PRINTED AND COATED RELEASE FILM

Abstract

The invention relates to a release film comprising a substrate layer, a printed image, and a release coating, wherein the printed image is disposed at least partially between the substrate layer and the release coating, wherein the printed image includes at least one UV-curable dye, and wherein the release coating includes a UV-curable polysiloxane.

Description

Printed and coated release film

[0001] The invention relates to a release film comprising a carrier layer, a printed image and a release coating, wherein the printed image is at least partially arranged between the carrier layer and the release coating, wherein the printed image comprises at least one UV-cured ink, and wherein the release coating comprises a UV-cured polysiloxane; the use of the release film as packaging material; and a method for producing the release film.

[0002] Release films are widely used as peelable protective films for adhesive tapes, self-adhesive labels, or adhesive sanitary and hygiene products to prevent these single- or double-sided adhesive products from sticking together during storage or processing. For this purpose, release films must exhibit good release properties against adhesives such as pressure-sensitive adhesives or other adhesive materials. To ensure these properties, release films often have a release coating, which may be based on a polysiloxane, for example.

[0003] Furthermore, it is often desirable to print on the release liners for informational, aesthetic, production-related, or other reasons. For example, colored tactile, control, and / or print marks—that is, colored markings—can be printed at specific intervals on the backing side next to or beneath the release coating of the release liner. These colored tactile, control, and / or print marks then enable precise optical positioning of the release liners and the products relative to each other during the manufacture or packaging of products such as sanitary or hygiene products in a dedicated device.

[0004] WO 1993 / 23310 concerns a flexible container for packaging products with a pressure-sensitive adhesive, such as sanitary napkins. The container is formed from a paper or plastic film coated on one side with a layer of silicone, the container being designed such that the silicone coating defines the inner surfaces of the container. Due to the non-stick properties of the silicone coating, the usual protective insert for the adhesive on the packaged product is unnecessary.

[0005] WO 1990 / 007560 discloses a method for providing at least one surface of a substrate (support element), in particular a liner, with at least one coating at least one release agent (sticky substance repellent) in such a way that partial areas with different release forces are formed in the form of a grid.

[0006] WO 2005 / 075592 concerns a release liner with a planar substrate and a release liner applied to it. The release liner is suitable for backing self-adhesive material with a layer of pressure-sensitive adhesive. It has a relief structure with raised ridges that essentially form complementary channels in the pressure-sensitive adhesive layer, allowing trapped air to escape during application.

[0007] WO 2007 / 079921 discloses a method for producing a liner for releasably covering adhesive surfaces, in particular for releasably covering adhesive surfaces of adhesive tapes or adhesive films, comprising the following steps: providing a carrier layer; applying one or more raised structures to at least one surface of the carrier layer, wherein the structure or structures are firmly bonded to this surface; and covering the surface and the structure or structures bonded to it with a detachable layer.

[0008] US 2004 / 137242 discloses cationic radiation-curable inks that do not exhibit ghosting when coated with solvent-free, radiation-curable silicone release agents. When aggressive solvent-based adhesives are poured onto ink applied to a substrate and removed after drying, no ghosting is observed. The result is the ability to print graphics onto a substrate and then cover the substrate with a silicone release agent and an adhesive layer that maintains acceptable clarity after the release agent is removed.

[0009] EP 2 576 383 Bl discloses a container with features that indicate tampering or previous attempts to open the container. The container includes a pull tab for opening it to gain access to the interior and its contents. The container also includes devices for the pull tab, which must be at least partially separated from a container substrate to allow access to the pull tab. Separation of the pull tab devices provides information about tampering attempts or previous attempts to open the container.

[0010] DE 19 820 274 ​​discloses a plastic film with a non-stick coating, in particular silicone, for producing a wrapping package with embossed edge closure strips.

[0011] DE 20 2014 105 973 Ul discloses a film with at least one layer containing at least one homo- or copolymer, wherein at least in certain areas above said layer a heat-resistant coating is applied and wherein a coating with at least one polysiloxane is applied over the heat-resistant coating, at least in some areas.

[0012] It is known from the prior art to print a carrier film with, for example, a solvent-based ink, e.g., based on nitrocellulose, in a first step and then, in a second step, to apply a release coating to the dried ink.

[0013] However, the production of such release films is comparatively complex due to the separate steps for printing and subsequent application of the release coating, and there is a need for improved release films which can be produced using improved processes.

[0014] It is an object of the invention to provide improved separating films and a method for their production.

[0015] This problem is solved by the subject matter of the patent claims.

[0016] A first aspect of the invention relates to a release film comprising a carrier layer, a printed image and a release coating, wherein the printed image is arranged at least partially between the carrier layer and the release coating, so that the printed image is at least partially covered by the release coating, wherein the printed image comprises at least one UV-cured ink, and wherein the release coating comprises a UV-cured polysiloxane.

[0017] It was surprisingly discovered that a work step (printing step) can be eliminated in the production of the release film according to the invention, thereby significantly reducing production time, possibly even halving it. Printing, curing of the printed image, application of the release coating, and curing of the release coating can be carried out within a few seconds in a single operation on a single device. On an existing production line, output can thus be significantly increased, possibly even doubled.

[0018] Furthermore, it was surprisingly found that more precise control is possible in the production of the release film according to the invention, since printing and application of the release coating can be carried out in a single, coordinated operation. Undesirable effects, which occur during the conventional second step for release coating using the film roll, can be suppressed in this way.

[0019] Furthermore, it was surprisingly found that the adhesion between the printed image and the release coating is improved during the production of the release film according to the invention, particularly when solvent-free printing inks are used. Otherwise, the release coating may develop insufficient adhesion to an ink layer that still contains residual solvent, for example, if this layer is nitrocellulose-based and therefore requires a solvent.

[0020] The film according to the invention is a release liner, i.e., it is suitable and intended for use as a peelable protective film for self-adhesive products, such as adhesive tapes, self-adhesive labels, or adhesive sanitary and hygiene products. The release liner according to the invention can also be referred to synonymously as a "protective film".

[0021] The separating film according to the invention is particularly suitable for use in packaging of sanitary or hygiene articles, preferably selected from the group comprising sanitary napkins and panty liners (sanitary napkin packaging, siliconized single wrap film).

[0022] Preferably, the separating film according to the invention has a total layer thickness of at least 5 pm, more preferably at least 10 pm. More preferably, the separating film according to the invention has a total layer thickness in the range of 5 pm to 50 pm, more preferably in the range of 10 pm to 45 pm, and even more preferably in the range of 15 pm to 40 pm. Suitable methods for determining the layer thickness are known to those skilled in the art. According to the invention, the layer thickness is preferably determined by microtome sectioning.

[0023] The film according to the invention comprises a carrier layer. In principle, any layer made of a printable material is suitable as a carrier layer within the meaning of the invention. Preferably, the carrier layer is based on a polymer or a mixture of several polymers, which are preferably thermoplastic, and particularly preferably selected from the group consisting of polyolefins, polyamides, polyesters and copolymers and / or mixtures of at least two monomers of the aforementioned polymers.

[0024] Particularly preferred are polyolefins, mixtures of several polyolefins, or mixtures of several polyolefins with one or more other polymers. The support layer is particularly preferably based on polyethylene, polypropylene, or a mixture of polyethylene and polypropylene.

[0025] Preferably, thermoplastic polyolefins, thermoplastic olefin homo- or copolymers of α,β-unsaturated olefins with 2 to 10 carbon atoms, such as polyethylene (PE, in particular LDPE or HDPE), polypropylene (PP), polybutylene (PB), polyisobutylene (PI), copolymers and / or mixtures of at least two of the aforementioned polymers, can be used to produce the support layer.

[0026] "LDPE" refers to low-density polyethylene, which has a density in the range of 0.86-0.93 g / cm³. 3 exhibits and is characterized by a high degree of branching of the molecules.

[0027] "HDPE" refers to high-density polyethylene, which has only a slight branching of the molecular chain, with a density in the range between 0.94 and 0.97 g / cm³. 3 It may be located. Preferred polyolefins for the production of the support layer are ethylene homo- or copolymers and propylene homo- or copolymers.

[0028] Where polyamides are used to produce the substrate layer, thermoplastic aliphatic, semi-aromatic, or aromatic polyamide homo- or copolymers are suitable. Such polyamides are polyamides made from diamines such as aliphatic diamines with 2-10 carbon atoms, in particular hexamethylenediamine, or aromatic diamines with 6-10 carbon atoms, in particular p-phenylenediamine, and dicarboxylic acids such as aliphatic or aromatic dicarboxylic acids with 6-14 carbon atoms, such as adipic acid, terephthalic acid, or isoterephthalic acid. Furthermore, the polyamides may be made from lactams with 4-10 carbon atoms, such as e-caprolactam. Particularly suitable polyamides for producing layer (a) are, for example, PA 6, PA 12, PA 66, PA 61, PA 6T, and / or mixtures of at least two of the aforementioned polyamides.

[0029] Thermoplastic, aliphatic, semi-aromatic, or aromatic polyesters, homo- or copolymers, can be used as polyesters for the production of the support layer. Such polyesters are derived from polyols such as ethylene glycol or 1,4-butanediol and dicarboxylic acids or dicarboxylic acid derivatives such as adipic acid and / or terephthalic acid. According to the invention, polycarbonates (PC) can also be used as polyesters for the production of the support layer(s). Polybutylene adipate (PBA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), or the corresponding copolymers are particularly suitable.

[0030] The substrate layer can be colored and optionally equipped with pigments, or it can be transparent to light. Colored substrate layer is preferred.

[0031] Preferably, the support layer according to the invention has a thickness of at least 5 mHi, more preferably at least 10 mHi. More preferably, the support layer according to the invention has a thickness in the range of 5 mHi to 50 mHi, more preferably in the range of 10 mHi to 45 mHi, and even more preferably in the range of 15 mHi to 40 mHi. Suitable methods for determining the layer thickness are known to those skilled in the art. According to the invention, the layer thickness is preferably determined by microtome sectioning.

[0032] To improve printability, at least one of the two surfaces of the substrate can be partially or fully pretreated, in particular by using methods that increase surface tension, especially plasma and corona treatments. The pretreatment is preferably carried out at least in those areas of the surface that will later be printed with the image. Preferably, the substrate has a surface tension of at least 30 mN / m on the front side facing the image, more preferably at least 35 mN / m, and even more preferably at least 40 mN / m.

[0033] The film according to the invention comprises a printed image which includes at least one color cured by UV radiation. Preferably, the printed image comprises several different colors cured by UV radiation. Suitable colors with which carrier films can be printed and which can be cured by UV radiation are known to those skilled in the art and are commercially available (e.g., UV product group, Siegwerk or FLEXOCURE GEMINI). ® Product group (FlintGroup).

[0034] In a preferred embodiment, the UV-cured paint is radically cured. In this case, the UV-cured paint is preferably based on a UV-curable acrylate composition (e.g., FLEXOCURE GEMINI). ® ;YELLOW, FlintGroup, FLEXOCURE GEMINI ® ;BLACK FlintGroup or UV 259, Siegwerk.

[0035] In another preferred embodiment, the UV-cured paint is cationically cured. In this case, the UV-cured paint is preferably based on a UV-curable epoxy composition (e.g., UV 16, Siegwerk).

[0036] Analytical methods are available to a specialist, which can be used to subsequently examine the finished release film to determine whether curing has occurred. A radical reaction or a cationic reaction occurred. This can be determined, for example, by spectroscopic methods such as NMR or IR spectroscopy.

[0037] In a preferred embodiment, the color cured by UV radiation comprises a fluorescent dye or a luminescent dye.

[0038] According to the invention, the printed area of ​​the image is not particularly limited. Preferably, not the entire surface of the substrate is printed with the image. The printed area of ​​the image preferably lies in the range of 1% to 99% of the surface of the substrate, more preferably in the range of 5% to 95%, and even more preferably in the range of 10% to 90%.

[0039] The film according to the invention comprises a release coating which includes a polysiloxane cured by UV radiation. Suitable coating compositions with which printed carrier films can be coated and which can be cured by UV radiation are also known to those skilled in the art and are commercially available (e.g., TEGO). ® RC, Evonik or SILFORCE ® UV, Momentive).

[0040] For the purposes of this invention, the term "polysiloxane" refers to compounds whose polymer chains are composed of alternating silicon and oxygen atoms. A polysiloxane is based on n repeating siloxane units (-[Si(R2)-O]-). n , each of which is independently disubstituted with two organic residues R, wherein R preferably represents R 1 or OR 1 stands and R 1 each represents an alkyl group or an aryl group.

[0041] Preferably, the cured polysiloxane according to the invention is based on a repeating dialkylsiloxane unit or on a repeating alkylarylsiloxane unit. Depending on how many Si-O bonds a single siloxane unit has, relative to one tetravalent silicon atom, these units can be distinguished into terminal monofunctional siloxanes (M) with one Si-O bond, difunctional siloxanes (D) with two Si-O bonds, trifunctional siloxanes (T) with three Si-O bonds, and tetrafunctional siloxanes (Q) with four Si-O bonds.

[0042] Preferably, the polysiloxane used according to the invention has a cross-linked ring- or chain-shaped structure, particularly preferably a cross-linked chain-shaped structure, which is linked by (D)-, (T)- , and / or (Q)- units to form a two- or three-dimensional network.

[0043] In a preferred embodiment, the UV-cured polysiloxane is radically cured. In this case, the UV-cured polysiloxane is preferably based on a UV-curable acrylate composition (e.g., TEGO). ® RC 702, Evonik).

[0044] In another preferred embodiment, the UV-cured polysiloxane is cationically cured. In this case, the UV-cured polysiloxane is preferably based on a UV-curable epoxy composition (e.g., TEGO). ® RC 1401, Evonik or SILFORCE ® UV9800, Momentive.

[0045] The release coating of the release film according to the invention is preferably based on at least one cured, i.e., cross-linked, polysiloxane selected from the group consisting of addition-cross-linked, preferably metal-catalyzed addition-cross-linked, condensation-cross-linked, radically cross-linked, and / or cationically cross-linked polysiloxanes. More preferably, the release coating of the release film according to the invention is based on at least one cured polysiloxane selected from the group consisting of polydialkylsiloxanes, preferably polydimethylsiloxanes, and polyalkylarylsiloxanes, preferably polymethylphenylsiloxanes, each of which is cured.

[0046] The basis weight of the release coating of the release film according to the invention is preferably < 5 g / m² 2 , especially preferably < 2 g / m³ 2 It is particularly preferred to be in the range of 0.1 g / m³ 2 up to 1.5 g / m² 2 .

[0047] Preferably, the separating film according to the invention has a silicone coating on one side only, i.e., only as one of its surface layers. Alternatively, the separating film according to the invention can have a silicone coating on both sides.

[0048] According to the invention, the area of ​​the release coating is not particularly limited. In a preferred embodiment, not the entire surface of the carrier layer is covered with the release coating (repeat). In another preferred embodiment, the entire surface of the carrier layer is covered with the release coating. The area of ​​the release coating preferably lies in the range of 1% to 100% of the surface of the carrier layer, more preferably in the range of 50% to 100%, and even more preferably in the range of 75% to 100%.

[0049] The printed image can be a single, coherent structure or comprise several separate structures. Preferably, such multiple, separate structures are printed in a single operation, with different colors preferably being printed sequentially, for example by flexographic printing.

[0050] In the film according to the invention, the printed image is at least partially arranged between the carrier layer and the release coating, so that the printed image is at least partially covered by the release coating. Preferably, the printed image is arranged completely between the carrier layer and the release coating, so that the printed image is fully covered by the release coating. Preferably, the area of ​​the release coating is larger than the printed area of ​​the image, so that unprinted areas of the carrier layer's surface are also covered by the release coating.

[0051] Preferably, the printed image borders directly on both the carrier layer and the release coating, i.e., it directly touches both the carrier layer and the release coating.

[0052] In a preferred embodiment, the release film according to the invention comprises at least one further layer on the reverse side of the carrier layer facing away from the printed image, preferably at least one further layer based on at least one thermoplastic polymer. In a preferred embodiment, the release film according to the invention comprises several further layers on the reverse side of the carrier layer facing away from the printed image, preferably each layer independently of one another, each based on at least one thermoplastic polymer.

[0053] In a preferred embodiment, a further layer is a barrier layer or several further layers are barrier layers, preferably an oxygen barrier layer, water vapor barrier layer or oil barrier layer.

[0054] For the production of barrier layers, at least one thermoplastic polymer is preferably suitable, and at least one thermoplastic polymer is particularly preferably selected from the group comprising polyamides, ethylene vinyl alcohol copolymers (EVOH), polyvinyl alcohols (PVOH) and a mixture of at least two of the aforementioned polymers.

[0055] The polyamides (PA) used to produce barrier layers are preferably the same polyamides described in more detail above that can also be used to produce the carrier layer of the release film according to the invention. The polyvinyl alcohols used to produce the barrier layer are obtained by complete or incomplete hydrolysis of corresponding polyvinyl acetates (PVA) and thus include both partially saponified polyvinyl acetates with a degree of saponification of 50 to 98 mol% and fully saponified polyvinyl acetates with a degree of saponification > 98%. The ethylene-vinyl alcohol copolymers (EVOH) used to produce the barrier layer are obtained by complete or incomplete hydrolysis of corresponding ethylene-containing polyvinyl acetates (EVAc) and mainly comprise fully saponified ethylene-containing polyvinyl acetates with a degree of saponification > 98 0 / “

[0056] The carrier layer according to the invention preferably exists as a component of a multilayer film, more preferably as a component of a multilayer blown or cast film or as a component of a multilayer film composite, preferably in the form of a tubular film. The carrier layer according to the invention is particularly preferably a component of a multilayer blown film.

[0057] Preferably, the carrier layer according to the invention is part of a multilayer film comprising a total of at least 2, 3, 4, or 5 layers, of which the carrier layer is one layer. The individual layers of the multilayer film can then serve different purposes according to the invention. For example, the sealability of the multilayer film can be influenced by the composition and thickness of the outer layer. Functionalization and / or matting of individual layers is also possible. Stabilization can preferably be achieved via the middle layer of the multilayer film.

[0058] According to the invention, one or more barrier layers can preferably prevent migratory components of the packaged goods, e.g. an adhesive on a sanitary napkin, from migrating through the multilayer film and thus reaching, for example, the outer packaging.

[0059] In a preferred embodiment, the carrier layer according to the invention is a component of a multilayer plastic film with a separating effect, consisting of at least 50 wt.% polyolefins and having a total thickness of < 18 mm, preferably < 12 pm, and having at least partial embossing on at least one surface. Preferred embodiments of this multilayer plastic film are described in WO 2015 / 139844, the entire disclosure of which is hereby incorporated herein by reference, also with regard to preferred embodiments of the invention.

[0060] In a further preferred embodiment, the carrier layer according to the invention is a component of a flexible plastic film which is at least monoaxially oriented and optionally embossed, and which has a tear strength that differs by at least 30% in the machine direction from the tear strength transverse to the machine direction. Preferred embodiments of this multilayer plastic film are described in WO 2015 / 139845, to the entire disclosure of which reference is hereby made, also with regard to preferred embodiments of the invention.

[0061] In another preferred embodiment, the carrier layer according to the invention is a component of a multilayer plastic film, consisting of at least 50 wt.% polyolefins, stretched at least monoaxially in the machine direction by at least 1:2, with a total thickness of < 18 g / m², preferably < 12 g / m², and exhibiting an elongation of up to a maximum of 1% at a tensile force of at least 3 N per 25 mm width according to DIN EN ISO 527-3. Preferred embodiments of this multilayer plastic film are described in WO 2015 / 139843, the entire disclosure of which is hereby incorporated herein by reference, also with regard to preferred embodiments of the invention.

[0062] In a further preferred embodiment, the carrier layer according to the invention is a component of a multilayer polyolefin film comprising a layer sequence of a) a sealable layer (a) based on a polyethylene component with a density in the range of 0.910 to 0.940 g / cm³ 3 and a melting point in the range of 110 °C to 130 °C, b) a layer (b) based on a polymer mixture of 51 - 85 wt.% of at least one polyethylene with a density of 0.910 to 0.940 g / cm³ 3 and 15 - 49 wt.%, based on the total weight of the polymer mixture, of at least one propylene homo- or copolymer, c) a sealable layer (c) based on a polyethylene component with a density in the range of 0.910 to 0.940 g / cm³ 3and a melting point in the range of 110 °C to 130 °C, wherein the melting point of layer (a) or layer (c) is at least 5 °C lower than the melting point of layer (b), wherein the tear strength in the machine direction [MD] is < 5 N and the tear strength transverse to the machine direction [CD] is at least four times higher than in [MD], in each case measured according to D1N 53356, and the tensile strength is approximately the same in the machine direction [MD] as transverse to the machine direction [CD] and is > 15 N, measured according to D1N 1SO 527-3. Preferred embodiments of this multilayer plastic film are described in WO 2017 / 016660, the entire disclosure of which is hereby incorporated by reference, also with regard to preferred embodiments of the invention.

[0063] In another preferred embodiment, the release film according to the invention comprises no further layers besides the carrier layer and the release coating; that is, the release film according to the invention then consists of the carrier layer and the release coating (as well as the printed image and any other printed images that may be present). The carrier layer according to the invention is then preferably a single-layer blown or cast film.

[0064] The release coating, the carrier layer, and any additional layer(s) of the release film according to the invention can each be applied independently, if necessary. The coating must be equipped or doped with additives, preferably selected from the group consisting of antiblocking agents, antistatic agents, antifog agents, antimicrobial agents, dyes, color pigments, stabilizing agents (preferably heat stabilizers), process stabilizers, process aids, flame retardants, nucleating agents, crystallizing agents (preferably crystal nucleation agents), lubricants, optical brighteners, flexibilizers, sealing agents, plasticizers, spacers, fillers, peel additives, waxes, wetting agents, surface-active compounds (preferably surfactants), and dispersing agents. The release effect of the silicone coating, i.e., the polysiloxane, must be maintained.

[0065] The release coating, the carrier layer, and any further layer(s) of the release film according to the invention may, if necessary, each contain independently of one another at least 0.01-30 wt.%, preferably at least 0.1-20 wt.%, based on the total weight of a single layer, at least one of the aforementioned additives.

[0066] In a preferred embodiment, the release film according to the invention comprises, in addition to the printed image on the carrier layer, a further printed image on its reverse side facing away from the printed image.

[0067] Preferably, the printed image and the subsequent printed image differ from each other. For example, it is preferred that one of the two printed images comprises operating instructions for the packaged goods and the other of the two printed images represents instructions for the disposal of the packaged goods after their intended use.

[0068] If the carrier layer is transparent, the printed image and the subsequent printed image can both be viewed from above, i.e., the subsequent printed image appears to pass through the transparent carrier layer.

[0069] In a preferred embodiment of the separating film according to the invention, the printed image and / or the further printed image is a tactile, control and / or print mark, which is preferably arranged in the edge area of ​​the separating film.

[0070] In a particularly preferred embodiment of the separating film according to the invention, the printed image and / or the further printed image comprises an additional tactile, control and / or print mark, which is preferably arranged in the edge area of ​​the separating film.

[0071] According to the invention, the "edge region of the separating film" preferably comprises the 20%, more preferably 10%, of the total extent of the separating film facing the edge at the respective point. If, for example, the separating film has a total extent (width) of 15 cm perpendicular to the edge, the edge region of the separating film at this point preferably comprises the 3 cm, more preferably 1.5 cm, facing the edge.

[0072] In a particularly preferred embodiment of the release film according to the invention, it has a release coating on at least part of its two outer surfaces, the composition of which is preferably identical on both sides. If the carrier layer is the only layer, then preferably both outer surfaces of the carrier layer have a release coating on at least part of their surface. If the carrier layer is part of a multilayer film, then the carrier layer has a release coating on at least part of its surface on the side facing the printed image, and the opposite outermost layer of the multilayer film, i.e., the other outer surface, also has a further release coating on at least part of its surface.

[0073] Another aspect of the invention relates to packaging for a sanitary or hygiene article, preferably selected from the group comprising sanitary napkins and panty liners, wherein the packaging comprises the separating film described above according to the invention.

[0074] The packaging according to the invention is preferably designed as a wrap-around package. Preferably, the entire packaging consists of the separating film and the packaged goods (hygiene products).

[0075] The carrier layer features a printed image, which is preferably completely or at least partially covered by the hygiene product in front of it. The hygiene product preferably has an adhesive backing, which secures the hygiene product to the release coating. By manually peeling it off, the adhesive can be detached from the release coating, and the hygiene product can be removed from the packaging. The adhesive strength of the adhesive on the hygiene product is preferably greater than the adhesive strength on the release coating, so that the adhesive remains on the hygiene product after removal from the packaging. Preferably, the adhesive can then perform further functions. For example, if the hygiene product is a sanitary napkin, it can be secured to the inside of underwear via the adhesive when used as intended.Removing the hygiene product reveals the printed image underneath, which can serve aesthetic purposes and / or include instructions for disposing of the hygiene product after its intended use, for example in the form of pictograms and / or text.

[0076] In a preferred embodiment, the carrier layer has a strip of pressure-sensitive adhesive in the edge region, which allows the packaging to be closed laterally when folded. Preferably, the packaging is resealable. A person skilled in the art will recognize that alternative methods, such as heat sealing, crimping, etc., can also be used for lateral closure. To ensure resealability, a pressure-sensitive adhesive is preferably used according to the invention.

[0077] In a preferred embodiment, the hygiene article is not arranged centrally to the carrier layer, but offset to the side, so that an area of ​​the hygiene article protrudes at the edge of the carrier layer.

[0078] To explain how the wrap-around packaging works, the resealing process is described below. When opening the wrap-around packaging for the first time, the corresponding steps are performed in reverse order. To illustrate how the packaging functions as a wrap-around package, the separating film can be conceptually divided into a narrow and a medium section by a first fold. Furthermore, the separating film can be divided into a medium and a wide section by a second fold.

[0079] When resealing, the narrow folding section is first folded inwards along the first fold, thereby aligning any additional printed image, possibly located on the back, with the front of the packaging and thus making it visible from above. This additional printed image can serve aesthetic purposes and / or, for example, include pictograms and / or text providing instructions for the proper removal of the sanitary napkin from the packaging. The adhesive applied to the edges then binds the middle folding section on the back and the narrow folding section on the front together to form a kind of sealed pouch, into the opening of which the folded sanitary napkin extends.

[0080] When resealing, in a second step the middle folded section and the narrow folded section above it are folded again along the second fold, thus placing another section of the additional printed image, which may be located on the back, on the front of the packaging and therefore visible from above. This additional printed image can also serve aesthetic purposes and / or, for example, include pictograms and / or text providing instructions for the proper removal of the sanitary napkin from the packaging. The preferred, edge-applied The adhesive forms a kind of sealed bag with the wide folding section on the back, the middle folding section on the front, and the narrow folding section in the middle, inside of which the twice-folded hygiene product is located.

[0081] Preferably, an overhanging portion of the release liner is not concealed by the wide folding section, thus remaining visible and serving, for example, as a tab for easier opening of the packaging by hand. A person skilled in the art recognizes that it can be advantageous if the reverse side of the carrier layer, or in the case of a multi-layer film, the outer reverse layer of the release liner, also has an additional release coating, at least in the edge area, so that the adhesive adheres to it and can also be removed from it again.

[0082] Another aspect of the invention relates to the use of the above-described separating film according to the invention as packaging material for a sanitary or hygiene article, preferably selected from the group comprising sanitary napkins and panty liners.

[0083] Another aspect of the invention relates to a method for producing the above-described separating film according to the invention, wherein the method comprises the steps: (a) Printing at least part of the surface of a substrate layer with at least one UV-curable ink; (b) Irradiating the curable paint with UV radiation; (c) Applying a coating composition comprising a UV-curable polysiloxane to at least part of the printed surface of the substrate; and (d) Irradiation of the curable polysiloxane with UV radiation.

[0084] The release film according to the invention can be produced using known manufacturing processes such as lamination or (co)-extrusion, preferably by co-extrusion. The carrier layer and / or any additional layer(s) can be formed by extrusion, preferably by cast extrusion or blown film extrusion, in particular by cast co-extrusion or blown film co-extrusion, with blown film co-extrusion being preferred according to the invention.

[0085] Preferably, the carrier layer and / or any additional layer(s) present can be produced and processed as a multi-layer film, possibly in the form of a tubular film.

[0086] The resulting single-layer or, preferably, multi-layer blown or cast film, or the entire possibly multi-layered film composite in the form of a tubular film, can be embossed directly afterwards without prior storage or, alternatively, during its production. Preferably, the single-layer or, more preferably, multi-layer blown or cast film, or the possibly multi-layered film composite in the form of a tubular film, is embossed during its production.

[0087] Preferably, steps (a) to (d) are carried out in alphabetical order, whereby it is possible that steps (a) and (b), steps (b) and (c), and / or steps (c) and (d) are carried out independently of one another, at least partially simultaneously. In particular, it is preferred according to the invention that the curing of the curable color, which is induced by UV radiation in step (b), need not yet be completely completed if the coating composition is already applied in step (c) and subsequently irradiated with UV radiation in step (d).

[0088] Preferably, step (d) is performed no later than 300 seconds after step (b), so that steps (a) to (d) are practically performed in a single operation. In preferred embodiments, step (d) is performed no later than 240 seconds, or no later than 180 seconds, or no later than 120 seconds, or no later than 60 seconds, or no later than 30 seconds, or no later than 10 seconds after step (b). In preferred embodiments, step (d) is performed no later than 9 seconds, or no later than 8 seconds, or no later than 7 seconds, or no later than 6 seconds, or no later than 5 seconds, or no later than 4 seconds after step (b). Since the method according to the invention is preferably carried out continuously, a person skilled in the art will recognize that the aforementioned time specifications in this case refer to specific sections of the separating film according to the invention, if these sections are, for example,The printing process begins with the application of the image and subsequent irradiation on a common central cylinder with several inking units connected in series. Immediately afterward, the release coating is applied and the surface is irradiated again. The time interval between steps (b) and (d) is determined by the spatial distance between the UV radiation sources on the circumference of the common central cylinder and the machine speed. Alternatively, the downstream printing unit for applying the coating composition can be mounted on a separate central impression cylinder.

[0089] Preferably, the machine speed is in the range of 100 and 800 m / min, preferably 200 m / min and 450 m / min, and depends on the type of carrier film, the number of different printing techniques and printing inks, or any necessary precise control of multiple printings or coatings.

[0090] Preferably, both the ink for the printed image and the release coating, e.g., a coating composition for producing UV-curable silicone layers, are printed in a single, simultaneous operation, e.g., on a common central cylinder in a first printing unit (printed image) and a second printing unit (release coating). The release coating can be applied to the entire surface or to a partial surface (repeat pattern).

[0091] In a preferred embodiment, the release coating is applied in a partially controlled manner (repeat), whereby the control can be effected by means of a tactile, control and / or print mark or the printed image below the release coating.

[0092] In a preferred embodiment, a further printed image is applied to the reverse side of the carrier film opposite the printed image, wherein the printing of this further printed image is preferably uncontrolled. In a preferred embodiment, the release coating is applied partially (repeat) in a controlled manner, wherein the control can be achieved using this further printed image on the reverse side of the carrier film opposite the printed image.

[0093] Tactile, control, and / or print marks are known to those skilled in the art and can fulfill various functions. According to the invention, preferably, the tactile, control, and / or print mark can serve to: - to determine the relative position of the printed image on the release film during printing in step (a); - if additionally available, to define the relative position of the further printed image on the release film during printing; - when applying the release coating in step (c), to determine the relative position of the release coating on the release film, especially if the release coating is only applied to part of the surface; and / or - to determine the relative position of the packaged goods or an adhesive material attached to the packaged goods on the release film or the release coating when the release film is later used, e.g. as packaging material.

[0094] Preferably, the UV radiation used in step (b) has essentially the same wavelength as the UV radiation used in step (d).

[0095] In this context, printing inks and / or coating compositions that are cationically curable (e.g., epoxy-based) sometimes have the advantage that the curing process is not affected by the in The oxygen contained in the air is affected, so the use of inert gas can be avoided. However, such printing inks and / or coating compositions sometimes tend to produce unpleasant odors.

[0096] In contrast, printing inks and / or coating compositions that can be cured by radicals (e.g., acrylate-based) sometimes have the advantage of not producing any unpleasant odors. However, such printing inks and / or coating compositions require the use of inert gases.

[0097] In preferred embodiments of the method according to the invention (i) the UV-curable paint is radically curable and the UV-curable polysiloxane is radically curable; (ii) the UV-curable paint is radically curable and the UV-curable polysiloxane is cationically curable; (iii) the UV-curable paint is cationically curable and the UV-curable polysiloxane is radically curable; or (iv) the UV-curable paint is cationically curable and the UV-curable polysiloxane is cationically curable.

[0098] In a preferred embodiment of the method according to the invention, steps (a) to (d) are carried out under a protective gas atmosphere.

[0099] In another preferred embodiment of the method according to the invention, steps (a) to (d) are carried out without a protective gas atmosphere.

[0100] In preferred embodiments of the V process according to the invention (i) the UV-curable paint contains a solvent and the UV-curable polysiloxane contains a solvent; (ii) the UV-curable paint contains a solvent and the UV-curable polysiloxane is solvent-free; (iii) the UV-curable paint is solvent-free and the UV-curable polysiloxane contains a solvent; or (iv) the UV-curable paint is solvent-free and the UV-curable polysiloxane is solvent-free.

[0101] Figure 1 schematically illustrates a preferred embodiment of the release film according to the invention, consisting of a carrier layer (1), a printed image (2), and a release coating (3). In the embodiment according to Figure 1, the release coating (3) is applied over the entire surface of the carrier layer (1) together with the printed image (2), so that the area of ​​the release coating (3) corresponds to the area of ​​the carrier layer (1).

[0102] Figure 2 schematically illustrates a preferred variant of the release film according to the invention, consisting of a carrier layer (1), a printed image (2), and a release coating (3). In the embodiment according to Figure 2, the release coating (3) is applied partially to the carrier layer (1) together with the printed image (2), so that the area of ​​the release coating (3) is smaller than the area of ​​the carrier layer (1); a border area (4) remains which is not covered by the release coating (3).

[0103] Figure 3 schematically illustrates a preferred variant of the release film according to the invention, consisting of a carrier layer (1), printed image (2) and release coating (3), which, in addition to the printed image (2), has a touch, control and / or print mark (5) in the edge area (4).

[0104] Figure 4 schematically illustrates a preferred variant of the release film according to the invention, consisting of a carrier layer (1), printed image (2), release coating (3), edge area (4), touch, control and / or print mark (5), and having a further printed image (6) on the reverse side.

[0105] Figure 5 schematically illustrates a preferred packaging according to the invention for a hygiene product, which includes the separating film according to the invention. The packaging is shown here as an example of a wrap-around package for a sanitary napkin, but can also be used for packaging other goods, particularly hygiene products. Preferably, the entire packaging consists of the separating film and the sanitary napkin. The separating film of the packaging according to the invention can include tactile, control, and / or printed markings, which, however, have been omitted in Figure 5 for the sake of clarity. Figures 5A to 5D show different states of the packaging according to the invention.

[0106] Figure 5A shows the packaging according to the invention in its fully unfolded state. The carrier layer (1) has a printed image which, in the shown state, is covered by the sanitary napkin (7) in front of it. A person skilled in the art will recognize that the printed image can alternatively be arranged offset from the sanitary napkin (7) or be designed to be so large that at least parts of it are not covered by the sanitary napkin (7), i.e., are visible. The release coating (3) is applied to the carrier layer (1) along with the printed image over a partial area, so that the area of ​​the release coating (3) is smaller than the area of ​​the carrier layer (1); a border area remains. (4), which is not covered by the release coating (3). The sanitary napkin (7) preferably has an adhesive on its back (not shown) by which it is fixed to the release coating (3). By manually peeling it off, the sanitary napkin, along with the adhesive, can be removed from the release coating (3). The adhesive can then be used to fix the sanitary napkin (7) to the inside of underwear when used as intended. On both long sides, the carrier layer (1) has a strip of adhesive (13) in the edge area (4) on each side, which allows the packaging to be closed by folding it over. Preferably, the packaging is resealable. A person skilled in the art will recognize that alternative methods can be used for closing the packaging, such as heat sealing, crimping, etc.The sanitary napkin (7) is preferably not centered on the carrier layer, but offset to the side, so that a portion (14) of the sanitary napkin protrudes beyond the edge of the carrier layer (1). The separating film can be conceptually divided by a first fold (8) into a narrow fold (10) and a medium fold (11). Furthermore, the separating film can be divided by a second fold (9) into the medium fold (11) and a wide fold (12).

[0107] Figure 5B shows the packaging according to the invention in its fully unfolded state after the sanitary napkin has been removed. The printed image (2) behind it becomes visible in this way and can serve aesthetic purposes and / or, for example, include instructions for disposing of the sanitary napkin after its intended use, for example in the form of pictograms and / or text.

[0108] Figure 5C shows the packaging according to the invention in a partially unfolded state. This state can be reached both when the packaging is first opened and when it is resealed. The narrow folding section (10) is folded along the first folding fold (8), whereby the additional printed image (6), which is located on the back in Figures 5A / B and therefore not yet visible in the top view shown there, is located on the front of the packaging according to Figure 5C and is therefore visible in the top view shown. The additional printed image can serve aesthetic purposes and / or, for example, include instructions for the proper removal of the sanitary napkin from the packaging in the form of pictograms and / or text.The adhesive (13) applied to the edge area (4) forms a kind of sealed pouch between the central folded section (11) on the back and the narrow folded section (10) on the front, into the opening of which the folded sanitary napkin (7) extends. The protruding area (14) of the sanitary napkin (7) is not covered by the narrow folded section (10) and therefore remains visible (on the back side compared to the illustration in Figure 5A).

[0109] Figure 5D shows the packaging according to the invention in its fully closed state. This state can also be reached both when the packaging is first opened and when it is resealed. The central folded section (11) and the narrow folded section (10) above it are folded again along the second folded edge (9), whereby another section of the additional printed image (6), which is located on the back in Figures 5A / B and therefore not yet visible in the top view shown there, is located on the front of the packaging as shown in Figure 5D and is therefore visible in the top view shown. The additional printed image can also serve aesthetic purposes and / or, for example, include instructions for the proper removal of the sanitary napkin from the packaging in the form of pictograms and / or text. The additional printed image (6) shown in Figure 5C is thus covered.The adhesive (13) applied to the edge region (4) forms a kind of sealed pouch with the wide rear fold section (12), the central front fold section (11), and the narrow central fold section (10), inside which the twice-folded sanitary napkin (7) is located. Preferably, a protruding area (15) of the release film is not covered by the wide fold section (12), thus remaining visible and serving, for example, as a tab for easier opening of the packaging by hand. A person skilled in the art will recognize that it can be advantageous if the reverse side of the carrier layer (1), or in the case of a multilayer film, the outer rear layer of the release film shown in Figures 5A / B, also has a further release coating, at least in the edge region, so that the adhesive (13) adheres to it and can also be removed from it.

[0110] Reference symbol list: 1 - Carrier layer 2 - Print image 3 - Release coating 4 - Edge area 5 - Tactile, control and / or print mark 6 - further print image 7 - Sanitary napkin 8 - first fold 9 - second fold 10 - narrow impact section 11 - middle impact section 12 - wide impact section 13 - Pressure-sensitive adhesive 14 - protruding area of ​​the sanitary napkin 15 - protruding area of ​​the separating film

[0111] The following examples serve to illustrate the invention, but are not to be interpreted restrictively.

[0112] A 24 m thick polyolefin film, pre-treated on one side with corona (42 mN / m), was used as the substrate. The machine speed was 250 m / min.

[0113] A conventional flexographic printing process was used, with the printing unit mounted on a central impression cylinder. The printing unit consisted of a printing cylinder that carried the printing sleeve with the print design. Ink was applied to the printing cylinder with the print design by an anilox roller, with excess ink being wiped off the surface of the anilox roller by a doctor blade (so-called "closed chambered printing unit").

[0114] The silicone coating process took place in a printing unit (consisting of a printing cylinder, anilox roller, and chambered doctor blade) located downstream of the color printing unit, where a silicone coating was printed onto the paper (the "silicone printing unit"). In the experiments, both the color printing unit and the silicone printing unit were mounted on a central impression cylinder.

[0115] The respective structure of the tested separating films is summarized in the following table, where examples Vl to V-8 are comparative examples and examples Bl to B-5 are according to the invention: EtOAc: Ethyl acetate Nitrocell: Nitrocellulose UV radical: UV radiation-induced radical curing reaction UV cation: cationic curing reaction induced by UV radiation

[0116] The number of work steps and the times required for each production process are summarized in the following table: Machine time: Pure machine time [min] = linear meters (roll) [m] / machine speed [m / min] Setup time: Pure setup time includes, among other things, the insertion and removal of the film roll, the setting of the colors, the adjustment effort, cleaning effort, etc.

[0117] The tear strength was determined at 70 °C using an electronic tear tester (resolution 0.02 N). Tesa tape A 7475, 25 mm wide, was used. The freshly siliconized samples were prepared in slabs of approximately 6 layers, approximately 24–29 cm long, and wrapped in black foil. These samples were then tempered. Tempering took place in a drying oven for 2 hours at 70 °C by wrapping the slabs around trays. This allowed air to circulate freely through the trays, ensuring even heating of the slabs. The samples were removed, and the adhesive tape was applied over the areas to be tested, ensuring no air bubbles were trapped. The tape was unwound four times using a roller at a speed of 20 cm / s. The release film was cut so that a 1 cm free border remained on each side of the tape. The samples were cut into strips of equal length (approximately 30 cm long) and labeled.The samples were then placed between thin metal plates and weighted down. The load was applied evenly. The number of weights depended on the number of samples per layer.

[0118] This corresponded to a load of 70 g / cm². 2 The samples were then stored in a drying oven at 70 °C for 20 hours and, after removal, adhered to a metal support plate. A stiff foil strip was attached to the test tape, and the metal support plate was secured in the lower clamp, while the stiff foil strip was secured in the upper clamp of the Zwick / Test device. After adjusting the load cell, the test tape was peeled off at an angle of 175° and a speed of 300 mm / min.

[0119] To determine the "rub-off" test, the silicone-coated film was placed flat on a smooth surface. Then, the silicone layer was rubbed 4-5 times with the thumb. If the silicone film partially detached, "rub-off" was noted. Otherwise, "test OK" was noted.

[0120] Separation values, hardening grades, anchorage and "rub off" are summarized in the following table: OK: OK

[0121] As the preceding experimental data demonstrate, the production of the release films according to comparative examples V1 to V-4 is labor-intensive and consequently time-consuming. While the release films according to comparative examples V-6 to V-8 do not exhibit these disadvantages, they do show ink transfer into the silicone printing unit (contamination) and rub-off.

[0122] In contrast, the release films according to examples B1 and B2 of the invention show no disadvantages whatsoever. However, with regard to the release films according to examples B3 to B5 of the invention, it must be taken into account that an unpleasant odor may arise as a result of the use of cationically curing paints or coating compositions.

Claims

Patent claims:

1. A release film comprising a carrier layer, a printed image and a release coating, wherein (a) the printed image is at least partially located between the substrate layer and the release coating; and (b) the printed image includes at least one color cured by UV radiation; and (c) the release coating comprises a polysiloxane cured by UV radiation.

2. The release film according to claim 1, wherein the printed image is directly adjacent to both the carrier layer and the release coating.

3. The release film according to claim 1 or 2, wherein the printed image is arranged completely between the carrier layer and the release coating.

4. The release film according to one of the preceding claims, wherein the carrier layer comprises a polyolefin.

5. The release film according to claim 4, wherein the carrier layer comprises a polyolefin selected from the group consisting of thermoplastic olefins; and / or thermoplastic olefin homo- or copolymers of α,β-unsaturated olefins with 2 to 10 carbon atoms; preferably selected from the group consisting of polyethylene, polypropylene, polybutylene, polyisobutylene (PI), copolymers and / or mixtures of at least two of the aforementioned polymers.

6. The release film according to one of the preceding claims, wherein the carrier layer is colored.

7. The release film according to any one of claims 1 to 6, wherein the carrier layer has a layer thickness in the range of 5 pm to 50 pm.

8. The support layer according to claim 7, wherein the support layer has a layer thickness in the range of 10 pm to 45 pm.

9. The support layer according to claim 8, wherein the support layer has a layer thickness in the range of 15 pm to 40 pm.

10. The release film according to any one of claims 1 to 9, wherein the carrier layer on the front side facing the printed image has a surface tension of at least 30 mN / m.

11. The release film according to claim 10, wherein the carrier layer on the front side facing the printed image has a surface tension of at least 35 mN / m.

12. The release film according to claim 11, wherein the carrier layer on the front side facing the printed image has a surface tension of at least 40 mN / m.

13. The release film according to one of the preceding claims, wherein the release coating is based on at least one cured polysiloxane selected from the group consisting of addition-crosslinked, preferably metal-catalyzed addition-crosslinked, condensation-crosslinked, radically crosslinked, and / or cationically crosslinked polysiloxanes.

14. The release film according to any one of claims 1 to 12, wherein the release coating is based on at least one cured polysiloxane selected from the group consisting of polydialkylsiloxanes, preferably polydimethylsiloxanes, and polyalkylaryl siloxanes, preferably polymethylphenylsiloxanes.

15. The release film according to one of the preceding claims, wherein the release coating has a basis weight of < 5 g / m² 2 , preferred < 2 g / m³ 2 and especially preferred in the range of 0.1 g / m³ 2 up to 1.5 g / m² 2 exhibits.

16. The separating film according to one of the preceding claims, which has a silicone coating on one or both sides as a surface layer(s).

17. The release film according to one of the preceding claims, wherein the color cured by UV radiation comprises a fluorescent dye or a luminescent dye.

18. The release film according to one of the preceding claims, which comprises at least one further layer on the reverse side of the carrier layer facing away from the printed image.

19. The release film according to one of the preceding claims, wherein the release coating, the carrier layer and any further layer(s) of the release film may each be equipped independently of one another with additives. which are selected from the group consisting of antiblocking agents, antistatic agents, antifog agents, antimicrobial agents, dyes, color pigments, stabilizing agents, preferably heat stabilizers, process stabilizers, process aids, flame retardants, nucleating agents, crystallizing agents, preferably crystal nucleating agents, lubricants, optical brighteners, flexibilizing agents, sealing agents, plasticizers, spacers, fillers, peel additives, waxes, wetting agents, surfactants, preferably surfactants, and dispersing agents; and / or wherein the weight fraction of the other additives is each independently at least 0.01 to 30 wt.%, preferably 0.1 to 20 wt.%, based on the total weight of the individual layer.

20. The release film according to one of the preceding claims, wherein the silicone layer, in the context of the FINAT adhesive strength test according to the test standard FTM 10, when the test adhesive tape is peeled off at a temperature of 70 °C, at a peel angle of 175 ° and a peel speed of 300 mm / min, corresponding to peel values ​​in the range of 2 to 25 cN / l0 cm, does not show any peeling phenomena referred to as ‘rub off’.

21. The release film according to one of the preceding claims, wherein the carrier layer comprises a further printed image on its reverse side facing away from the printed image.

22. The separating film according to one of the preceding claims, wherein the printed image and / or the further printed image is or comprises a tactile, control and / or print mark.

23. The separating film according to claim 22, wherein the touch, control and / or print mark is arranged in the edge region of the separating film.

24. The release film according to one of the preceding claims, wherein the UV-cured paint and / or the UV-cured polysiloxane is radically or cationically cured.

25. Packaging for a hygiene product comprising a separating film according to any of the preceding claims.

26. A use of a separating film according to any one of claims 1 to 24 as packaging material for a hygiene article.

27. A method for producing a release film according to any one of claims 1 to 24 comprising the steps (a) Printing at least part of the surface of a substrate layer with at least one UV-curable ink; (b) Irradiating the curable paint with UV radiation; (c) Applying a coating composition comprising a UV-curable polysiloxane to at least part of the printed surface of the substrate; and (d) Irradiation of the curable polysiloxane with UV radiation.

28. The method of claim 27, wherein step (d) is performed no later than 300 seconds after step (b).

29. The method according to claim 27 or 28, wherein the machine speed is in the range of 100 to 800 m / min, preferably from 200 to 450 m / min.

30. The method according to one of claims 27 to 29, wherein both the ink for the printed image and the release coating are printed in a single, common operation immediately one after the other.

31. The method according to any one of claims 27 to 30, wherein the UV radiation used in step (b) has essentially the same wavelength as the UV radiation used in step (d).

32. The method according to any one of claims 27 to 31, wherein (i) the UV-curable paint is radically curable and the UV-curable polysiloxane is radically curable; (ii) the UV-curable paint is radically curable and the UV-curable polysiloxane is cationically curable; (iii) the UV-curable paint is cationically curable and the UV-curable polysiloxane is radically curable; or (iv) the UV-curable paint is cationically curable and the UV-curable polysiloxane is cationically curable.

33. The method according to any one of claims 27 to 32, wherein (i) the UV-curable paint contains a solvent and the UV-curable polysiloxane contains a solvent; (ii) the UV-curable paint contains a solvent and the UV-curable polysiloxane is solvent-free; (iii) the UV-curable paint is solvent-free and the UV-curable polysiloxane contains a solvent; or (iv) the UV-curable paint is solvent-free and the UV-curable polysiloxane is solvent-free.

34. The method according to any one of claims 27 to 33, wherein steps (a) to (d) are performed under The procedure will be carried out in a protective gas atmosphere.

35. The method according to any one of claims 27 to 33, wherein steps (a) to (d) without The procedure will be carried out in a protective gas atmosphere.