Printable film
Abstract
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Term
3.2 yearsto projected expiry
Projected expiry 8 December 2029, counted from filing; an application has no term until it is granted.
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13 claims: 7 independent, 6 dependent
- 1Zastrzeżenia patentowe 1. Folia nadająca się do zadrukowania zawierająca podłoże i co najmniej jedną warstwę powierzchniową wytworzoną z kompozycji powłokowej zawierającej spoiwo będące dyspergowalnym w wodzie polimerem, etylenowo nienasycony związek, który jest dyspergowalny w wodzie i mieszalny lub związany z tym dyspergowalnym w wodzie polimerem, oraz środek sieciujący, przy czym środek sieciujący jest odpowiedni do wiązania i skutecznego przyczepiania powłoki do podłoża, etylenowo nienasycony związek zachowuje co najmniej część swojego nienasycenia po reakcji ze środkiem sieciującym, a folia nie zawiera warstwy podkładu.
- 2Folia nadająca się do zadrukowania, jak zastrzeżona w zastrzeżeniu 1, w której wiązanie w końcowym produkcie występuje między środkiem sieciującym a etylenowo nienasyconym związkiem.
- 3Folia nadająca się do zadrukowania, jak zastrzeżona w dowolnym z poprzednich zastrzeżeń, w której:dyspergowalny w wodzie polimer jest obecny w ilości od 10 do 98% wagowych po wysuszeniu kompozycji powłokowej i/lub etylenowo nienasycony związek jest obecny w ilości od2 do 90% wagowych po wysuszeniu kompozycji powłokowej i/lub środek sieciujący jest obecny w ilości od1 do 5% wagowych po wysuszeniu kompozycji powłokowej.
- 4Folia nadająca się do zadrukowania, jak zastrzeżona w dowolnym z poprzednich zastrzeżeń, w której:dyspergowalny w wodzie polimer jest wybrany spośród dyspergowalnych w wodzie akrylanów, uretanów, uretanoakrylanów, kopolimerów styren butadien / bezwodnik maleinowy oraz ich mieszanin i/lub środek sieciujący obejmuje karbodiimidowy środek sieciujący lub azyrydynowy środek sieciujący.
- 5Folia nadająca się do zadrukowania według dowolnego z poprzednich zastrzeżeń, w której etylenowo nienasycony związek może tworzyć wiązanie kowalencyjne z farbą dzięki etylenowo nienasyconym grupom pozostałym w powłoce w czasie, gdy jest na nią nakładana farba.
- 6Folia nadająca się do zadrukowania według dowolnego z poprzednich zastrzeżeń, w której albo:folia zawiera drugą warstwę powierzchniową, odpowiednią dla przyczepności, ewentualnie, w której druga warstwa powierzchniowa jest wytworzona z kompozycji powłokowej, jak określona w dowolnym z zastrzeżeń od1 do 5, niezawierającej warstwy podkładu, albo tylko jedna strona jest powleczona warstwą powierzchniową, a przeciwna strona podłoża jest pokryta warstwą kleju przylepcowego.
- 7Folia nadająca się do zadrukowania, jak zastrzeżona w dowolnym z poprzednich zastrzeżeń, w której podłoże jest wybrane z grupy obejmującej folie polimerowe, folie poliolefinowe, orientowane folie poliolefinowe, papiery, papiery syntetyczne, tkaniny, włókniny, arkusze ceramiczne, arkusze z włókna metalicznego, EP 2 355 982 B1 arkusze metalizowane (folia), folie metaliczne, płyty metaliczne i arkusze wielowarstwowego kompozytu wytworzonego przez połączenie tych materiałów.
- 8Folia zadrukowana obejmująca folię nadającą się do zadrukowania, jak zastrzeżona w dowolnym z poprzednich zastrzeżeń, na którejponadto znajduje sięnadruk.
- 9Sposób wytwarzania folii nadającej się do zadrukowania, jak zastrzeżona w jednym z poprzednich zastrzeżeń od1 do 7,obejmujący etap powlekaniaco najmniejjednej strony podłoża wodną dyspersją zawierającą kompozycję powłokową, jak określonawdowolnymz zastrzeżeń od 1 do 5 i obejmujący ponadto etap suszenia tak otrzymanej powłoki.
- 10Sposób wytwarzania folii zadrukowanej, jak zastrzeżona w zastrzeżeniu 8, obejmujący etapy według 10 zastrzeżenia 9 i obejmujący ponadtoetapy:nanoszenia farby utwardzalnej przez napromienianie na wysuszoną powłokę i utwardzania farby za pomocą promieniowania UV lub EB.
- 11Sposób według zastrzeżenia10, w którym farbęnanosi sięna powłokę, w czasie gdy powłokę nanosi się na folię w etapie powlekaniaapowleczonąfoliędostarcza sięna stanowisko drukarskie.
- 12Folia zadrukowana, jak zastrzeżona w zastrzeżeniu 8,w postaci etykiety, która tofoliajest połączona 15 przedlubpo drukowaniuz warstwą kleju przylepcowego i ewentualnie z folią osłonową.
- 13Pojemnik, na przykład butelka, oznaczony etykietą,jak zastrzeżona wzastrzeżeniu12. EP 2 355 982 B1 Bez pod kład owe podłoże drukowe etykiety Bezpodkładowa powłoka wierzchnia Obróbka koronowa w atmosferze powietrza Polimer zewnętrzny - funkcjonalny polimer wytłaczalny, tj. terpolimer propylen-etylen-butylen Polimer rdzeniowy;albo homopolimer izotaktyczny, polipropylen, albo kopolimer bezładny, propylen - etylen oraz ewentualnie środki matujące i/lub pigmentujące. Polimer zewnętrzny - funkcjonalny polimer wytłaczalny , tj. terpolimer propylen-etylen-butylen Fig. 1 EP 2 355 982 B1 Lista odnośników cytowanych przez zgłaszającego ma jedynie służyć wygodzie czytelnika. Nie stanowi ona części europejskiego dokumentu patentowego. Mimo że wyboru odnośników dokonano z wielką starannością, nie można wykluczyć błędów lub przeoczeń, a EUP nie bierze żadnej odpowiedzialności w tym względzie. ODNOŚNIKI CYTOWANE W OPISIE Dokumenty patentowe cytowane w opisie • EP 410051 Α1 [0006] • WO 02048260 A [0007] • WO 0160878 A [0008] US 20020098340 A [0009] EP 0202812 A[0013] WO 0231016 A [0045]
Independent claims13
166 paragraphs in 5 sections, as filed
[0001] The present invention relates to an improved coating that can be printed. In particular, although not exclusively, the present invention relates to an improved film that is printable, having good adhesion properties when used with radiation curable paint.
[0002] In recent years, the diversity of printed products has required printing on a larger number of different materials in sheets, for example, on paper, synthetic papers, polymeric films, such as thermoplastic resin films, metallic films, metallized sheets, etc. These printed components are printed by methods such as offset printing, gravure printing, flexography, screen printing and letterpress printing. Among these printing methods, the method of using radiation curable paint has recently become popular because the radiation curable paints dry quickly and the method of printing using radiation curable ink is the best to use. It is known that radiation curable paints are useful for printing packaging, labels and non-absorbent printing materials. Radiation curable paints usually contain unsaturated acrylates, polyesters, photoinitiators and additives. However, photoinitiators may be omitted for electron beam hardened paints.
[0003] After depositing the radiation-curable paint on the printing element, the print is exposed to radiation and cures in a split second. Printing speeds of up to 300 m / min are achieved during continuous printing. There is currently a huge demand for sheet-like printable items.
[0004] In printing methods, the printing sheet preferably has the property of good sheet movement and anti-blocking properties, resulting in uniform distribution of paint on the sheet surface, as well as anti-static properties. In addition to these generally required properties, in printing methods using radiation curable ink, the printing sheet requires in particular strong adhesion to radiation curable ink.
[0005] In particular, polymer films printed with radiation curable paint, intended for use as labels, for example in the bottle labeling market, should be resistant to both water freezing conditions (to allow storage of the obtained product in refrigerators or ice containers) and for the sterilization process, for example by exposing them to steam (to ensure that the previously marked bottles can be filled).
[0006] European Patent Application EP-A1-410051 discloses printing sheets comprising a carrier layer and a surface layer on at least one side of this carrier, wherein the surface layer comprises at least an acrylate-based polymer and an unsaturated compound (cinnamic acid or its derivatives ). This document does not contain information on the possibility of replacing cinnamic acid with other monomers.
[0007] WO-A-02/048260 discloses, as it is called, improved binders, ink-receiving compositions and coated substrates containing a binder, particulate filler and mortar. Preferred binders include one or more acrylic copolymers made with at least one monomer that improves wet abrasion resistance. The coating compositions disclosed therein are completely saturated, with the ability to receive ink provided by the mortar and / or filler.
[0008] WO-A-01/60878 discloses mixed polyurethane-poly (vinyl ester) compositions for use as coatings designed for protection and not the ability to absorb ink. IN
This document suggests the use of a water-dispersible hybrid UV coating that is completely cured in the production process.
[0009] US 2002/0098340 discloses a printable film comprising a substrate and at least a surface layer that covers at least one side of the substrate and which contains a water dispersible polymer and an ethylenically unsaturated compound. However, this product can be expensive and difficult to manufacture due to its multi-component nature. This document contains information on applying an intermediate primer between the substrate and the surface layer to ensure a satisfactory level of adhesion.
[0010] However, the above-mentioned materials formed into sheets, especially polymeric films, do not adhere sufficiently to the radiation-curable paint after printing and curing, especially in these extreme conditions. Thus, the printing ink used for printing and radiation cured is problematic because it separates from the polymer film.
[0011] In the field of printable films, improvements are necessary to obtain a product that is economically effective, easy to manufacture, and which also has adequate adhesive properties.
[0012] In a first aspect, the present invention provides a printable film according to claim 1.
[0013] Suitable substrates that can be used as facestock in this invention are polymeric films, in particular polyolefin films, papers, synthetic papers, fabrics, nonwovens, ceramic sheets, metallic plates and sheets of multilayer composite made by combining these materials . For printing films intended for use as labels, polyolefin films are preferred, especially oriented polypropylene films, and even more preferably oriented polypropylene film according to EP-A-0202812.
[0014] The printable films discussed here are films that can be directly coated with paint, i.e. films whose surface layer is strong enough to withstand the pulling of sticky paint, otherwise areas of the surface layer may be peeled off from the surface, which causes a defect known as picking.
[0015] The coating formulation, obtained coating and coated products do not contain a primer. This brings benefits not only in terms of cost, but also in terms of production equipment and its simplicity. In addition, linerless systems enable improved printability. Much of the prior art regarding undercoats contains information unrelated to the undercoat system of the present application.
[0016] In some prior art systems, the printable surface is produced by the interaction between the polymer (e.g. acrylic polymer) and ethylenically unsaturated compound.<sub>®</sub> kiem (for example, Ebecryl<sup>®</sup> from Cytec Industries Inc.). When the film is printed, wet paint adheres to the coated surface, and then, when the printed film is irradiated, the UV initiators (contained in the paint) start a radical curing reaction that causes Ebecryl to crosslink with each other and with the paint and thus binds the paint to the surface foil. One skilled in the art typically avoids the use of crosslinkers to bond the coating to the film because of the fear that a hard, unprintable film will be produced; instead, in prior art systems, a separate primer layer is typically used between them to bond the film to the coating.
[0017] The inventors of the present invention have surprisingly found that a crosslinking agent can be used in the coating formulation to affect the binding without losing other advantages such as good printability. The inventors have found that a crosslinker can be used to bind functional groups on the film surface to functional groups in the components of the coating composition. The cross-linking agent also ensures the film's water resistance without excessive hardening of the product, which means that the surface can still be easily printed. In fact, there is an improvement in printability.
[0018] A crosslinker is used that can provide effective adhesion (and possibly also water resistance), also resulting in effective printability. Nonisocyanate crosslinkers are preferred because the inventors have found that the isocyanate can crosslink spontaneously, resulting in the formation of a hard, non-ink-resistant polyurea component. The inventors have obtained good results with carbodiimide and especially aziridine crosslinkers, and therefore these crosslinkers are preferred. It is clear to those skilled in the art that other crosslinkers that provide a binding effect and provide effective printability are also within the scope of the present invention.
[0019] The system of the present invention can again be contrasted with prior art systems based on primers, in which the bonding is formed by means of a separate primer layer present only between the film and the protective top coat and not present in the top coat itself.
[0020] In the present invention, the crosslinker may usually react with an ethylenically unsaturated compound that may form part of the water dispersible polymer backbone or may not form part of it, and / or may be "hanging groups" attached to the water dispersible polymer backbone. Alternatively, the chemical interaction is a three-way interaction, involving these two substances, as well as a polymer that effectively forms a prepolymer on the film surface to absorb paint and then cure by radiation.
[0021] In addition, the crosslinker is usually present in the coating composition in excess of the amount required for stoichiometric cross-linking of the water-dispersible polymer. This allows a certain amount of crosslinker to remain available for reaction with the ethylenically unsaturated compound.
[0022] In the primer system of the present invention, the crosslinker is preferably present in the entire coating. The crosslinker preferably passes from the film (substrate), where it binds to the functional groups present in it (e.g. acid, hydroxyl and amino), through the entire top protective coating, where it cross-links the polymer and chemically interacts with the ethylenically unsaturated compound, to the surface where blocks ethylenically unsaturated compound, but leaves its functional groups that can bind paint. A key feature of the present invention is that the ethylenically unsaturated compound present in the system retains at least some of its unsaturation at the time paint is introduced into the system. In other words, the coating contains an ethylenically unsaturated compound that is not cured to such an extent that it would completely remove the ethylenic unsaturation from this compound and prevent it from binding to the paint applied to the surface of the coating. The ethylenically unsaturated compound used in the coating formulation of the invention must be capable of (through one or more of its ethylenically unsaturated groups) binding to the paint applied to the coating. A coating formulation initially formulated with an ethylenically unsaturated compound, but then cured before applying the paint, so that the coating remains insufficient for paint adhesion, the number of ethylenically unsaturated groups is not in accordance with the invention.
[0023] The combination of ingredients is such that the crosslinker can be used in excess without producing too cross-linked, hard, non-printable film. The use of beneficial crosslinkers avoids the disadvantage of excessive crosslinking by hydrolysis. The following factors may also play a role and can be changed by a specialist in an appropriate manner: reaction with an ethylenically unsaturated compound; three-way interaction involving the polymer; specific functionality of the substance, including, for example, a limited level of acid functionality in the polymer produced; amount of crosslinker; and monomers selected during the initial polymerization. [0024] The mechanism of chemical interaction between the crosslinking agent and the ethylenically unsaturated compound may optionally be a base-induced nucleophilic addition reaction at the site of the unsaturated (ethylene) bond, for example Michael addition or alternatively / additionally Baylis-Hillman reaction.
[0025] The coating composition is preferably an aqueous composition; alternatively, a solvent based system (e.g. MEK - methyl ethyl ketone - or isopropyl acetate) may be used. Organic solvent based systems can optionally be used in combination with polyester binders and / or aromatic crosslinkers.
[0026] The ethylenically unsaturated compound is preferably dispersible or miscible (as opposed to soluble) in water.
[0027] The coating of the present invention may form a layer that covers at least one side of the substrate mentioned above. The water-dispersible polymer can be selected as a non-limiting example from water-dispersible acrylates, urethanes, urethaneacrylates, styrene butadiene / maleic anhydride copolymers and mixtures thereof. The water-dispersible polymer forms a smooth, film-forming and paint-receiving surface.
[0028] Acrylic polymers used as the water-dispersible polymer include (co) polymers obtained by free radical addition polymerization of at least one (meth) acrylic type monomer and optionally other vinyl or allyl compounds. Acrylic polymers provide a smooth, film-forming and paint-receiving surface.
[0029] Many different acrylic polymers meet this requirement. Suitable acrylic polymers are homopolymers of (meth) acrylic acid or alkyl (meth) acrylate, the alkyl radical containing from 1 to 10 carbon atoms, or copolymers of two or more of these (meth) acrylic monomers and optionally other vinyl or allyl compounds.
[0030] As stated above, a water-dispersible urethane polymer can also be used. As with acrylic polymer, it is important that this urethane polymer can provide a smooth, film-forming and paint-receiving surface.
[0031] Many different urethane polymers meet this requirement. Suitable urethane polymers are, for example, the reaction product of an isocyanate-terminated polyurethane prepolymer formed by reacting at least an excess of organic polyisocyanate, an organic compound containing at least two isocyanate-reactive groups and an isocyanate-reactive compound containing anionic salt function (or acid group, which can then be converted into these anionic salt groups) or nonionic groups and a chain-extender containing active hydrogen.
[0032] The water-dispersible polymer has sufficiently low levels of reactive functional groups to limit the crosslinking density to provide sufficient water resistance for the properties of the final film, while leaving a surface that accepts printing inks, these inks being curable UV, water or solvent based. The preferred content of reactive functional groups is below 10% by weight.
[0033] The amount of water-dispersible polymer is for example from 10 to 98%, preferably 60-95%, more preferably 74-92% by weight after drying the coating composition.
[0034] The surface layer also contains an ethylenically unsaturated compound.
[0035] The ethylenically unsaturated compound is selected so that it is miscible in the wet stage in the aqueous phase and is compatible in the dry stage with the water-dispersible polymer alone. As a result, the ethylenically unsaturated compound acts as a plasticizer for the surface layer after curing, allowing easy penetration through radiation-curable paint. Alternatively, or also, an ethylenically unsaturated compound may be provided as part of the water-dispersible polymer itself - for example in the form of its functional side chain.
[0036] The ethylenically unsaturated compound must also, when the printed film is irradiated to cure the paint, be able to react with unsaturated paint components that have penetrated into the surface layer.
[0037] This reaction between the ethylenically unsaturated surface layer compounds and the radiation-curable unsaturated paint compounds creates chemical bonds between these compounds and at the same time crosslinks the surface layer, thereby producing a final resistant product.
[0038] Preferably, the ethylenically unsaturated compound contains from 1 to 10 double bonds per molecule, and even more preferably from 2 to 5 double bonds per molecule (or per functional group in which the compound is provided in the form of a side chain or otherwise as part of a water dispersible polymer).
[0039] Suitable ethylenically unsaturated compounds are [alpha], [beta] -ethylenically unsaturated ester derivatives such as acrylic or methacrylic acids, itaconic or cytraconic acids, maleic acid or fumaric acid, etc. with polyols or alkoxylated polyols. ethylenically unsaturated alcohols and methoxylated varieties such as Desmodur (Bayer), trifunctional isocyanate reacted with hydroxyethyl methacrylate. In other words, the ethylenically unsaturated compounds used in the present invention may contain one or more urethane bonds in addition to or instead of one or more ester bonds.
[0040] Suitable polyols include saturated aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, neopentyl glycol, 1,3- and 1,4-butanediol, 1,5-pentanediol, and 2-methyl-1,3-propanediol. Glycerol, 1,1,1-trimethylolpropane, bisphenol A and its hydrogenated derivatives may also be used. Suitable alkoxylated polyols include ethoxylated or propoxylated polyols derived from the above.
[0041] Examples of ethylenically unsaturated compounds that can be used according to the invention are polyfunctional acrylates such as difunctional acrylates, e.g. 1,4-butanediol diacrylate, 1,6-hexane diacrylate
Diol, neopentyl glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, 2,2-dionol diacrylate, bisphenol A diacrylate, etc., trifunctional acrylates such as triproprylate triacrylate acrylate ., tetrafunctional acrylates, etc.
[0042] It should be understood that methacrylate derivatives corresponding to these acrylate derivatives can also be used.
[0043] In addition, polyallyl derivatives such as tetraallyloxyethane have also been found to be suitable. Suitable materials in this regard are commercially available from Cytec Industries Inc. under the trade name Ebecryl.
[0044] The amount of ethylenically unsaturated compound may, for example, be from about 2 to about 90% by weight of the acrylic polymer, and preferably is from about 2 to about 15% or from 2 to 10% (in this specification all percentages are given relative to dry weight).
[0045] Suitable crosslinkers include carbodiimide and aziridine crosslinkers and crosslinkers disclosed for example in WO 02/31016. These crosslinkers can form bonds between carboxy, hydroxyl or amino functional groups at the junction of the substrate and the top protective coating.
[0046] The crosslinking agent may also improve the hardness and / or water resistance of the surface layer deposited on the film and, consequently, the final product, while obtaining a surface layer which, when cured, allows it to easily penetrate radiation curable paint by irradiation.
[0047] For example, 1-10% crosslinker may be used or more preferably 1-5% or 2.5%.
[0048] For example, if the polymer is an acrylic polymer, the amount of crosslinker may be up to 10% by weight of the acrylic polymer, and preferably is from 1 to 5% by weight of the acrylic polymer.
[0049] The surface layer may, if necessary, contain all other additional agents to prevent adhesion of one sheet to another and to improve sheet movement properties, anti-static properties, non-translucency properties etc. These additional agents are generally added in a total amount not exceeding about 40% by weight of the polymer acrylic. As already stated, an additional agent can be used, for example a pigment such as polyethylene oxide, silica, silica gel, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, aluminum oxide , zinc oxide, titanium oxide, lithopone, satin white, etc., and cationic, anionic, antistatic, etc.
[0050] For example, an ink adhesion promoter and surface hardener, e.g. colloidal silica, can be used. The ink adhesion promoter and surface hardener may be present, for example, in an amount of from 5 to 20%.
[0051] Suitable anti-blocking substances that can be used include silica, clays, non-film-forming polymers (e.g. PMMA dispersions and granules), for example in an amount of from 0.1 to 3%, preferably from 0.1 to 1.0%.
[0052] Water can be used in an amount resulting in a coating having a solids content of about 5 to 20%. [0053] According to the present invention, the surface layer can be applied to the substrate in the form of a<sub>2</sub> water content in an amount from about 0.5 to about 2.5 g / m2<sup>2</sup> roller coating method, scraper coating 6
In this case, spray coating, coating with an air knife, coating with a dosing rod, gravure coating with reverse gravity etc., followed by drying, e.g. in an air oven (hot air oven).
[0054] Thus, after the drying step, the surface layer comprises a water-dispersible polymer, easily cross-linked with a crosslinker and, incorporated into the acrylic polymer matrix, an ethylenically unsaturated compound. This allows easy penetration of the curable by irradiating the paint deep into the surface layer, as well as its subsequent reaction with an ethylenically unsaturated compound.
[0055] The present invention does not use a primer. However, before applying the surface layer, if a sufficient number of functional groups are not available at the surface of the substrate, it may optionally be pre-treated in a conventional manner to improve wetting and adhesion. To this end, the substrate may be pre-treated, for example, using a corona effect, corona, flame or oxidizing chemical agents, but it should be understood that all known techniques to improve the surface of the sheet-like element in terms of applying the composition may be appropriate.
[0056] The opposite side of the substrate, namely the side not covered with the surface layer, may be covered with a pressure-sensitive adhesive layer, which includes a commonly used pressure-sensitive adhesive. In addition, if necessary, a pressure sensitive adhesive layer may be covered by a film or cover sheet comprising an release agent. This laminate comprising the printing sheet according to the invention can be used as an adhesive label that can be applied to most types of surfaces.
[0057] A further aspect of the invention therefore relates to a printable film intended for labels, comprising a substrate whose only one side is coated with a surface layer and whose other side is coated with a layer of pressure-sensitive adhesive, which layer is covered with a film or cover sheet.
[0058] Another aspect of the present invention relates to a method of producing a printable film, comprising the step of coating at least one side of a substrate with an aqueous dispersion comprising a water dispersible polymer and an ethylenically unsaturated compound and a suitable crosslinking agent and optionally conventional additives, and further comprising a drying step such produced coating.
[0059] The method of producing the printable film may optionally include, prior to the coating step of at least one side of the substrate, an additional substrate pretreatment step (such as corona treatment).
[0060] In a particular embodiment regarding the production of the label, only one side of this substrate is coated with a surface layer and the thus obtained one-sided coated substrate is coated with pressure-sensitive adhesive or, in another version, the pressure-sensitive adhesive can be transferred from the casing material with which the coated substrate is connected.
[0061] A further object of the present invention relates to a printed film comprising a substrate, at least one side of which is coated with a surface layer comprising a water dispersible polymer and an ethylenically unsaturated compound, and a suitable crosslinking agent, said coated side of the substrate being printed by conventional methods such as printing offset, gravure printing, flexography, screen printing and letterpress printing, using radiation curable paint and then radiation curable.
[0062] Paint formulations intended for radiation cure usually contain pigments, carrier, solvent and additives. Solvents in these systems are low viscosity monomers that can react on their own (i.e. used as reactive solvents). The carrier usually consists of a resin derived from unsaturated monomers, prepolymers or oligomers, such as derivatives of acrylates, which can react with an ethylenically unsaturated surface layer compound. In the case of UV paint, "additives" contain a large amount of photoinitiators that react to photons of UV light, starting the reaction of the system.
[0063] The UV paint formulation can be generally represented as follows:
Pigment
Prepolymers Carrier Photoinitiators Other additives
15-20% 20 - 35% 10-25% 2-10% 1-5%.
[0064] In the case of electron beam curable paint, the "additives" generally contain no photoinitiator. [0065] Low viscosity monomers, sometimes called diluents, have the ability to chemical reactions that cause their complete incorporation into the final polymer matrix.
[0066] The carrier provides a "hard resin" formulation part. Usually derived from synthetic resins, such as urethanes, epoxies, polyesters modified by reaction with compounds containing ethylene groups, such as, for example, (meth) acrylic acid, hydroxyethyl (meth) acrylate, reaction product of caprolactone with unsaturated compounds hydroxyl and the like.
[0067] Appropriate modifications may be made in the selection of prepolymers and monomers used to obtain the viscosities required for the various application methods.
[0068] Another aspect of the invention relates to a method of making a printed film comprising the steps of:
a) coating the substrate with an aqueous dispersion comprising a water-dispersible polymer, an ethylenically unsaturated compound and a suitable cross-linking agent;
b) drying the coating thus obtained;
c) applying irradiation paint to the dried coating;
d) curing the paint with UV or EB radiation.
[0069] It should be noted that the various steps of this process can be carried out under the same conditions (speed, costs, etc.) as with a conventional surface layer.
[0070] Finally, the invention also relates to a printed film obtained by applying ink to a printable film according to the invention, and in particular to the printed label thus obtained.
[0071] An example of the coated film of the present invention is shown schematically and without scale, in Figure 1.
EP 2 355 982 B1
EXAMPLES [0072] The following Examples are provided to illustrate the present invention and can be used to coat a substrate, film, standard techniques.
[0073] The raw materials used in these examples are from the following suppliers: Cytec Surface Specialties SA / NV Anderlechtstraat, 33, 1620 Drogenbos; European headquarters Alberdingk Boley GmbH, ul. Duesseldorfer 53, 47829 Krefeld, Germany; Cray Valley Laporte Road, Stallingborough, North East Lincolnshire, DN41 8DR; Xama Aziridenes Flevo Chemie (Netherlands) BV, Havendijk 8a, 3846 AD Harderwijk, the Netherlands; Gasil Silica INEOS Silicas Limited, Warrington, England WA5 1AB; Baxenden Chemicals Ltd, Paragon Works, Worsiey Street, Rising Bridge, Accrington, BB5 2SL; Bayer Material Science 100 Bayer Road, Pittsburgh, PA 15205; Grace Davison Oak Park Business Center, Alington Road, Little Barford, St. Neots, Cambs PE19 6WL; NIPPON SHOKUBAI EUROPE NV Haven 1053, Nieuwe Weg1, B2070 Zwijndrecht, Belgium; Nissando Industries Inc. 1-2-3, Onodai Midori-ku, China; DSM NeoResins + Sluisweg 12, PO Box 123 5140 AC Waalwijk, The Netherlands.
Sample 1 [0074]
Acrylic copolymer (Craymul 8500; Cray Valley) Krzemionka (Gasil HP250; Crossfield)
Colloidal silica (Ludoxx30; GRACE Davison) Ebecryl 160 (Cytec)
82,8(74,0-90,9)%
0,2(0,1-1,0)% (5-20)% (2-10)%
XAMA - 7 (polyfunctional aziridine crosslinker; Bayer Polymers) 2 (2-5)%
Water for solids in the coating in an amount of approx
Sample 2 [0075]
Acrylic copolymer (Craymul 8405; Cray Valley) Silica (Seahostar KE250; Nippon Shokubai) Colloidal silica (Bindzil 15/500; GRACE Davison) Ebecryl 160 (Cytec)
5-20%
81,5(74,0-90,9)%
0,5(0,1-1,0)%
5-20% (2-10)%
PFAZ 322 (polyfunctional aziridine crosslinker; Bayer Polymers) 3 (2-5)%
Water for solids in the coating in an amount of approx
Sample 3
5-20% [0076]
EP 2 355 982 B1
PU dispersion (Witcobond 315-40; Baxenden Chemicals)
Acrylic copolymer (Craymul 8500; Cray Valley)
Silica (Seahostar KE250; Nippon Shokubai)
Colloidal silica (Ludox x30; GRACE Davison)
Ebecryl 160 (Cytec)
XAMA-2 (polyfunctional aziridine crosslinker; Bayer Polymers) 3.7 (2-5)% Water for obtaining solids in the coating in an amount of about 5-20%
33%
42,8 (41,0 - 57,9)%
0.5 (0.1 - 1.0)% (5 - 20)% (2-10)% [0077] (The preferred ranges of the listed substances in samples from 1 to 3 are given in brackets, and the numbers before the brackets are suggested preferred ranges, are examples of the compositions contemplated). [0078] The following more specific formulations of the invention were prepared, optionally in a form suitable for laboratory testing, in the absence of said anti-blocking component, and tested as described:
Example 1 [0079]
<td>Ingredient</td><td>% dry matter</td><td>Description</td>
<td>Alberdingk U3305</td><td> 76,96</td><td>PU-acrylate dispersion</td>
<td>Ludox X30</td><td> 10,00</td><td>Colloidal silica</td>
<td>Anti-blocking agent</td><td> 1,00</td><td>PMMA in the form of particles</td>
<td>Sartomer CN133</td><td> 7,00</td><td>Aliphatic Oligomer Triacrylate</td>
<td>Dowfax 2A1</td><td> 0,04</td><td>Surfactant, dispersion</td>
<td>CX 100</td><td> 5,00</td><td>Aziridine Crosslinker (DSM)</td>
Example 2 [0080]
<td>Ingredient</td><td>% dry matter</td><td>Description</td>
<td>Ucecoat 7655</td><td> 85,00</td><td>PU Acrylate from Cytec with ethylenic unsaturation built on a polymer backbone</td>
<td>Ludox X30</td><td> 10,00</td><td>Colloidal silica</td>
<td>Anti-blocking agent</td><td> 1,00</td><td>PMMA in the form of particles</td>
<td>PZ-28</td><td> 4,00</td><td>Aziridine Crosslinker (PolyAziridine, LLC)</td>
Example 3 [0081]
EP 2 355 982 B1
<td>Ingredient</td><td>% dry matter</td><td>Description</td>
<td>Alberdingk U3305</td><td> 76,96</td><td>PU-acrylate dispersion</td>
<td>Ludox X30</td><td> 10,00</td><td>Colloidal silica</td>
<td>Anti-blocking agent</td><td> 1,00</td><td>PMMA in the form of particles</td>
<td>Sartomer CN 133</td><td> 7,00</td><td>Aliphatic Oligomer Tri-acrylate</td>
<td>Dowfax 2A1</td><td> 0,04</td><td>Surfactant, dispersion</td>
<td>Carbodilite E-03A</td><td> 5,00</td><td>Carbodiimide crosslinker (Nissindo Industries)</td>
Example 4 [0082]
<td>Ingredient</td><td>% dry matter</td><td>Description</td>
<td>Ucecoat 7655</td><td> 64,56</td><td>PU Acrylate from Cytec with ethylenic unsaturation built on a polymer skeleton</td>
<td>Ludox X30</td><td> 10,00</td><td>Colloidal Silica (Grace Davidson)</td>
<td>Anti-blocking agent</td><td> 1,00</td><td>PMMA in the form of particles</td>
<td>CX 100</td><td> 4,00</td><td>Aziridine Crosslinker (DSM)</td>
<td>R610</td><td> 20,00</td><td>PU dispersion (DSM)</td>
Example 5 [0083]
<td>Ingredient</td><td>% dry matter</td><td>Description</td>
<td>Ucecoat 7655</td><td> 77,96</td><td>PU Acrylate from Cytec with ethylenic unsaturation built on a polymer skeleton</td>
<td>Ludox X30</td><td> 10,00</td><td>Colloidal silica</td>
<td>Anti-blocking agent</td><td> 1,00</td><td>PMMA in the form of particles</td>
<td>CX 100</td><td> 4,00</td><td>Aziridine crosslinker</td>
<td>Sartomer 454</td><td> 7,00</td><td>Ethoxylated TMPTA (Sartomer)</td>
<td>Dowfax 2A1</td><td> 0,04</td><td>Surfactant, dispersion</td>
[0084] Other more specific formulations of the invention contemplated are as follows: Example 6 [0085]
EP 2 355 982 B1
<td>Ingredient</td><td>% dry matter</td><td>Description</td>
<td>Alberdingk U3305</td><td> 76,96</td><td>PU-acrylate dispersion</td>
<td>Bindzil 30/310</td><td> 10,00</td><td>Colloidal silica</td>
<td>Anti-blocking agent</td><td> 1,00</td><td>PMMA in the form of particles</td>
<td>Ebecryl1160</td><td> 7,00</td><td>Ethoxylated TMPTA (Cytec)</td>
<td>Dowfax 2A1</td><td> 0,04</td><td>Surfactant, dispersion</td>
<td>CX 100</td><td> 4,00</td><td>Aziridine crosslinker</td>
Example 7 [0086]
<td>Ingredient</td><td>% dry matter</td><td>Description</td>
<td>Alberdingk U3305</td><td> 76,96</td><td>PU-acrylate dispersion</td>
<td>Bindzil 30/310</td><td> 10,00</td><td>Colloidal silica</td>
<td>Anti-blocking agent</td><td> 1,00</td><td>PMMA in the form of particles</td>
<td>Sartomer 454</td><td> 7,00</td><td>Ethoxylated TMPTA</td>
<td>Dowfax 2A1</td><td> 0,04</td><td>Surfactant, dispersion</td>
<td>Ucarlink XL29SE</td><td> 5,00</td><td>Carbodiimide Crosslinker (Dow Chemicals)</td>
[0087] The systems of these samples and examples should have a service life of about 8 to 12 hours before the crosslinker is used. However, adding an additional amount of crosslinker activates the formulation without significantly affecting the properties of the final film.
[0088] After coating the film with the above specific formulations of Examples 1 to 5, the resulting coated film was dried in an air oven and then printed in a screen printing process using <sub>2</sub> commercially available UV curable inks in an amount of 5 to 15 g / m2<sup>2</sup>. Examples are RN752 and 650-CWHD paints from FUJIFILM SERICOL, UVSF-172 paint from PARAGON INKS, paints from the RSP series from NORCOTE or Combiwhite USW90004 and UVOSCREEN II (™) from FLINT INKS.
[0089] The thus obtained printed film was UV cured, using typical UV lamp capacities 100-200 W / cm, at typical press speeds of 50-100 m / min.
[0090] The printed film finally obtained was tested by the following method:
Exposure to extreme humidity at high temperatures (usually> 90 ° C) and low temperatures (0 ° C) followed by immediate scratches. Each of Examples 1 to 5 successfully passed the high temperature test, and Example 3 successfully passed the modified low temperature test, 4 ° C.
[0091] Similar results are expected for each of Examples 6 and 7 and specific Examples formulated with Samples 1 to 3.
[0092] These results show that the new layless system of the present invention provides excellent printed film suitable for labeling, for example in the beverage industry.
EP 2 355 982 B1
Contents5
73 members in 17 offices
Priority claims8
| Document | Office | Kind | Date |
|---|---|---|---|
| 0822412 | United Kingdom | A | |
| 0822412 | United Kingdom | A | |
| 09771403 | European Patent Office (EPO) | A | |
| 2009051670 | United Kingdom | W | |
| 2009051670 | United Kingdom | W | |
| EP20090771403 | – | – | – |
| GB20080022412 | – | – | – |
| WO2009GB51670 | – | – | – |
Members73
| Document | Office | Kind | |
|---|---|---|---|
| AU2009326206A1 | Australia | A1 | |
| CA2743388A1 | Canada | A1 | |
| WO2010067111A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2010067111A3 | World Intellectual Property Organization (WIPO) | A3 | |
| GB201106616D0 | United Kingdom | D0 | |
| MX2011005716A | Mexico | A | |
| GB2476438A | United Kingdom | A | |
| EP2355982A2 | European Patent Office (EPO) | A2 | |
| KR20110098808A | Republic of Korea | A | |
| US2011236611A1 | United States of America | A1 | |
| CN102227315A | China | A | |
| GB201115729D0 | United Kingdom | D0 | |
| GB2476438B | United Kingdom | B | |
| US2011300349A1 | United States of America | A1 | |
| US2012040153A1 | United States of America | A1 | |
| GB2483169A | United Kingdom | A | |
| MY145643A | Malaysia | A | |
| GB201202209D0 | United Kingdom | D0 | |
| GB201203170D0 | United Kingdom | D0 | |
| GB201204032D0 | United Kingdom | D0 | |
| GB2485933A | United Kingdom | A | |
| US2012156403A1 | United States of America | A1 | |
| US2012156411A1 | United States of America | A1 | |
| GB2486831A | United Kingdom | A | |
| GB2486835A | United Kingdom | A | |
| US2012164362A1 | United States of America | A1 | |
| US2012164404A1 | United States of America | A1 | |
| US2012171436A1 | United States of America | A1 | |
| US2012171458A1 | United States of America | A1 | |
| GB2483169B | United Kingdom | B | |
| JP2012136700A | Japan | A | |
| GB2485933B | United Kingdom | B | |
| DE112009003530T5 | Germany | T5 | |
| JP2012197439A | Japan | A | |
| DE112009005034A5 | Germany | A5 | |
| GB2486831B | United Kingdom | B | |
| GB2486835B | United Kingdom | B | |
| DE112009005259A5 | Germany | A5 | |
| DE112009005296A5 | Germany | A5 | |
| US8497013B2 | United States of America | B2 | |
| US8551605B2 | United States of America | B2 | |
| US8551606B2 | United States of America | B2 | |
| US8557371B2 | United States of America | B2 | |
| US8563119B2 | United States of America | B2 | |
| US8568863B2 | United States of America | B2 | |
| KR101359335B1 | Republic of Korea | B1 | |
| US8658253B2 | United States of America | B2 | |
| US2014141186A1 | United States of America | A1 | |
| CA2743388C | Canada | C | |
| EP2355982B1 | European Patent Office (EPO) | B1 | |
| DK2355982T3 | Denmark | T3 | |
| ES2525647T3 | Spain | T3 | |
| EP2821238A1 | European Patent Office (EPO) | A1 | |
| PL2355982T3This record | Poland | T3 | |
| AU2009326206B2 | Australia | B2 | |
| CN104693927A | China | A | |
| JP2016006181A | Japan | A | |
| US9238750B2 | United States of America | B2 | |
| HK1207105A | Hong Kong, China | A | |
| HK1207105A1 | Hong Kong, China | A1 | |
| BRPI0921545A2 | Brazil | A2 | |
| JP5912581B2 | Japan | B2 | |
| US9376590B2 | United States of America | B2 | |
| JP6199345B2 | Japan | B2 | |
| US9816005B2 | United States of America | B2 | |
| US2018044548A1 | United States of America | A1 | |
| EP2355982B2 | European Patent Office (EPO) | B2 | |
| ES2525647T5 | Spain | T5 | |
| PL2355982T5 | Poland | T5 | |
| EP2821238B1 | European Patent Office (EPO) | B1 | |
| BRPI0921545B1 | Brazil | B1 | |
| PL2821238T3 | Poland | T3 | |
| ES2823980T3 | Spain | T3 |
Numbers
- Publication, DOCDB
- 2355982
- Publication, EPODOC
- PL2355982T
- Application
- 771403
- Application, DOCDB
- 09771403
- Application, EPODOC
- PL20090771403T
Titles2
- English
- PRINTABLE FILM
- Polish
- Folia nadająca się do zadrukowania
Classification
- CPC, 56
- C09D175/14
- B41M5/5254
- B41M5/0011
- B41M5/50
- C09D175/04
- C09D7/61
- C09D7/63
- B41M5/52
- B41M7/0072
- B41M2205/24
- Y10T428/1476
- Y10T428/13
- Y10T428/24802
- Y10T428/2848
- Y10T428/2839
- Y10T428/28
- Y10T428/1352
- Y10T428/24934
- Y10T428/31895
- Y10T442/60
- Y10T428/31678
- Y10T428/31938
- Y10T428/31554
- Y10T442/378
- Y10T428/31924
- Y10T428/31692
- Y10T442/3602
- Y10T428/249924
- Y10T428/31667
- Y10T428/31928
- Y10T428/31909
- Y10T428/31699
- Y10T442/30
- Y10T428/31609
- Y10T428/31993
- Y10T442/20
- Y10T428/31551
- Y10T428/31573
- Y10T428/31855
- Y10T428/31906
- Y10T428/31591
- Y10T442/659
- Y10T442/678
- Y10T428/31935
- Y10T428/31587
- Y10T442/656
- Y10T428/31703
- Y10T428/31598
- Y10T428/31913
- Y10T428/31605
- Y10T442/3886
- Y10T442/3415
- C09D133/08
- C09D125/08
- C09D175/16
- B32B1/00
- IPC, 3
- B41M5 52
- B32B1 00
- B41M5 00