen barrier coating layers consisting of metals and chlorinated pol ymers, oxygen barrier coating layers have been suggested that are made from polyvinyl alcohol (PVOH) (e.g. US-5,508,113 A).

While, such layers address the environmental and health problems mentioned above, they are typically applied as an aqueous solu tion and do not dry sufficiently fast when being applied onto a conventional substrate such as a film made from polyethylene (PE) or polypropylene (PP). Accordingly, subsequent layers such as ink layers cannot be applied onto said oxygen barrier layer with the printing speed required for commercial applications.

This problem cannot be overcome by first printing the other lay ers such as ink layers onto the substrate, and only then apply- PSIEG032WO /04.07.2022 3 PSIEG032WO-2022090238 ing the oxygen barrier coating layer. It has been found that a manufacturing process with said sequence of steps results in a product that does not have satisfactory oxygen barrier proper ties, as determined by the oxygen transmission rate (OTR) of said product.

It was therefore the problem of the present invention to provide a product such as a flexible packaging for food applications that overcomes the above drawbacks of the prior art.

According to the present invention, the above problem has been solved by the subject-matter defined in the claims.

In one embodiment, the present invention is related to a kit, comprising a) a composition for preparing an oxygen barrier coating com prising a polymer having reactive hydroxyl groups, b) a composition for preparing a layer selected from the group consisting of an ink layer and an overprint varnish layer, c) optionally a composition for preparing an adhesive layer, characterized in that at least one of compositions b and c) com prises a component that is capable of crosslinking with the pol ymer of composition a) when compositions a) and b) and optional ly c) are applied one after another onto an uncoated or coated substrate such that at least one of compositions b) and c) that comprises said component that is capable of crosslinking with the polymer of composition a) is applied adjacent to composition a).

It has been found that when an oxygen barrier coating composi tion comprising a polymer having reactive hydroxyl groups, pref erably a polymer selected from the group consisting of polyvinyl alcohol and esters and acetals thereof, and copolymers and ter- PSIEG032WO /04.07.2022 4 PSIEG032WO-2022090238 polymers of vinylalcohol and esters and acetals thereof, is ap plied in combination with a composition that comprises a compo nent that is capable of crosslinking with said polymer, a se quence of layers is obtained wherein the reactive hydroxyl groups of said polymer in said oxygen barrier coating layer are reacted with said component in said other adjacent layer, re sulting in a crosslinking reaction between these adjacent lay ers. In consequence, the manufacturing process of the present invention can be carried out with a printing speed similar to commercial printing processes.

In addition, it was found that according to the present inven tion less coating weight of the oxygen barrier coating layer has to be applied in order to achieve the desired oxygen transmis sion rate (OTR).

The term "capable of crosslinking with the polymer of composi tion a) when compositions a) and b) and optionally c) are ap plied one after another" means that the respective components in adjacent layers may undergo a crosslinking reaction under typi cal conditions of application of layers onto a substrate, pref erably under typical printing conditions, more preferably under typical conditions of flexographic or gravure printing. Those conditions are known in the art (e.g. Leach/Pierce (eds.), The Printing ink manual, Blueprint 5 ^th ed. 1993, e.g. p. 33-52). In other words, the coated product comprises reaction products of the reactive groups, preferably hydroxyl groups, of the polymer of composition a) and the component capable of crosslinking with the polymer of the oxygen barrier layer disposed between the ox ygen barrier layer and the layer adjacent to said oxygen-barrier coating layer. PSIEG032WO /04.07.2022 5 PSIEG032WO-2022090238

The term "reactive hydroxyl groups" means that the respective polymer exhibits hydroxy groups that may undergo the crosslink ing reaction defined above. Said term comprises free hydroxyl groups and modified hydroxyl groups (e.g. hydroxyl groups modi fied with a protective group) that become free hydroxyl groups under the applied crosslinking conditions. The hydroxyl groups may be primary hydroxyl groups, secondary hydroxyl groups, ter tiary hydroxyl groups or any combination thereof.

A composition for preparing an oxygen barrier coating comprising a polymer having reactive hydroxyl groups, preferably a polymer selected from the group consisting of polyvinyl alcohol and es ters and acetals thereof, and copolymers and terpolymers of vi- nylalcohol and esters and acetals thereof is known.

The polymer in said oxygen barrier coating composition may be a homopolymer. Said homopolymer may preferably be selected from the group consisting of polyvinyl alcohol (PVOH), polyvinyl ace tate (PVA), and polyvinyl butyral (PVB).

The polymer in said oxygen barrier coating composition may be a copolymer. Said copolymer may preferably be selected from the group consisting of ethylene-vinyl alcohol copolymer (EVOH), bu- tenediol-vinyl alcohol copolymer (BVOH), vinyl acetate-vinyl al cohol copolymer, acrylate-vinyl alcohol copolymer, and acrylate- vinyl acetate copolymer. In the case of vinyl alcohol-containing copolymers, also esters and acetals thereof may be used. Prefer ably, the weight average molecular weight of the polymer and/or copolymer to be used in said oxygen barrier coating composition is in a range of between 5000 and 50000 g/mol.

According to another preferred embodiment of the present inven tion, also terpolymers of the monomers vinyl alcohol, vinyl ace- PSIEG032WO /04.07.2022 6 PSIEG032WO-2022090238 tate, ethylene, butenediol, and acrylate may be used. In the case of vinyl alcohol-containing terpolymers, also esters and acetals thereof may be used.

According to another preferred embodiment of the present inven tion, also blends of the above polymers, copolymers and terpoly mers optionally with additional polymers may be used. Such op tional additional polymers must not exhibit a detrimental effect on the barrier properties of the final oxygen barrier coating layer. For example chlorinated polymers conventionally used in oxygen-barrier coating compositions, such as poly(vinyl chlo ride) (PVC) and poly(vinylidene chloride) (PVDC), may be present in composition a) of the kit of the present invention.

According to the present invention, it is necessary that the composition a) of the kit of the present invention provides a sufficient amount of free OH groups for the reaction with the component in the composition b) and optionally c) that is capa ble of crosslinking with said polymer. According to a preferred embodiment of the present invention, said composition a) of the kit of the present invention has a hydroxyl value of at least 5 mg KOH/g, preferably at least 10 mg KOH/g, and even more pre ferred at least 20 mg KOH/g. The upper limit of the hydroxyl values is not particularly limited and may be 600 mg KOH/g, preferably 400 mg KOH/g.

The hydroxyl value is a known parameter that defines the number of free hydroxy groups in a chemical compound. It is typically expressed by the amount of KOH (in mg) equivalent to the number of hydroxy groups in 1 g of the substance to be examined. It may be determined, for example, by acetylation of the free hydroxy groups of a substance with acetic anhydride. After completion of the reaction, water is added, and the remaining unreacted acetic PSIEG032WO /04.07.2022 7 PSIEG032WO-2022090238 anhydride is converted to acetic acid and measured by titration with potassium hydroxide.

The composition a) in the kit of the present invention comprises the polymer described above in an amount of preferably 5-50 wt.- %, more preferably 10-40 wt.-%, and even more preferred 12-30 wt.-%, based on the weight of the entire composition a).

The composition a) in the kit of the present invention may fur thermore comprise at least one solvent, preferably a combination of solvents. The exact nature of the solvent to be used depends on the polymer and its respective water-solubility that is used in the composition a). The solvent may be water, an organic sol vent or both water and an organic solvent. Any organic solvent that is conventionally used in coating compositions may be used. Examples are esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, or neopentyl acetate, ketones such as ace tone, or alcohols such as ethanol, n-propanol or isopropanol.

The composition a) in the kit of the present invention may com prise at least one solvent described above in an amount of pref erably 44 to 95 wt.-%, more preferably 55 to 85 wt.-%, and even more preferably 65 to 83 wt.-%, based on the weight of the en tire composition a).

The composition a) in the kit of the present invention may op tionally comprise at least one additive that is conventionally used in oxygen barrier coating compositions. Examples are bio cides, fungicides, adhesion promoters and crosslinkers such as polyethyleneimine, surfactants, and wetting aids that do not ad versely affect the oxygen barrier properties of the oxygen bar rier coating layer manufactured from composition a). The compo sition a) in the kit of the present invention comprises at least PSIEG032WO /04.07.2022 8 PSIEG032WO-2022090238 one additive described above, if present at all, in an amount of preferably 0,1 to 5 wt.-%, more preferably 0,2 to 3 wt.-%, and even more preferably 0,5 to 2 wt.-%, based on the weight of the entire composition a).

The kit of the present invention furthermore comprises a compo sition b). Said composition b) is used for manufacturing a layer selected from the group consisting of an ink layer and an over print varnish layer. Such compositions are known in the art and will be explained below. The compositions b) of the kit of the present invention preferably differ, however, from known compo sitions by the additional presence of a component that is capa ble of crosslinking with the polymer of composition a) when com positions a) and b) are applied one after another onto an un coated or coated substrate. It is to be understood, however, that in embodiments where an optional composition c) is also used that comprises said component that is capable of crosslink ing with the polymer of composition a), and wherein said compo sitions a) and c) are applied one after another onto an uncoated or coated substrate, said composition b) does not necessarily have to comprise said component that is capable of crosslinking with the polymer of composition a).

Compositions for making ink layers are generally known. While the composition can be applied on a substrate by any standard technique, according to the present invention it is preferred to use ink compositions that are adapted for application by flexo graphic or gravure printing.

Compositions for making ink layers for flexible packaging mate rials comprise a binder component. According to the present in vention, any binder conventionally used for making ink layers for flexible packaging materials is suitable. Suitable examples PSIEG032WO /04.07.2022 9 PSIEG032WO-2022090238 are acrylic or methacrylic acid resins, polyurethane resins, rosin-based resins, polyamide resins, polyvinylchloride, polyes ters such as polyester polyols, cellulose and derivatives such as nitrocellulose or cellulose acetate butyrate, lignin and de rivatives such as nitro lignin, and combinations thereof.

Preferably, the composition b) of the kit of the present inven tion for making ink layers comprises 10 to 60 wt.-%, more pref erably 20 to 40 wt.-%, based on the weight of the entire compo sition, of said binder component.

Compositions for making ink layers for flexible packaging mate rials furthermore comprise at least one solvent. According to the present invention, any solvent conventionally used for mak ing ink layers for flexible packaging materials is suitable. Suitable examples are water or preferably an organic solvent such as methyl ethyl ketone, an alcohol such as ethanol or iso propanol, ethyl acetate, isopropyl acetate, tetrahydrofuran, di- chloromethane, acetone, dimethyl formamide, acetonitrile, dime thyl sulfoxide, and combinations thereof.

Preferably, the composition b) of the kit of the present inven tion for making ink layers comprises 10 to 30 wt.-%, more pref erably 15 to 25 wt.-%, based on the weight of the entire compo sition, of said at least one solvent.

Compositions for making ink layers for flexible packaging mate rials preferably comprise at least one colorant, preferably a dye or a pigment, especially preferred a pigment. According to the present invention, any colorant conventionally used for mak ing ink layers for flexible packaging materials is suitable.

Depending on the kind of colorant used, the composition may pro vide a colored layer or a white layer. PSIEG032WO /04.07.2022 10 PSIEG032WO-2022090238

If a colored layer is to be provided, the colorant may be se lected from the group consisting of a cyan pigment, a magenta pigment, a yellow pigment, and a black pigment.

Such pigments are generally known in the art. Examples of suita ble commercially available pigments are Permanent Yellow DHG, Permanent Yellow GR, Permanent Yellow G, Permanent Yellow NCG- 71, Permanent Yellow GG, Hansa Yellow RA, Hansa Brilliant Yellow 5GX-02, Hansa Yellow X, NOVAPERM YELLOW HR, NOVAPERM YELLOW FGL, Hansa Brilliant Yellow 10GX, Permanent Yellow G3R-01, HOS- TAPERM YELLOW H4G, HOSTAPERM YELLOW H3G, HOSTAPERM ORANGE GR, HOSTAPERM SCARLET GO, Permanent Rubine F6B, L74-1357 Yellow, L75-1331 Yellow, L75-2337 Yellow, DALAMAR YELLOW YT-858-D, CROMOPHTHAL YELLOW 3 G, CROMOPHTHAL YELLOW GR, CROMOPHTHAL YELLOW 8 G, IRGAZINE YELLOW 5GT, IRGALITE RUBINE 4BL, MONAS TRAL MAGENTA, MONASTRAL SCARLET, MONASTRAL VIOLET, MONASTRAL RED, MONASTRAL VIOLET, LUMOGEN LIGHT YELLOW, PALIOGEN ORANGE, HELIOGEN BLUE L 690 IF, HELIOGEN BLUE TBD 7010, HELIOGEN BLUE K 7090, HELIOGEN BLUE L 710 IF, HELIOGEN BLUE L 6470, HELIOGEN GREEN K 8683, HELIOGEN GREEN L 9140, QUINDO MAGENTA, INDOFAST BRILLIANT SCARLET, QUINDO RED 6700, QUINDO RED 6713, INDOFAST VIOLET, Maroon B STERLING NS BLACK, STERLING NSX 76, and MOGUL L.

According to a preferred embodiment of the present invention, the ink layer to be manufactured from composition b) of the kit of the present invention is a white ink layer. In this embodi ment, composition b) comprises as a colorant a white pigment. Suitable white pigments are generally known in the art. Examples are T1O2, calcium carbonate, zinc oxide, alumina-Ti0 ₂ , barium sulphate and mixtures thereof. PSIEG032WO /04.07.2022 11 PSIEG032WO-2022090238

Preferably, the composition b) of the kit of the present inven tion for making ink layers comprises 0 to 70 wt.-%, more prefer ably 20 to 60 wt.-%, based on the weight of the entire composi tion, of said colorant, preferably pigment, most preferably white pigment.

Compositions for making ink layers for flexible packaging mate rials may optionally comprise at least one additive. According to the present invention, any additive conventionally used for making ink layers for flexible packaging materials is suitable. Typically used additives may be selected from the group consist ing of a wax, surfactants, biocides, adhesion promoters and crosslinkers such as polyethyleneimine, fillers, materials for pH adjustment, sequestering agents, preservatives, antioxidants (e.g. Irganox 1010), plasticizers, compatibility additives, emulsifiers, and adhesion promoters (such as Vertec PI-2 from Johnson Mathey; this is a titanate coupling agent (Ethoxy iso- propoxy titanium bis(2, 4-pentanedionate)). Such additives are known.

Typical fillers are calcium carbonate, magnesium carbonate, chi na clay, or mixtures thereof.

Typical waxes are polyethylene or paraffin waxes.

Preferably, the composition b) of the kit of the present inven tion for making ink layers comprises 0 to 20 wt.-%, more prefer ably 0,1 to 10 wt.-%, based on the weight of the entire composi tion, of at least one additive.

Compositions for making overprint varnish (OVP) layers are also generally known. While the composition can be applied on a sub strate by any standard technique, according to the present in- PSIEG032WO /04.07.2022 12 PSIEG032WO-2022090238 vention it is preferred to use overprint varnish (OVP) composi tions that are adapted for application by flexographic or gra vure printing.

Overprint varnish (OVP) compositions generally differ from ink compositions by the absence of a colorant such as a pigment. Thus, the above description for compositions b) for making ink layers also applies with respect to the binder component, at least one solvent, and the optional additives. However, the com position b) of the kit of the present invention for making over print varnish (OVP) layers preferably comprises 20 to 80 wt.-%, more preferably 30 to 75 wt.-%, based on the weight of the en tire composition, of said binder component.

The kit according to the present invention may comprise an op tional composition c) for preparing an adhesive layer. Adhesive layers are known in the art. For the purposes of the present in vention, any adhesive layer conventionally used to bond films in flexible laminates may be employed. One adhesive type used to bond separate films into flexible composite laminates is polyu rethane, which may be solvent-based, solvent-free or water- based. Solvent based and solvent free polyurethane adhesives are preferred. Polyurethane adhesives are based on reaction of an isocyanate moiety containing component with an isocyanate re active component. In one component (IK) variations the isocya nate moiety containing component is reacted with the isocyanate reactive component to form an isocyanate moiety containing, moisture reactive, oligomer or prepolymer. The prepolymer is disposed between substrates to be bonded and exposed to moisture from the atmosphere and substrate surfaces to initiate cross- linking and bonding of the substrates. The prepolymer must be prepared and stored under moisture free conditions until use.

In two component (2K) variations the isocyanate moiety contain- PSIEG032WO 704.07.2022 13 PSIEG032WO-2022090238 ing component and the isocyanate reactive component are stored separately and only mixed shortly before use. Mixing the two components initiates a crosslinking reaction with the reaction products typically being an insoluble, thermoset solid. The mixed adhesive is disposed between substrates to be bonded wherein the crosslinked adhesive bonds the substrates. The iso cyanate moiety containing component can be a polyisocyanate, an isocyanate containing oligomer or prepolymer or a combination thereof. Polyisocyanates useful by themselves or as a reactant with a polyol for preparing an isocyanate functional oligomer or prepolymer are described herein. MDI and/or its isomers is one useful polyisocyanate. The isocyanate reactive component typi cally comprises one or more polyols. Polyols that can be used include those polyols typically used for the production of poly urethanes, including, without limitation, polyether polyols, polyester polyols, polybutadiene polyols, polycarbonate poly ols, polyacetal polyols, polyamide polyols, polyesteramide poly ols, polyalkylene polyether polyols, polythioether polyols and mixtures thereof; preferably polyether polyols, polyester poly ols, polycarbonate polyols and mixtures thereof; and more pref erably polyester polyols, polyether polyols and combinations thereof .

Examples of a solvent free and water free 2K polyurethane adhe sive include LOCTITE LIOFOL LA7732 / LA6159, LA7780 / LA6159 and LA1139-04/LA6029 (all commercially available from Henkel).

As stated above, the composition b) of the kit of the present invention differs from conventional ink compositions and over print varnish (OVP) compositions in that composition b) compris es a component that is capable of crosslinking with the polymer of composition a) when compositions a) and b) are applied one PSIEG032WO /04.07.2022 14 PSIEG032WO-2022090238 after another onto an uncoated or coated substrate such that composition b) is applied in contact with composition a).

Said component that is capable of crosslinking with the polymer of composition a) may be contained in or added directly to com position b) described above. However, according to the present invention it is preferred to provide a two-component (2k) system comprising composition b) and said component that is capable of crosslinking with the polymer of composition a) separately. A similar 2K system may also be used with respect to the optional composition c) and said component that is capable of crosslink ing with the polymer of composition a).

According to the present invention, any component that is capa ble of crosslinking with the polymer of composition a) may be used, i.e. any component that is capable of reacting with free functional groups of the polymer of composition a). The free functional groups of the polymer of composition a) are most preferably hydroxyl groups.

According to a preferred embodiment of the present invention, the said component that is capable of crosslinking with the pol ymer of composition a) thus comprises functional groups that are capable of reacting with hydroxyl groups. Preferably, said com ponent that is capable of crosslinking with the polymer of com position a) thus comprises at least one functional group that is selected from the group consisting of isocyanate, isocyanurate, carbodiimide, aziridine, epoxide, styrene maleic anhydride, silane and polyethylene imine, or combinations thereof. Accord ing to the present invention, said component that is capable of crosslinking with the polymer of composition a) preferably com prises isocyanate groups. PSIEG032WO 704.07.2022 15 PSIEG032WO-2022090238

According to a preferred embodiment of the present invention, the isocyanate is a polyisocyanate. The polyisocyanate may, for example, be an aromatic polyisocyanate such as naphthalene 1,5- diisocyanate, polyphenylene polymethylene polyisocyanate, 4,4'- diphenylmethane diisocyanate including its isomers (hereinafter referred to as MDI), 2,4-tolylene diisocyanate (hereinafter re ferred to as 2,4-TDI) or 2,6-tolylene diisocyanate (hereinafter referred to as 2,6-TDI); an aralkyl polyisocyanate such as xy- lylene diisocyanate or tetramethylxylylene diisocyanate; an ali phatic polyisocyanate such as hexamethylene diisocyanate (here inafter referred to as HDI); an alicyclic polyisocyanate such as isophorone diisocyanate (hereinafter referred to as IPDI) or 4,4 '-methylenebis(cyclohexyl isocyanate); an isocyanate func tional oligomer or prepolymer; or a modified product such as an urethane modified product, an allophanate modified product, a carbodiimide modified product or an isocyanurate modified prod uct, obtainable from such a polyisocyanate. Particularly pre ferred is a polyisocyanate having two isocyanate groups, such as hexamethylene diisocyanate, isophorone diisocyanate, 2,4- tolylene diisocyanate or 2,6-tolylene diisocyanate.

Examples of suitable epoxy-containing components include glyc- idyl acrylate, glycidyl methacrylate, and combinations thereof.

According to the present invention, said component that is capa ble of crosslinking with the polymer of composition a) may be a monomer, dimer, trimer, an oligomer, pre-polymer or a polymer.

According to the present invention, the term "oligomer " refers to a molecule that consists of a few repeating units which are derived from monomers. An oligomer differs from a polymer with respect to the number of repeating units, said number being smaller in oligomers. There is no sharp distinction between oli- PSIEG032WO /04.07.2022 16 PSIEG032WO-2022090238 gomers and polymers. Typically, a molecule comprising 5-100 re peating units is referred to an oligomer, whereas a molecule having more than 100 repeating units is referred to as "poly mer ".

According to the present invention, the term "pre-polymer " re fers to a monomer or system of monomers that have been reacted to an intermediate molecular mass state. This material is capa ble of further polymerization by reactive groups to a fully cured high molecular weight state. A difference between an oli gomer and a pre-polymer is that a pre-polymer is an intermediate product of a reaction leading to a polymer.

According to the present invention, said component that is capa ble of crosslinking with the polymer of composition a) is pre sent in composition b) in a ratio of 1-40 wt.-%, preferably 5-30 wt.-%, based on the total weight of the composition. Said compo nent that is capable of crosslinking with the polymer of compo sition a) is present in optional composition c) in a ratio of 50-100 wt.-% for one component polyurethane adhesives and 40-70 wt.-% for two component polyurethane adhesives, in each case based on the total weight of the composition c). In certain em bodiments that the optional composition c) is at least one poly urethane, the mixing ratio by weight of the isocyanate moiety containing component and the isocyanate reactive component is no less than 0,8:1, preferably no less than 1,0:1, more preferably no less than 1,2:1, and in particular no less than 1,5:1.

In the preferred embodiment of the present invention wherein there is provided a two-component (2k) system comprising compo sition b) and said component that is capable of crosslinking with the polymer of composition a) separately, said component PSIEG032WO /04.07.2022 17 PSIEG032WO-2022090238 that is capable of crosslinking with the polymer of composition a) is provided as a separate composition comprising said compo nent that is capable of crosslinking with the polymer of compo sition a) and a solvent. A similar 2K system may also be used with respect to the optional composition c) and said component that is capable of crosslinking with the polymer of composition a).

According to the present invention, any solvent conventionally used for making ink layers for flexible packaging materials is suitable. Suitable examples are water or preferably an organic solvent such as methyl ethyl ketone, an alcohol such as ethanol or isopropanol, ethyl acetate, isopropyl acetate, tetrahydrofu- ran, dichloromethane, acetone, dimethyl formamide, acetonitrile, dimethyl sulfoxide, and combinations thereof.

Preferably, the separate composition comprising said component that is capable of crosslinking with the polymer of composition a) and a solvent comprises 5 to 50 wt.-%, more preferably 15 to 40 wt.-%, based on the weight of the entire separate composi tion, of said at least one solvent. The remaining portion of the separate composition (i.e. 50-90 wt.-&, preferably 60-85 wt.-%) is the component that is capable of crosslinking with the poly mer of composition a). Optionally, any of the additives de scribed above may be present in the amount described above for composition b).

The kit of the present invention may be provided in any suitable form. Preferably, said kit may be in form of a container (such as a cardboard package) comprising separate compartments (such as bags, bottles, cartridges, hobbocks, drums, IBC containers, liquid totes, etc.) for composition a), composition b), optional composition c) and optionally (in the preferred embodiment where PSIEG032WO /04.07.2022 18 PSIEG032WO-2022090238 composition b) is a 2K system) for the separate composition com prising said component that is capable of crosslinking with the polymer of composition a).

According to the the preferred embodiment of the present inven tion where composition b) and/or optional composition c) is a 2K system, composition b) and the separate composition comprising said component that is capable of crosslinking with the polymer of composition a) are preferably added together directly before printing. It has been found that this has resulted in an im proved OTR result.

The kit of the present invention may be used for providing a coated product with improved oxygen barrier properties.

Accordingly, the present invention is also related to a coated product, comprising a substrate and a sequence of layers applied on at least one surface of said substrate, said sequence of lay ers comprising: an oxygen-barrier coating layer comprising a polymer having reactive hydroxyl groups, and a layer adjacent to said oxygen-barrier coating layer, optionally an adhesive layer adjacent to said oxygen-barrier coating layer, characterized in that said oxygen-barrier coating layer and said layer and/or said optional adhesive layer adjacent to said oxy gen-barrier coating layer are crosslinked due to a reaction of said polymer in said oxygen-barrier coating layer with a compo nent in said layer adjacent to said oxygen-barrier coating lay er.

In other words, the coated product comprises reaction products of the reactive groups, preferably hydroxyl groups, of the poly- PSIEG032WO /04.07.2022 19 PSIEG032WO-2022090238 mer and the component capable of crosslinking with the polymer of the oxygen barrier layer disposed between the oxygen barrier layer and the layer adjacent to said oxygen-barrier coating lay er.

The coated product that is prepared with the kit of the present invention comprises a substrate.

According to the present invention, the substrate may be any ma terial suitable for use in a flexible packaging material. Exam ples of substrates suitable according to the present invention are a film of polyethylene such as MDO-PE (machine direction oriented PE), biaxially oriented polyethylene (BOPE), biaxially oriented polypropylene (BOPP), polyethylene terephthalate (PET), oriented polyamide (OPA) or polylactic acid (PLA). It is also possible to use paper, metallized paper or cardboard as a sub strate.

According to the present invention, the dimensions of the sub strate are not particularly limited. Preferably, said substrate has a thickness of more than 10 pm, preferably 10-150 pm.

Onto at least one surface of said substrate, there may be ap plied directly a sequence of oxygen barrier coating layer and ink layer or overprint varnish layer, and optionally adhesive layer, using the kit of the present invention. In the case where an ink layer is provided, preferably a white ink layer, a se quence of substrate-ink layer-oxygen barrier layer-optional ad hesive layer is preferably provided.

In the case where an overprint varnish layer is provided, a se quence of substrate-oxygen barrier layer-overprint varnish layer is preferably provided. PSIEG032WO 704.07.2022 20 PSIEG032WO-2022090238

In the case where an optional adhesive layer is provided, a se quence of substrate-ink layer-oxygen barrier layer-adhesive lay er is preferably provided.

According to a preferred embodiment of the present invention, the coated product is a composite laminate structure, compris ing: a substrate having a surface; at least one color layer disposed on the substrate surface; an oxygen barrier layer disposed on the substrate surface, the oxygen barrier layer comprising a polymer having reac tive hydroxyl groups; a backing layer disposed on the oxygen barrier layer, the backing layer comprising a component that is capable of crosslinking with the polymer of the oxygen barrier layer; and reaction products of the reactive hydroxyl groups and the compo nent capable of crosslinking with the polymer of the oxygen bar rier layer disposed between the oxygen barrier layer and the backing layer.

The backing layer may be selected from the group consisting of an ink layer, an overprint varnish layer and an adhesive layer.

According to another preferred embodiment of the present inven tion said composite laminate structure comprises an ink layer disposed between said at least one ink layer and said oxygen barrier layer, said ink layer comprising a component that is ca pable of crosslinking with the reactive hydroxyl groups of the polymer; and reaction products of the reactive hydroxyl groups and the component capable of crosslinking with the polymer of the oxygen PSIEG032WO /04.07.2022 21 PSIEG032WO-2022090238 barrier layer disposed between the oxygen barrier layer and the additional ink layer.

According to a preferred embodiment of the present invention, composition a) is applied in a dry solids coating weight in the range from 0,2 g/m ² to 2 g/m ² , preferably 0,5 g/m ² to 1,5 g/m ² , more preferably 0,6 g/m ² to 1,2 g/m ² . An oxygen barrier coating layer obtained therefrom exhibits a desired OTR value as meas ured at 0% relative humidity of less than 50 cm ³ /m ² /24h, prefera bly less than 30 cm ³ /m ² /24h, more preferably less than 20 cm ³ /m ² /24h, even more preferably less than 5 cm ³ /m ² /24h, and espe cially preferred less than 1 cm ³ /m ² /24h. OTR values can be meas ured by any method known in the art, preferably with the method described in the examples.

According to a preferred embodiment of the present invention, one or more color layers are preferably provided onto at least one surface of said substrate, and on the uppermost of said col or layers the sequence of oxygen barrier coating layer and ink layer or overprint varnish layer, and optional adhesive layer, is provided.

One of said color layers may also be a white layer.

According to a preferred embodiment of the present invention, 1 to 10, preferably 4-7, additional color layers are provided onto at least one surface of said substrate, and on the uppermost of said color layers the sequence of oxygen barrier coating layer and ink layer or overprint varnish layer, and optional adhesive layer, is provided.

According to the present invention, the color layers may be made from any ink composition conventionally used for flexible pack- PSIEG032WO /04.07.2022 22 PSIEG032WO-2022090238 aging. Compositions for making such ink layers are generally known. While the composition can be applied on a substrate by any standard technique, according to the present invention it is preferred to use ink compositions that are adapted for applica tion by flexographic or gravure printing. Reference can be made to the above description where composition b) of the kit of the present invention is a composition for making an ink layer, the composition without the component that is capable of crosslink ing with the polymer of composition a).

In the case of this preferred embodiment where a white ink layer is provided from said kit of the present invention, the sequence of substrate-color layer(s)-white layer-oxygen barrier layer- optional adhesive layer is preferably provided.

In the case of this preferred embodiment where an overprint var nish layer is provided from said kit of the present invention, the sequence of substrate-color layer(s)-oxygen barrier layer- overprint varnish layer is preferably provided.

According to a further embodiment of the present invention, the coated product that is prepared with the kit of the present in vention is a laminate. According to the present invention, the term "laminate" refers to a product that consists of a sequence of layers, wherein an outermost layer or a core layer is defined as substrate or substrate layer. A laminate may also preferably comprise more than one of those substrate layers, most prefera bly as outermost layers, and in between these substrate layers there may be provided a coated layer or several coated layers.

According to a preferred embodiment of the present invention, said laminate comprises the following sequence of layers: Sub- PSIEG032WO /04.07.2022 23 PSIEG032WO-2022090238 strate-color layer(s)-white ink layer-oxygen barrier coating layer-adhesive layer-substrate (sealant film).

In said preferred embodiment, the white ink layer may either be a conventional white ink layer as described above, or a white ink layer made from composition b) of the kit of the present in vention, i.e. comprising a component that is capable of cross- linking with the polymer of composition a) of the kit of the present invention.

In said preferred embodiment, the adhesive layer may either be a conventional adhesive layer as described above, or an adhesive layer comprising a component that is capable of crosslinking with the polymer of composition a) of the kit of the present in vention.

It is necessary according to the present invention that at least one of said white ink layer and said adhesive layer comprises a component that is capable of crosslinking with the polymer of composition a) of the kit of the present invention.

In said preferred embodiment, the substrate provided on top of said adhesive layer may be a substrate as described above, or preferably it may be a heat weldable or sealable film, more preferably a heat weldable or sealable film made from a polyole fin such as polyethylene.

The layers described above can be applied onto the substrate by any conventional coating technique, preferably by flexographic or gravure printing.

Gravure and flexography are the major printing processes for printing packing materials. These processes can be used for PSIEG032WO 704.07.2022 24 PSIEG032WO-2022090238 printing a large variety of substrates, such as paper, card board, or plastic substrates. The gravure and flexographic printing processes are well-known. Reference may be made, for example, to Leach/Pierce (Eds.), The printing ink manual, Blue print, London, 5 ^th ed. 1993, p, 33-53. Also the characteristics of gravure and flexographic inks are known to the skilled man. Reference may be made, for example, to Leach/Pierce (Eds.), The printing ink manual, Blueprint, London, 5 ^th ed. 1993, p, 473-598. The respective content of those chapters is incorporated herein by reference.

The layers described above are applied, according to a preferred embodiment of the present invention, in such an amount that a coating weight of 0.2-1.5 g/m ² , preferably 0.4-1.3 g/m ² , and es pecially preferred 0.6-1.0 g/m ² is obtained for each layer. With respect to the oxygen barrier coating layer, reference is made to the description above.

The present invention is thus also related to a method for mak ing a coated product, comprising the steps: a) providing a substrate having a surface; b) providing a liquid composition a) for preparing an oxygen barrier coating layer, the liquid composition a) comprising a polymer having reactive hydroxyl groups; c) providing a liquid composition b) for preparing a layer se lected from the group consisting of an ink layer and an overprint varnish layer, and optionally providing a liquid composition c) for preparing an adhesive layer, wherein at least one of compositions b) and c) comprises a component that is capable of crosslinking with the polymer of composition a); d) optionally applying at least one color layer onto the sur face of said substrate; PSIEG032WO /04.07.2022 25 PSIEG032WO-2022090238 e) applying, in either sequence, the liquid composition a) and the liquid composition b) onto the surface of the substrate or the at least one color layer to form a sequence of layers comprising an oxygen barrier layer and an ink layer or an overprint varnish layer adjacent to said oxygen barrier lay er, f) optionally applying the liquid composition c) onto the se quence of layers obtained in step e), so as to form an adhe sive layer, g) crosslinking the component in at least one of compositions b) and c) with the polymer in composition a).

In step d), a color or white ink layer or a sequence of color and white ink layers may be applied onto said at least one sur face of said substrate.

Optionally, in a further step an additional substrate such as a heat weldable or sealable film may be applied onto the optional adhesive layer formed in step f).

As described above, the layers described above can be applied onto the substrate by any conventional coating technique, pref erably by flexographic or gravure printing.

According to a preferred embodiment of the present invention, the method is conducted as an in-line printing process. An in line printing process is a process where a layer is applied di rectly onto a previously applied layer in a single process and while the substrate is in continuous motion.In an in-line pro cess, a layer is applied onto a previously applied layer which is still wet (wet-on-wet process). Alternatively, a drying step may be performed before application of the layer onto a previ ously applied layer, wherein said drying step is performed in- PSIEG032WO /04.07.2022 26 PSIEG032WO-2022090238 line and does not interrupt the process. In-line printing pro cesses are generally known.

The method of the present invention may be performed in-line, using conventional equipment and conventional equipment line speeds in contrast to previous methods for providing an oxygen barrier coating.

According to the present invention, said coated product is pref erably a composite laminated structure useful to form flexible packaging .

Many articles such as food articles are stored in flexible pack aging, i.e. sealed packaging surrounding the food article which is made of a material which shows some flexibility and can thus undergo certain modifications of its shape.

Flexible packagings are widely used in areas like food packaging (e.g., retortable bags, frozen food packaging, refrigerated food packaging, shelf stable food packaging, dry goods packaging, liquid food packaging, fast food wrappers and bags), pharmaceu tical packaging (e.g., primary packaging, secondary packaging, booklets and instructions), personal hygiene packaging (e.g. soap packaging, hair care packaging, baby care packaging, femi nine care packaging, male care packaging), home care packaging (e.g. detergent packaging, cleaner packaging), agricultural packaging (e.g., herbicide packaging, pest control packaging, fertilizer bags), industrial packaging (e.g. shopping bags, con struction wrappers and bags), and pet care packaging (e.g., pet food bags, pet medical packaging, pet hygiene packaging).

The present invention will be described hereafter with respect to non-limiting examples and drawings. PSIEG032WO /04.07.2022 27 PSIEG032WO-2022090238

Fig. 1 shows an embodiment of a kit according to the present invention

Fig. 2 shows a first embodiment of a coated product in accord ance with the present invention Fig. 3 shows a second embodiment of a coated product in ac cordance with the present invention Fig. 4 shows a third embodiment of a coated product in accord ance with the present invention Fig. 5 shows a fourth embodiment of a coated product in ac cordance with the present invention Fig. 6 shows the result of OTR measurements for a first set of examples

Fig. 7 shows the result of OTR measurements for a second set of examples

Fig. 8 shows the result of OTR measurements for a third set of examples

In the figures, same reference signs denote the same components.

Fig. 1 shows an embodiment of a kit K according to the present invention. In Fig. 1, said kit K is a package comprising two cartridges. A first cartridge comprises a compartment Cl in which the composition a) of the kit of the present invention is stored. A second cartridge comprises a compartment C2 in which the composition b) of the kit of the present invention is stored, but without the component that is capable of crosslink ing with the polymer of composition a). Said component that is capable of crosslinking with the polymer of composition a) is stored in a third compartment C3. According to this embodiment, the composition b) of the kit of the present invention is a 2K composition. PSIEG032WO /04.07.2022 28 PSIEG032WO-2022090238

Fig. 2 shows a first embodiment of a coated product 1 in accord ance with the present invention. The product 1 comprises a sub strate la, such as polyolefin film. For example, a film made of BOPP (biaxially oriented polypropylene) may be used as substrate la.

On one surface of said substrate la, a sequence of layers is ap plied using the kit K of the present invention. In the embodi ment according to Fig. 2, first a white ink layer lb is applied using the composition b) of the kit K of the present invention. Said composition b) of the kit K of the present invention com prises a component that is capable of crosslinking with the pol ymer of composition a). Thereafter, an oxygen barrier coating layer lc is applied using the composition a) of the kit K of the present invention. When layers lb, lc have been applied adjacent each other, a crosslinking reaction takes place, as indicated in Fig. 2 by the shaded region between layers lb, lc.

Fig. 3 shows a second embodiment of a coated product 1 in ac cordance with the present invention. The second embodiment dif fers from the first embodiment of Fig. 1 in the presence of col or layers Id, le, If, lg. In Fig. 3, four exemplary purposes 4 color layers are shown. This is a non-limiting embodiment. For example, the color layers Id, le, If, lg may be (in arbitrary sequence) a black color layer, a cyan color layer, a magenta color layer and a yellow color layer.

In the embodiment according to Fig. 3, the layers Id, le, If, lg are first applied onto one surface of the substrate la. Thereaf ter, as in the embodiment of Fig. 2, sequence of layers lb, lc is applied using the kit K of the present invention. PSIEG032WO /04.07.2022 29 PSIEG032WO-2022090238

Fig. 4 shows a third embodiment of a coated product 1 in accord ance with the present invention. The third embodiment differs from the second embodiment of Fig. 2 in the presence of an over print varnish layer lh applied on one surface of the oxygen bar rier coating layer lc. In the embodiment according to Fig. 4, the layer lb is a conventional white ink layer without a compo nent that is capable of crosslinking with the polymer of compo sition a). The sequence of oxygen barrier coating layer lc and overprint varnish layer lh is applied using the kit K of the present invention. When layers lc, lh have been applied adjacent each other, a crosslinking reaction takes place, as indicated in Fig. 4 by the shaded region between layers lc, lh.

Fig. 5 shows a fourth embodiment of a coated product 1 in ac cordance with the present invention. The fourth embodiment dif fers from the third embodiment of Fig. 3 instead of the over print varnish layer lh in Fig. 3, here an adhesive layer li has been applied onto the oxygen barrier coating layer lc. The se quence of oxygen barrier coating layer lc and adhesive layer li is applied using the kit K of the present invention. When layers lc, li have been applied adjacent each other, a crosslinking re action takes place, as indicated in Fig. 5 by the shaded region between layers lc, li.

Finally, onto one surface of the adhesive layer li a further substrate lk is applied. In Fig. 5, substrate lk is a heat weld able or sealable film, for example a polyethylene (PE) film.

Comparative example 1 (CE 1 )

A first white ink was formulated with the components indicated in table 1. PSIEG032WO 704.07.2022 30 PSIEG032WO-2022090238

Table 1

This ink was diluted with ethyl acetate to a printing viscosity of 28 seconds flow on a #2 GE Zahn cup. The ink was applied to 70 gauge biaxially oriented polypropylene (BOPP) film using a hand proofer (supplied by Early Manufacturing, Brevard, NC, USA; equipped with a 360 lpi (142 lines per cm), 5.0 bcm (3.23 cm ³ ) anilox roller). The resulting prints were manually dried using an electric hair dryer.

An oxygen-barrier coating composition was formulated with the components indicated in table 2.

Table 2

Said oxygen barrier coating was applied directly upon the sur face of the dried white ink using a K-Coater fitted with a #3 wire-wound coating rod (RD Specialties) to yield a dry solids PSIEG032WO /04.07.2022 31 PSIEG032WO-2022090238 coating weight of 0.5 g/m ² . After manual drying using a hair dry er, the resulting print was placed in a laboratory oven at 50°C for one hour to facilitate complete drying of the printed sam ples.

Example 1

Comparative example 1 was repeated, but the white ink composi tion of table 1 was blended before printing with the composition according to table 3.

Table 3

The compositions according to tables 1 and 3 were blended in a ratio of 70:30 (i.e. 70 wt.% of the white ink composition of ta ble 1 and 30 wt.-% of the crosslinking composition of table 3).

This blend was used instead of the white ink composition of ta ble 1 alone. After the oxygen barrier coating was applied and dried manually, the resulting print was placed in a laboratory oven at 50°C for 16 hours.

Comparative example 2 (CE 2) Comparative example 1 was repeated, but the white ink composi tion of table 1 was replaced by the white ink composition ac cording to table 4. PSIEG032WO /04.07.2022 32 PSIEG032WO-2022090238

Table 4

Example 2 Example 1 was repeated, but the white ink composition of table 1 was replaced by the white ink composition according to table 4. The compositions according to tables 4 and 3 were blended in a ratio of 90:10. OTR tests for examples 1 and 2 and comparative examples 1 and 2

The print samples obtained in examples 1 and 2 and comparative examples 1 and 2 were subjected to oxygen transmission rate (OTR) measurements using an Ox-Tran 2/22 OTR Analyzer (Ametek Mocon, Brooklyn Park, MN, USA). Print samples were mounted to the sample cells such that the BOPP film was oriented toward the test gas (100% Oxygen). The full test parameters are specified below:

The following results were obtained: PSIEG032WO /04.07.2022 33 PSIEG032WO-2022090238

Table 5

The results are also shown in Fig. 6. It can be seen that for both used white ink compositions a significant improvement of the OTR value of the oxygen barrier coating applied adjacent to the respective white ink layer was obtained when a component that is capable of crosslinking with the polymer of the oxygen barrier coating composition with reactive hydroxyl groups was added.

Example 3 and comparative example 3

In a commercial rotogravure printing press, conventional black, cyan, magenta and yellow inks were printed in said sequence onto the BOPP substrate of comparative example 1, followed by appli cation of the oxygen barrier coating composition of table 2 with a coating weight of 1 g/m ² . The line speed of the rotogravure printing press was 135 m/min, and the drying temperatures in a double drier unit at the end of the printing line were 70°C/100°C.

Samples of the same printed material were further modified by applying a PVC-based overprint varnish according to table 6 di rectly onto the oxygen barrier coating layer. PSIEG032WO /04.07.2022 34 PSIEG032WO-2022090238

Table 6

For example 3, the overprint varnish composition of table 6 was blended with the crosslinking composition of table 3 before ap- plication onto the oxygen barrier coating layer. The composi tions according to tables 6 and 3 were blended in a ratio of 85:25.

For comparative example 3, the overprint varnish composition of table 6 was applied as such.

OTR measurements were made as described above. The following re sults were obtained (also shown in Fig. 7): Table 7

It can be seen that a significant improvement of the OTR value of the oxygen barrier coating applied adjacent to the respective white ink layer was obtained when a component that is capable of crosslinking with the polymer of the oxygen barrier coating com position with reactive hydroxyl groups was added to the over print varnish composition. PSIEG032WO /04.07.2022 35 PSIEG032WO-2022090238

Example 4 and comparative example 4

In a commercial rotogravure printing press, conventional black, cyan, magenta and yellow inks as well as a conventional white ink were printed in said sequence onto the BOPP substrate of comparative example 1, followed by application of the oxygen barrier coating composition of table 2 with a coating weight of 0,8 g/m ² . The line speed of the rotogravure printing press was 180 m/min, and the drying temperatures in a double drier unit at the end of the printing line were 70°C/100°C.

In example 4, the obtained sample was hand laminated following typical laboratory methods. An adhesive layer (LOCTITE LIOFOL LA 1139-04/LA1139-81B solvent free adhesive from Henkel) containing a component that is capable of crosslinking with the polymer of the oxygen barrier composition was applied to the barrier coat ing on the print samples, using a K-Coater and RDS coating rod. The coating weight of adhesive applied was ~1.2 g/m ² . A clear polyethylene heat weldable or sealable film was then placed onto the adhesive, and the laminated constructs cured at 25°C for sev en days prior to OTR measurements.

In comparative example 4, no lamination was carried out. OTR measurements were made as described above. The following re sults were obtained (also shown in Fig. 8):

Table 8 PSIEG032WO /04.07.2022 36 PSIEG032WO-2022090238

It can be seen that a significant improvement of the OTR value of the oxygen barrier coating applied was obtained when lamina tion with an adhesive layer composition comprising a component that is capable of crosslinking with the polymer of the oxygen barrier coating composition with reactive hydroxyl groups was carried out.

Examples 5a, 5b and Comparative Example 5

In a commercial rotogravure printing press conventional black, cyan, magenta and yellow inks as well as a white ink according to comparative example 1 was printed onto a BOPP substrate of comparative example 1, followed by application of the oxygen barrier coating composition of table 2 with a coating weight of 0,8 g/m ² . The line speed of the rotogravure printing press was 180 m/min, and the drying temperatures in a double drier unit at the end of the printing line were 70°C/100°C.

In example 5a, the obtained sample was hand laminated following typical laboratory methods. An adhesive layer (LOCTITE LIOFOL LA1139-04/LA6029 solvent free adhesive from Henkel mixed in a 1:1 ratio by weight) containing a component that is capable of crosslinking with the polymer of the oxygen barrier composition was applied to the barrier coating on the print samples, using a K-Coater and RDS coating rod. The coating weight of adhesive ap plied was ~1.8 g/m ² . A clear polyethylene sealable film was then placed onto the adhesive, and the laminated construct was cured at 25°C for seven days prior to OTR measurements.

In example 5b, the obtained sample was hand laminated following typical laboratory methods. An adhesive layer (LOCTITE LIOFOL LA1139-04/LA6029 solvent free adhesive from Henkel mixed in a 1.5:1 ratio by weight) containing a component that is capable of PSIEG032WO /04.07.2022 37 PSIEG032WO-2022090238 crosslinking with the polymer of the oxygen barrier composition was applied to the barrier coating on the print samples, using a K-Coater and RDS coating rod. The coating weight of adhesive ap plied was ~1.8 g/m ² . A clear polyethylene sealable film was then placed onto the adhesive, and the laminated constructs cured at 25°C for seven days prior to OTR measurements.

In comparative example 5, no adhesive lamination was carried out.

OTR measurements were made as described above. The following re sults were obtained.

Table 9

Commercially, the LA1139-04/LA6029 adhesive is used at a mixed ratio of 1:1 by weight to provide the resulting laminate struc ture with more than suitable adhesion strength to the sealable film. As shown in Example 5a the adhesive at a 1:1 mix ratio not only provides adhesion but also provides a significant im provement of the laminate OTR value. A mix ratio to 1.5 LAI139- 04 to 1 LA6029 is not typically used for commercial lamination of flexible packaging laminates as it introduces undesirable cost and complexity into the process and resulting product. Surprisingly, changing the mix ratio to 1.5 LOCTITE LIOFOL

LAI139-04 to 1 LOCTITE LIOFOL LA6029 as done in example 5b im proved OTR value of the resulting laminate even further. PSIEG032WO /04.07.2022 38 PSIEG032WO-2022090238

Examples 6a , 6b and 6c

In a commercial rotogravure printing press conventional black, cyan, magenta and yellow inks as well as a white ink according to example 1 was printed onto a BOPP substrate of comparative example 1, followed by application of the oxygen barrier coating composition of table 2 with a coating weight of 0,8 g/m ² . The line speed of the rotogravure printing press was 180 m/min, and the drying temperatures in a double drier unit at the end of the printing line were 70°C/100°C.

In example 6a, the obtained sample was hand laminated following typical laboratory methods. An adhesive layer (LOCTITE LIOFOL LA1139-04/LA6029 solvent free adhesive from Henkel mixed in a typical commercially used 1:1 ratio by weight) containing a component that is capable of crosslinking with the polymer of the oxygen barrier composition was applied to the barrier coat ing on the print samples, using a K-Coater and RDS coating rod. The coating weight of adhesive applied was ~1.8 g/m ² . A clear polyethylene sealable film was then placed onto the adhesive, and the laminated construct was cured at 25°C for seven days pri or to OTR measurements.

In example 6b, the obtained sample was hand laminated following typical laboratory methods. An adhesive layer (LOCTITE LIOFOL LA1139-04/LA6029 solvent free adhesive from Henkel mixed in a 1.5:1 ratio by weight) containing a component that is capable of crosslinking with the polymer of the oxygen barrier composition was applied to the barrier coating on the print samples, using a K-Coater and RDS coating rod. The coating weight of adhesive ap plied was ~1.8 g/m ² . A clear polyethylene sealable film was then placed onto the adhesive, and the laminated constructs cured at 25°C for seven days prior to OTR measurements. PSIEG032WO /04.07.2022 39 PSIEG032WO-2022090238

In example 6c, no adhesive lamination was carried out.

OTR measurements were made as described above. The following re sults were obtained.

Table 10

As shown in Example 6a the combination of white ink including a component that is capable of crosslinking with the polymer of the oxygen barrier coating composition and adhesive at a 1:1 mix ratio provides a substantial improvement of the laminate OTR value. Surprisingly, changing the mix ratio to 1.5 LOCTITE LI- OFOL LAI139-04 to 1 LOCTITE LIOFOL LA6029 improved OTR value of the resulting laminate even further.