RU2787108C1 - Method for manufacturing a structured product by application of a removable protective layer and a structured product obtained by the specified method - Google Patents

Abstract

FIELD: structured surfaces obtaining.

SUBSTANCE: invention relates to the field of obtaining structured surfaces, which are used to influence the optical, bionic and/or tactile properties of material surfaces. A method for manufacturing a structured product (A1M1), in which the material (M1) contains at least one micro- and/or nanostructured surface (SU1), including a number of micro- and/or nano-sized surface elements, is covered with at least a partially cured layer (C2) coatings to form a composite material (M1C2), said composite material (M1C2) is attached to the object (A1) and the coating layer (C2) is at least partially removed to form a structured article (A1M1). The present invention also relates to a composite material (M1C2), wherein the surface elements of the structured material (M1) are coated with a protective coating layer (C2).

EFFECT: invention provides a method for manufacturing a structured article by using a structured material, whereby the structure of the material is not damaged during packaging, transportation and attaching the structured surface to the product, the method is suitable for the manufacture of large structured objects or blanks and allows the structured material to be attached at the place of manufacture of the object, and also Suitable for a range of items and allows easy attachment of structured material to the item without the use of special tools or chemicals.

15 cl, 4 tbl

Description

The present invention relates to a method for manufacturing a structured article (A1M1), in which a material (M1) containing at least one micro- and/or nano-structured surface (SU1), including a number of micro- and/or nano-sized surface elements, is covered with at least least partially cured layer (C2) of the coating, to obtain a composite material (M1C2), the specified composite material (M1C2) is attached to the object (A1), and the layer (C2) of the coating is at least partially removed, to obtain a structured product (A1M1 ). The present invention also relates to a composite material (M1C2) in which the surface elements of the structured material (M1) are coated with a protective coating layer (C2).

Prior Art

It is now common in a number of industrial applications to provide workpiece surfaces with structures whose structural characteristics are in the micrometer range or even in the nanometer range. Such structures are also called microstructures (structures with characteristics in the micrometer range) or nanostructures (structures with characteristics in the nanometer range). Such structures are, for example, used to influence the optical, bionic and/or tactile properties of material surfaces. Structures of this type are also called embossments, embossed structures or structured surfaces.

One of the common ways to obtain such structured surfaces is to transfer these structures to the coating material. The transfer of structures to the coating material is often achieved by an embossing operation during which a cliché containing the microstructures and/or nanostructures to be used for shaping is brought into contact with and pressed into the coating material in a negative form. The coating material is typically cured in situ resulting in permanently formed structures.

Since the direct embossing methods described above cannot be used on large blanks or objects such as aircraft wings, wind turbine blades, or architectural cladding, for example, a material that has a nanometer or micrometer structure on its surface is pressed or glued to a workpiece or object. In order to ensure a strong connection of the structured material, it is necessary to apply pressure, usually in combination with percussive movements that create frictional forces on the surface, to permanently attach the structured surfaces to said workpiece or object. However, the application of pressure, usually in combination with percussive motions, can result in at least partial damage to the structured surface, thus leading to deterioration in the characteristics or visible physical properties of the surface once attached to the workpiece or object.

If the attachment of said structured coating is carried out at the place of manufacture of the workpiece or object, then these structured surfaces must be packaged and transported to the destination. However, said packaging and transport may also result in damage to the structured surface due to frictional forces, shock or pressure generated during packaging and transport.

For this reason, structured surfaces require additional packaging and/or protection to maintain the integrity and appearance of the structured surface. It is known from the prior art to use a foil to protect a structured surface. However, the foil generally only covers the protruding parts of the surface, which makes it difficult to adhere and, for this reason, the foil can easily slide over said structured surface, which makes it difficult to apply pressure during application without inadvertently removing the foil while attaching said structured surface to workpiece or object. Moreover, reduced adhesion also results in a high risk of damage to the structured surface. Alternatively, adhesive-coated foil is used. In this case, often adhesion is also still problematic, or adhesive residue remains on the structured surface after removal of the foil.

It is also known from the prior art to use protective coating layers which are applied to a structured surface as a liquid coating, cured and removed by dissolution after being attached to the object. However, this method of protection is not suitable when the workpieces or objects are not immersed in the solvent during their normal use. Moreover, the use of solvents reduces the environmental balance of said protective coating layer, since additional solvents must be used to remove the protective layer. Moreover, this method cannot be applied when the structured surface is to be attached to workpieces or objects that are sensitive to solvents, such as electronic components.

Thus, there remains a need to provide a protective coating layer that can be easily applied to a structured surface, resulting in excellent surface protection during packaging, transport and attachment, but at the same time, can be easily removed without the use of special tools or chemicals, and does not damage or contaminate the structured surface.

A task

Therefore, it is an object of the present invention to provide a method for manufacturing a structured article by using a structured material, wherein the structure of the material is not damaged during packaging, transport, and attaching the structured surface to the article. This method must be suitable for the manufacture of large structured objects or blanks, and must allow the attachment of the structured material at the place of manufacture of the object. In addition, said method should be suitable for a variety of objects and allow easy attachment of the structured material to the object without the use of special tools or chemicals.

Technical solution

This problem is solved with the help of the object declared in the claims, and also with the help of the preferred embodiments of the specified object, which are described below.

Accordingly, the first aspect of the present invention is a method for manufacturing a structured article (A1M1), said method comprising the following steps:

(1) obtaining a material (M1) containing at least one micro- and/or nanostructured surface (SU1), including a number of micro-sized and/or nano-sized surface elements;

(2) coating the surface (SU1) of the material (M1) with at least one coating composition (C2a);

(3) at least partially curing the coating composition (C2a) on the surfaces (SU1) of the material (M1), to obtain a composite material (M1C2), wherein the dry film thickness of the at least partially cured composition (C2) for coating the composite material (M1C2) is at least 5 microns;

(4) at least partially attaching a composite material (M1C2) to at least one item (A1) to obtain an article (A1M1C2); and

(5) at least partially removing the at least partially cured coating composition (C2) from the article (A1M1C2) to obtain a structured article (A1M1).

An additional object of the present invention is a composite material (M1C2) containing

- at least one material (M1) containing at least one micro- and/or nanostructured surface (SU1), including a number of micro-sized and/or nano-sized surface elements and

- at least one partially cured coating composition (C2), wherein at least one partially cured coating composition is insoluble in water, and wherein the at least partially cured coating layer (C2) does not exhibit surface features of the material (M1 ) on the outer surface of the at least partially cured coating composition (C2).

Coating the structured material (M1) with at least one coating layer (C2) results in easy and effective protection of the structured surface of the material (M1). Since the use of composition (C2a) for coating allows full coverage of the protrusions and recesses of the structured surface (SU1) of the material (M1), while the risk of inadvertent removal of the protective layer (C2) during attachment of the protected structured composite material (M1C2) to the object ( A1) is significantly reduced compared to the use of films as protective layers. Moreover, complete coverage of the protrusions and depressions of said structured surface (SU1) results in effective protection of the surface against shear forces, impacts and pressures generated during packaging, storage, transport and attachment of the structured material (M1). Therefore, the method according to the invention makes it possible to attach the structured surface on a permanent basis, since the attachment can be facilitated by the application of pressure and, if necessary, impact movements, without damaging the structured surface (SU1) due to the presence of the protective layer. Said protective layer can be easily removed after being attached to the object, either without removing portions of the structured surface or leaving behind undesirable residues on the structured surface (SU1). Since solvents are not needed to remove the protective coating (C2), said protected structured material can also be attached to solvent-sensitive items, or to items that cannot be immersed in a solvent to remove the protective layer.

Detailed description

Where an official standard is referred to in the context of the present invention, the reference refers to the version of the standard that was in effect on the filing date of the application, or, if there was no current version on that date, to the latest version in effect.

In this specification, for convenience, the terms "polymer" and "resin" are used interchangeably, and cover resins, oligomers, and polymers.

The term "poly(meth)acrylate" means both polyacrylates and polymethacrylates. Therefore, poly(meth)acrylates may consist of acrylates and/or methacrylates, and may contain additional ethylenically unsaturated monomers such as, for example, styrene or acrylic acid. The term "acryloyl" and, respectively, "(meth)acryloyl" in the sense of the present invention covers methacryloyl compounds, acryloyl compounds and mixtures thereof.

In the context of this invention, C ₁ -C ₄ -alkyl means methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably methyl, ethyl and n-butyl, more preferably methyl and ethyl, and most preferably methyl.

The term "structured article" in the sense of the present invention means an article, preferably a blank or assembled article, which contains at least one surface, including a number of micro-sized and/or nano-sized surface elements. Therefore, the term "item (A1)" means the workpiece that is used to assemble the product or the product itself.

Method according to the invention:

Stage (1):

In step (1) of the process according to the invention, a material (M1) is obtained containing at least one micro- and/or nano-structured surface (SU1) comprising a number of micro- and/or nano-sized surface elements. In this case, microstructures are structures - in terms of structure width and/or structure height - that have characteristics in the micrometer range. Nanostructures in this case are structures - in terms of structure width and/or structure height - that have characteristics in the nanometer range. Microstructures and nanostructures in this case are structures that have a structure width in the nanometer range and a structure height in the micrometer range, or vice versa. The terms "structure height" and "structure depth" are used interchangeably here. The width of the structure and the height of the surface structure (SU1) can be determined by mechanical scanning of the surface. In this case, the height of the structure is measured at at least 10 points on the line, evenly distributed over the width of the sample, while making sure that the scanning device does not compress the structured surface.

Receive material (M1):

The material (M1) provided in step (1) of the method according to the invention can be obtained by various methods, for example, lithographic methods such as nanoimprinting lithography, laser lithography and photolithography, hot stamping of polymer films, self-assembly of monolayers and expansion or swelling of the polymer material. Option 1 comprising steps a-I) or a-II), b) and c) embossing the coating composition at regular intervals in the pattern, curing said coating composition, and removing the structured and cured coating composition (i.e., material (M1)) from the embossing device. Thus, the preferred material (M1) provided in step (1) is obtained by

a-I) applying a coating composition (P1a) to a substrate (F1) to obtain a composite material (F1P1a), and at least partially embossing the coating composition (P1a) with at least one embossing device (E2) containing at least one cliché (e2) for embossing

or

a-ii) applying the coating composition (P1a) to at least a portion of the at least partially embossed surface of at least one embossing tool (E2) containing at least one embossing plate (e2) and optionally applying a substrate (F1)

and

b) at least partially curing the coating composition (P1a), to obtain at least partially embossed coating material, optionally containing a substrate (F1), wherein the coating composition (P1a) is in contact with the embossing tool (E2) during curing, and

c) removing the at least partially embossed coating material, optionally containing a substrate (F1), from the embossing tool (E2) to obtain material (M1).

The term "embossing" refers to a method in which at least part of the surface of the coating composition (P1a) after step a-I)/a-II) or at least part of the surface of the material (M1) after step b) shows an embossed structure . In this case, at least a certain area of the coating composition (P1a) or material (M1) is provided with an embossed structure. Preferably, the entire surface of the coating composition (P1a) or material (M1) is provided with an embossed structure. Similar comments apply to the term "embossing" referring to at least a partially embossed composite material (S1C1) used as an embossing die (e2) of an embossing tool (E2).

The embossing tool (E2) which is used in steps a-I) or a-II) can either be an embossing tool made of polymeric material or an embossing tool made of metal and is preferably reusable, i.e. it can be used to transfer at least one embossed structure to composition (P1a) for recoating. The embossing tool (E2) has a "negative structure" ("negative shape"), i.e. a mirror image of the embossed structure which is transferred to the composition (P1a) in steps a-I) or a-II) of the method according to the invention for coating and, after step b), the material (M1). The embossing tool (E2) contains at least one embossing plate (e2). Said embossing plate (e2) may be a resin embossing plate (e2) or a metal embossing plate (e2), preferably a resin embossing plate (e2).

An embossing tool (E2) containing a resin embossing plate (e2):

In the case of using an embossing tool (E2) containing a polymer embossing plate (e2), it is preferable if the composite material (S1C1) contains a micro- and/or nano-structured surface, including a number of micro-sized and/or nano-sized surface elements polymeric material (C1), and the substrate (S1), are used as at least one cliché (e2) for embossing at least one device (E2) for embossing. Said composite material (S1C1) which is used in steps a-I) or a-II) is also referred to below as "reference substrate". By analogy, the coating (C1) on the reference substrate is hereinafter referred to as "at least partially cured reference coating" or "reference coating layer", and the coating composition (C1a) that is used to obtain the cured reference coating is referred to as " reference cover.

The composite material (S1C1) which is used as at least one embossing plate (e2) of the embossing device (E2) consists of an at least partially embossed and at least partially cured coating (C1) and a substrate (S1). Thus, the substrate (S1) is the carrier material for the coating composition (C1a) or the cured coating (C1), respectively. In this case, additional layers can be present between (S1) and (C1) in the composite material (S1C1), for example, adhesion-enhancing layers, preferably being permeable to UV radiation. However, it is preferable if there are no additional layers between (S1) and (C1) in the composite material (S1C1). The substrate (S1) or, if a coated substrate is used, the layer located on the surface of the substrate (S1) and in contact with the coating composition (C1a), preferably consists of at least one thermoplastic polymer, in particular selected from the group consisting of polymethyl (meth) acrylates, polybutyl (meth) acrylates, polyethylene terephthalates (PET), polybutylene terephthalates (PBT), polyvinylidene fluorides, polyvinyl chlorides, polyesters, including polycarbonates and polyvinyl acetate, preferably polyesters such as PBT and PET, polyamides, polyolefins such as polyethylene, polypropylene, polystyrene, as well as polybutadiene, polyacrylonitrile, polyacetal, polyacrylonitrile-ethylene-propylene-diene-styrene copolymers (A-EPDM), polyetherimides, phenolic resins, urea resins, melamine resins, alkyd resins, epoxy resins, polyurethanes, including thermoplastic polyurethane (TPU), polyetherketones, polyphenylene sulfides, polyethers, polyvinyl sp irts, and their mixtures. Particularly preferred substrates or layers on their surface are polyolefins such as, for example, PP (polypropylene) which may alternatively be isotactic, syndiotactic or atactic and alternatively may be non-oriented or oriented due to uniaxial or biaxial stretching. , SAN (styrene-acrylonitrile copolymers), PC (polycarbonates), PMMA (polymethyl methacrylates), PBT (poly(butylene terephthalate)s), PA (polyamides), ASA (acrylonitrile-styrene-acrylic ester copolymers) and ABS (acrylonitrile copolymers, butadiene and styrene), as well as their physical mixtures (combinations). Particularly preferred are PP, SAN, ABS, ASA, and combinations of ABS or ASA with PA or PBT or PC. Particularly preferred are PET, PBT, PP, PE, as well as polymethyl methacrylate (PMMA) or high impact PMMA. Particularly preferred for use as the substrate material (S1) is polyester, most preferably PET. Alternatively, the substrate (S1) as such, optionally regardless of the layer of at least one of the above polymers deposited on it, can be made from different materials such as glass, ceramic, metal, paper and/or cloth. In this case, the substrate (S1) is preferably a plate, and can be used, for example, in a roll-to-plate embossing machine (R2P). The radiation permeability of the substrate (S1) preferably corresponds to the absorption maximum of at least one photoinitiator that is used in the coating composition (C1a).

The thickness of the substrate (S1) is preferably 2 µm to 5 mm. Particularly preferred is a layer thickness of 25-1000 µm, in particular 50-300 µm.

Preferably the substrate (S1) is a film, more preferably a roll of film, very preferably a continuous roll of film. In this case, the substrate (S1) can preferably be used in the roll-to-roll embossing apparatus (R2R). In the sense of the present invention, the term "continuous film" or "continuous roll of film" preferably refers to a film that has a length of 100 m to 10 km.

The coating composition (C1a) or reference coating preferably contains

a) at least one crosslinkable polymer and/or oligomer,

b) at least one reactive diluent,

c) at least one photoinitiator and

d) at least one additive.

The at least one crosslinkable polymer and/or oligomer is preferably selected from (meth)acrylated oligomeric or polymeric compounds, urethane (meth)acrylates, vinyl (meth)acrylates, epoxy (meth)acrylates, polyester (meth)acrylates, poly (meth)acrylates, polyether(meth)acrylates, polyether(meth)acrylates, olefin(meth)acrylates, (meth)acrylated oils, silicone(meth)acrylates and mixtures thereof, preferably from urethane(meth)acrylate and silicone oligomers (meth)acrylates. The term "oligomer" refers to compounds with a relatively low molecular weight, consisting of several, usually less than 10, monomeric units. Monomeric units may be structurally the same or similar, or they may differ from each other. Generally, oligomeric compounds are liquid at room temperature and ambient pressure, provided that the dynamic viscosity is preferably less than 500 Pa*s, and more preferably less than 200 Pa*s at 23°C measured according to DIN EN ISO 2555 (Brookchild method). The term "crosslinkable" refers to polymers or oligomers that have on average at least one, preferably at least two, unfinished unsaturated groups capable of generating free radicals for crosslinking reactions. The crosslinkable oligomeric and/or polymeric compounds are preferably soluble in one or more reactive diluents.

Particularly preferably, the reference coating (C1a) contains exactly one crosslinkable polymer and/or oligomer selected from urethane (meth) acrylate oligomers or silicone (meth) acrylate oligomers, in particular from urethane (meth) acrylate oligomers or silicone (meth ) acrylate oligomers containing an average of 2-3 unsaturated groups.

Preferred reference coatings (C1a) contain at least one crosslinkable polymer and/or oligomer in a total amount of 5-50% by weight, more preferably 10-35% by weight, based on the total weight of the reference coating (C1a).

Suitable reactive diluents can be polymerized with oligomeric and/or polymeric compounds to form a reference substrate containing the copolymerized elastomeric network of the cured reference coating (C1a). The term reactive diluent refers to low molecular weight monomers that are capable of participating in a polymerization reaction to form a polymeric material. The weight average molecular weight M _w of such monomeric compounds is preferably less than 1000 g/mol, and more preferably less than 750 g/mol, as determined by GPC.

Preferably, the reactive diluents are free radical polymerizable monomers and include, for example, ethylenically unsaturated monomers such as (meth)acrylates, styrene, vinyl acetate, and mixtures thereof. Preferred monomers include (meth)acryloyl functional monomers such as, for example, alkyl(meth)acrylates, aryloxyalkyl(meth)acrylates, hydroxyalkyl(meth)acrylates, N-vinyl compounds, and combinations thereof. Suitable monomers are known to the person skilled in the art and are, for example, listed in WO 2012/006207 A1.

Particularly preferred reference coatings (C1a) contain at least one polyfunctional ethylenically unsaturated monomer, i.e. a compound that has at least two polymerizable double bonds in one molecule, as a reactive diluent to increase cross-link density. Representative examples of such polyfunctional monomers are listed, for example, in WO 2012/006207 A1. Particularly preferred reactive diluents are selected from hexanediol diacrylate and/or compounds containing at least two, preferably exactly three, structural units, which may be different from each other or be the same, of the general formula (I)

wherein

the radicals R ¹ , independently of one another, are C ₂ -C ₈ alkylene, very preferably C ₂ alkylene groups,

the R ² radicals are independently H or methyl, and

the variables m, independently of each other, are an integer in the range from 1 to 15, very preferably from 1 to 4 or 2 to 4, but with the proviso that in at least one of the structural units of formula (I) the variable m is at least 2, preferably exactly 2.

" к главной цепи указанного реактивного разбавителя. Указанное связывание предпочтительно происходит предпочтительно посредством установления связи атома кислорода радикала

- с атомом углерода главной цепи компонента. Таким образом, по меньшей мере два, предпочтительно по меньшей мере три, структурных звена общей формулы (I) присутствуют в одном компоненте, а именно, в реактивном разбавителе б). Подходящие главные цепи, например, выбирают из неопентилгликоля, триметилолпропана, триметилолэтана или пентаэритритола.All structural units of the general formula (I) are attached by means of the symbol "

to the main chain of said reactive diluent. Said coupling preferably takes place preferably by linking the oxygen atom of the radical

- with the carbon atom of the main chain of the component. Thus, at least two, preferably at least three, structural units of the general formula (I) are present in one component, namely, in the reactive diluent b). Suitable backbones are, for example, selected from neopentyl glycol, trimethylol propane, trimethylol ethane or pentaerythritol.

Said compound preferably contains a total number of "-OR ¹ -" ether groups of the general formula in the range of 4 to 18, more preferably in the range of 5 to 15, very preferably in the range of 6 to 12. Said compound preferably has a molecular weight (M _n ) in the range from 300 to 2000 g/mol, more preferably from 400 to 1000 g/mol, which is determined by GPC.

Particularly preferred compounds containing at least two structural units of general formula (I) are (meth)acrylates of neopentyl glycol, trimethylol propane, trimethylol ethane or pentaerythritol, with a total of 4-fold - 20-fold or 4-fold - 12- multiple alkoxylation, such as ethoxylated, propoxylated or ethoxylated and propoxylated, and in particular exclusively ethoxylated, neopentyl glycol, trimethylol propane, trimethylol ethane or pentaerythritol. Most preferred are the corresponding (meth)acrylates prepared from alkoxylated trimethylolpropane.

The reference coating preferably contains a total amount of 40-95% by weight, preferably 55-80% by weight, based on the total weight of the coating composition (C1a), of at least one reactive diluent, preferably hexanediol diacrylate and/or ( meth)acrylates obtained from 6-fold ethoxylated trimethylolpropane.

The at least one photoinitiator contained in the reference coating (C1a) is preferably selected from phosphine oxides, benzophenones, a-hydroxyalkylaryl ketones, thioxanthones, anthraquinones, acetophenones, benzoins and benzoin ethers, ketals, imidazoles or phenylglyoxylic acids and mixtures of the above. Particularly preferred photoinitiators are diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, benzophenone, 1-benzoylcyclohexan-1-ol, 2-hydroxy-2,2-dimethylacetophenone and 2,2-dimethoxy-2-phenylacetophenone and mixtures thereof. The at least one photoinitiator is preferably present in a total amount of 0.01-15% by weight, preferably 0.5-10% by weight, based on the total weight of the coating composition (C1a).

The reference coating (C1a) may further contain at least one additive. Said additive is preferably selected from the group consisting of flow control additives, surface active agents such as surfactants, wetting agents and dispersants, as well as thickeners, thixotropic agents, plasticizers, lubricating and antiblocking agents, and mixtures of the said. Examples of additives available on the market are Efka® SL 3259, Byk® 377, Tego® Rad 2500, Tego® Rad 2800, Byk® 394, Byk-SILCLEAN 3710, Silixan® A250, Novec FC 4430 and Novec FC 4432. Suitable total amounts at least one additive is, for example, 0.01-5% by weight, 0.2 or 0.5-3% by weight, based on the total weight of the coating composition (C1a).

Thus, particularly preferred reference coatings (C1a) contain - based on the total mass (C1a) - the following components:

- 10-35% by weight of exactly one urethane (meth) acrylate oligomer or silicone (meth) acrylate oligomer containing an average of 2 unsaturated groups,

- 55-80% by weight of hexanediol diacrylate and/or (meth)acrylates obtained from 6-fold ethoxylated trimethylolpropane (i.e. a compound containing three structural units of the general formula (I)),

- 0.5-10% by weight of ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate and/or 1-benzoylcyclohexan-1-ol and

- 0.2 or 0.5-3% by weight of a lubricating additive and/or an anti-blocking additive.

The double bond conversion of the at least partially cured reference coating layer (C1) obtained from (C1a) is preferably at least 70%, more preferably at least 75%, even more preferably at least 80%, very preferably at least at least 85%, in particular at least 90%.

The composite material (S1C1) which is used as the die (e2) for embossing the embossing tool (E2) can be obtained by applying a radiation-curable composition (C1a) to at least a portion of the substrate (S1) and curing said composition ( C1a). The application of the radiation-curable composition C1a) is preferably carried out on a moving substrate (S1). After applying the coating composition (C1a) to the surface of the moving substrate (S1), the embossing tool (E1), comprising at least one embossing plate (e1), optionally wetted with the coating composition (C1a), is preferably pressed against at least partially, to the applied coating composition (C1a). Then, the coating composition (C1a) is at least partially cured by radiation, preferably through the substrate (S1), while it is in contact with at least one embossing plate (e1) in the device (E1) for embossing, for transferring the microstructure and/or nanostructure in the form of an embossed structure to at least a partially cured coating composition (C1) of the composite material (S1C1). Radiation curing can be carried out at elevated temperatures, for example at 30-100°C or up to 80°C. Finally, the composite material (S1C1) is removed from the embosser (E1). The thickness of the coating (C1) is preferably 0.1 to 500 µm, more preferably 1 to 300 µm.

The structure width of the corresponding embossed structure in the coating (C1) of the composite material (S1C1) is preferably in the range of 10 nm to 500 µm, in particular in the range of 100 nm to 100 µm. The structure height of the respective embossed structure in the coating (C1) of the composite material (S1C1) is preferably in the range of 10 nm to 500 µm, in particular in the range of 100 nm to 200 µm.

The device for obtaining a composite material (S1C1) preferably contains the following means:

a) a moving means for moving the substrate (S1), preferably a conveyor belt,

b) means for applying preferably a radiation-curable composition (C1a) for coating at least a portion of the surface of the moving substrate (S1),

c) an embossing tool (E1) comprising at least one embossing plate (e1), preferably located downstream of the means for applying the radiation-curable coating composition (C1a), as viewed in the direction of the moving substrate (S1),

d) optional heating means, preferably a heating roller, optionally in combination with an IR radiation means,

e) optional means for cooling, preferably a chill roll, and

e) means for radiation, preferably UV radiation.

The embossing tool (E1) may preferably be an embossing calender, which preferably comprises a wire force application mechanism, more preferably a wire roller mechanism. Said calender has counter-rotating rolls, preferably arranged one above the other in the height direction, with a certain spacing, and wherein the composite material (S1C1a) to be provided with an embossed structure is fed onto the rolls and guided through the formed gap between the rolls, moreover, the width of the gap can be adjusted depending on the need. In this case, the mesh mechanism of the rolls preferably comprises a first roll, such as a metal roll, such as a steel roll, a steel roll coated with another metal layer, such as a copper layer or a nickel layer, optionally containing small amounts of phosphorus, or a roll, covered with a nickel casing, which optionally contains small amounts of phosphorus, and a second roller. The first roller (embossing roller) functions in this case as an embossing tool (E1) and contains embossing plates (e1) which have a negative shape of the embossed structure to be embossed on the surface of the composite material (S1C1a). The second roller serves as a pressing or pressure roller. The embossing occurs at the gap between the rolls, formed by counter-rotating rolls located at a certain distance from each other. The embossing tool (E1) used, which can also be a conventional impression cylinder, which has a negative embossed structure shape to be embossed on the surface of the composite material (S1C1a) and can be pressed against the composite material (S1C1a) for at least partial embossing. The positive shape of the structure to be embossed is created on the embossing tool (E1) in accordance with methods accepted and known to the person skilled in the art; depending on the structure and materials, particular methods may be particularly preferred. The embossing tool (E1) may preferably be a metal embossing tool, more preferably made of steel, of steel plated with a metal layer such as a copper layer or a nickel layer, optionally containing small amounts of phosphorus, or a roll coated with nickel. a casing which optionally contains small amounts of phosphorus, very preferably made of nickel-plated steel, optionally containing small amounts of phosphorus. Accordingly, the embossing die (e1) is preferably metal, more preferably made of steel, copper or nickel, in particular made of nickel which contains small amounts of phosphorus. However, as an alternative, soft materials such as polydimethylsiloxanes (PDMS) can also be used for the production of clichés (e1). Moreover, rolls which are coated with at least one plastic material can be used. Moreover, the embossing plate embossing tool (E1) (E1) may have a structured coating such as a UV coating.

If curing is carried out at elevated temperatures, the composite material (S1C1a) first passes through a heating roller, optionally followed by infrared irradiation, before the actual embossing procedure, i.e., curing occurs upon contact with the embossing tool (E1). After embossing and curing, the embossed composite material (S1C1) optionally passes through a chill roll for cooling. Alternatively, curing can also take place with cooling: in this case, before the actual embossing procedure described above takes place, the embossing composite (S1C1a) first passes through a chill roller. Instead of using a separate heating roller or curing roller, it is also possible to heat or cool the embossing tool (E1).

Examples of suitable radiation sources for radiation curing include low pressure, medium pressure, and high pressure mercury sources, as well as fluorescent lamps, pulsed light sources, metal halide light sources (halogen lamps), lasers, LEDs, and, in addition, electronic pulse equipment. , providing radiation curing without a photoinitiator, or excimer radiation sources. Radiation curing occurs due to exposure to high energy radiation, ie UV radiation or sunlight, or due to high energy electron bombardment. The dose of radiation, usually sufficient for crosslinking in the case of UV curing, is in the range from 80 to 3000 mJ/cm ² . Of course, it is also possible to use two or more radiation sources for curing, for example two to four. Each of these sources can also emit in different wavelength ranges.

The composite material (S1C1) can be used as a reusable die (e2) for continuous embossing of the embossing tool (E2) and allows a very effective separation between the composite material (S1C1) and the structured material (M1) containing the structured surface (SU1). In addition, the embossed material structure (M1) can be obtained with high molding precision and high reproduction success by using said composite material (S1C1) as the embossing plate (e2).

Metal tool (E2) for embossing:

In the case where a metal embossing tool (E2) is used, it is preferable if said embossing tool is selected from copper or nickel embossing tools, in particular nickel embossing tools that contain small amounts of phosphorus compounds. The width of the structure and the height of the structure of the corresponding embossed structure of the metal embossing tool then correspond to the values previously described in connection with the composite material (S1C1). According to the invention, to obtain a structured material (M1), it is preferable to use metal embossing tools (E2).

Stage a-I) or a-II)

In accordance with the first possible variant of stage a), i.e. stage a-I), of the method for obtaining the material (M1) provided in stage (1) of the method in accordance with the invention, the coating composition (P1a) is applied to at least a part surface of the substrate (F1) and at least partially embossed with at least one embossing tool (E2) containing at least one embossing plate (e2).

According to the second possible variant of step a), i.e. step a-II), the coating composition (P1a) is applied to at least a portion of the at least partially embossed surface of at least one embossing tool (E2) containing at least one embossing plate (e2), and said coating composition (P1a) is optionally coated with a substrate (F1).

The substrate (F1), or if no substrate (F1) is used, the at least one embossing plate (e2) is the carrier material for the coating composition (P1a) and the resulting cured coating layer. Suitable materials and thicknesses of the substrate (F1) include the same materials and thicknesses as already mentioned above in connection with the substrate (S1). In this case, they refer directly to the corresponding places in the description. In addition, the substrate (F1) can also be selected from polymer substrates coated on one side (I) with one-sided or double-sided adhesive tape, optionally containing a protective film, or coated (II) with a self-adhesive layer, or the substrate can be selected from self-adhesive polymer substrates. The substrate (F1) is preferably a film, more preferably a roll of film, very preferably a continuous roll of film.

Preferably, at least partial embossing in step a-I) occurs at the level of the gap between the rolls, which is formed by two rolls opposite each other, rolls rotating in opposite directions or rotating in the same direction, and

- at least one stamping plate (e2) for embossing at least one embossing device (E2), while facing the composition (P1a) for coating the composite material (F1P1a) or

- a composition (P1a) for coating at least a portion of an at least partially embossed surface of at least one embossing tool (E2) containing at least one embossing plate (e2), while facing the substrate (F1) .

If the substrate (F1) is used in step a-II), at least partial embossing in said step preferably occurs at the level of the gap between the rollers, which is formed by two opposite rollers rotating in opposite directions or in the same direction, and the composition (P1a) for coating at least one embossing plate (e2), the embossing tool (E2) faces the substrate (F1). At least partial embossing in this case is preferably achieved by pressing the substrate (F1) against the coating composition (P1a) which has been applied to at least one embossing plate (e2) of the embossing tool (E2).

In the case where no substrate (F1) is used in step a-II), at least partial embossing in said step preferably takes place by pressing the applied coating composition (P1a) onto at least one plate (e2) for embossing the tool (E2) for embossing. Said application of pressure may, for example, be achieved by means such as a roller or a mesh roller mechanism, including at least one rolling after application of the coating composition (P1a). The grid mechanism of the rolls in this case preferably comprises a metal roll such as a steel roll, a steel roll plated with a metal layer such as a copper layer, a nickel layer optionally containing small amounts of phosphorus, or a nickel-jacketed roll optionally containing small amounts of phosphorus, or even a quartz-based roller, or a roller coated with at least one plastic material.

The coating composition (P1a) which is used in steps a-I) or a-II) to obtain the structured material (M1) is referred to as "product coating". Said product coating composition (P1a) is preferably a physically curable, thermally curable, chemically curable and/or radiation curable coating composition. Preferably, the coating composition (P1a) is a chemically curable, thermally curable and/or radiation curable coating composition, more preferably a radiation curable coating composition. Accordingly, at least partial curing according to step b) preferably takes place by means of radiation curing.

Physical curing here preferably refers to the curing of the coating composition (P1a) on the product by simply evaporating the solvent(s) from said coating composition (P1a). Thermal curing in this case preferably causes a curing mechanism that is associated with temperatures above room temperature (>23°C). This may be, for example, the formation of radicals or ions, preferably radicals, from an initiator which breaks down at elevated temperatures and thus initiates a radical or ionic polymerization. Examples of such thermally activated initiators are initiators which have a half-life at 80° C. that is less than 100 hours. Chemical curing preferably refers to the reaction of at least two different and complementary reactive functional groups, for example, a polycondensation reaction such as the reaction of a -OH group with a COOH group, or a polyaddition reaction (reaction of an NCO group with a -OH group or an amino group). In addition, chemical curing preferably refers to a curing mechanism that is associated with temperatures below room temperature (<23°C), for example through the formation of anions or cations as a result of the use of appropriate catalysts. Radiation curing refers to the curing of composition (P1a) for coating the product due to the formation of radicals, preferably with an initiator capable of generating radicals.

If the coating composition (P1a) is a physically curable, thermally curable and/or chemically curable coating composition, it is prepared using at least one conventional polymer known to the person skilled in the art as a binder. In the case of thermally or chemically curable coating compositions, therefore, said binder preferably has crosslinkable functional groups. Any conventional crosslinkable functional group known to the person skilled in the art is suitable in the indicated context. In particular, crosslinkable functional groups are selected from the group consisting of hydroxyl groups, amino groups, carboxylic acid groups, thiol groups, isocyanates, polyisocyanates and epoxides. The polymers can preferably be cured or crosslinked exothermically or endothermically, preferably in the temperature range from -20°C to 250°C, or from 18°C to 200°C. Particularly suitable polymers are at least one selected from the group consisting of polyurethanes, polyethers, polyesters, polyamides, polyureas, polyvinyl chlorides, polystyrenes, polycarbonates, poly(meth)acrylates, epoxy resins, phenol-formaldehyde resins, melamine-formaldehyde resins. Said polymers may in particular have an OH functional group. In this case, they may be referred to under the general term "polyols". Such polyols may, for example, be poly(meth)acrylate polyols, polyester polyols, polyether polyols, polyurethane polyols, polyurea polyols, polyester polyacrylate polyols, polyester polyurethane polyols, polyurethane-polyacrylate polyols, polyurethane-modified alkyd resins modified with fatty acid polyesters of polyurethane polyols, as well as mixtures of said polyols. Preferred are poly(meth)acrylate polyols, polyester polyols and polyether polyols.

In this case, it is possible to use at least one polymer which cures with the participation of isocyanate and/or oligomerized isocyanate groups, very preferably at least one corresponding polyurethane and/or at least one corresponding polyurea (for example, which are called "aliphatic binders" ). Aliphatic binders are components that are obtained by reacting compounds with amino groups, in particular secondary amines, with isocyanates. If at least one polyurethane is used, then particularly suitable are polyurethane-based resins, which can be obtained by polyaddition reaction between hydroxyl-containing components, such as polyols, and at least one polyisocyanate (aromatic and aliphatic isocyanates, di-, tri- and/or polyisocyanates). As a rule, in this case, a stoichiometric reaction of the OH groups in the polyols with the NCO groups in the polyisocyanates is required. However, the stoichiometric ratio used can also be varied, as the polyisocyanate may be added to the polyol component in such an amount that "over-crosslinking" or "under-crosslinking" may occur. If epoxy resins, i.e. epoxy-based resins, are used, epoxy-based resins are preferably suitable which are prepared from glycidyl ethers having epoxy-terminated groups and, intramolecularly, hydroxyl groups as a functional group. These are preferably the reaction products of bisphenol A and epichlorohydrin and/or bisphenol F with epichlorohydrin, as well as mixtures thereof, which are also used in the presence of reactive diluents. The curing or cross-linking of such epoxy-based resins is usually accompanied by the polymerization of the epoxy groups of the epoxy ring, by means of a polyaddition reaction in the form of an addition reaction of other reactive compounds, such as curing agents, in a stoichiometric amount, with the epoxy groups, and in this case, respectively, it is necessary the presence of one active hydrogen equivalent per epoxy group (ie, one H equivalent per epoxy equivalent is needed for curing), or by polycondensation via epoxy groups and hydroxyl groups. Examples of suitable curing agents are polyamines, in particular (hetero)aliphatic, (hetero)aromatic and (hetero)cycloaliphatic polyamines, polyamidoamines, polyaminoamides, as well as polybasic carboxylic acids and their anhydrides.

The coating composition (P1a) is preferably a radiation-curable coating composition. Here, the terms "radiation curing" and "radiation curing" are used interchangeably. The term "radiation curing" preferably refers to the radical polymerization of polymerizable compounds under the action of electromagnetic radiation and/or particle radiation, examples of which are radiation from visible to (B)IR radiation in the wavelength range of λ=400-1200 nm , preferably 700-900 nm, and/or UV radiation in the wavelength range of λ=100-400 nm, preferably λ=200-400 nm, and more preferably λ=250-400 nm, and/or radiation electrons in the range from 150 to 300 keV, and more preferably with a radiation dose of at least 80, preferably 80-3000 mJ/cm ² . Particularly preferably, radiation curing is carried out using UV radiation. The coating composition (P1a) can be cured by using a suitable radiation source. Therefore, (P1a) is preferably a UV curable coating composition.

Thus, a preferred composition (P1a) for coating a product contains

a) at least one compound having an average of at least two unsaturated groups,

b) optionally at least one photoinitiator and

c) optionally at least one additive.

Compound a) preferably has an average of at least two unsaturated carbon double bonds, more preferably (meth)acrylic groups. For this purpose, compound a) can be selected from urethane(meth)acrylates, vinyl(meth)acrylates, epoxy(meth)acrylates, polyester(meth)acrylates, poly(meth)acrylates, polyether(meth)acrylates, olefin (meth)acrylates, (meth)acrylated oils, silicone (meth)acrylates, unsaturated polyester resins, di- and/or trifunctional (meth)acrylic esters, polyfunctional unsaturated monomers such as polyfunctional unsaturated (meth)acrylic esters, or mixtures of the specified. Said compound a) is preferably present in a total amount of 70-99% by weight, preferably 80-97% by weight, more preferably 85-92% by weight, based on the total weight of the coating composition (P1a).

If curing is by visible, (B)IR and/or UV radiation, the coating composition (P1a) preferably contains at least one photoinitiator capable of forming polymerization initiating radicals when irradiated with radiation having a certain wavelength. In contrast, in the case of electron emission curing, the presence of such photoinitiators is not required. Suitable photoinitiators are the same as those listed above in connection with component (c) of coating composition (C1a). If present, the photoinitiator is preferably contained in a total amount of 0.1-15% by weight, preferably 0.5-10% by weight, very preferably 1-8% by weight, based on the total weight of the composition (P1a) for coating.

In addition, the coating composition (P1a) may contain at least one additional additive. In this case, it is possible to use the same components as mentioned above in connection with component (d) of the coating composition (C1a). The at least one additive is preferably present in a total amount of 0.1-10% by weight, preferably 0.3-8% by weight, very preferably 0.7-4% by weight, based on the total weight of the composition (P1a) for coating.

The coating composition (P1a) may be a solvent-based composition or a solid coating composition. In order to promote fast curing and prevent the formation of a large amount of evaporating solvents during curing, the coating composition (P1a) is preferably a solid coating composition or a coating composition containing a small amount of solvents. Thus, it preferably has a solids content of 75-100% by weight, based on the total weight of the coating composition (P1a), as determined according to DIN EN ISO 3251:2008-06 at a temperature of 125°C and 60 min. Moreover, it preferably contains a total amount of compounds (a) to (c) of 90-100% by weight, more preferably 95-100% by weight, based on the total weight of the coating composition (P1a).

Stage b)

In step b), the applied coating composition (P1a) is at least partially cured to form an at least partially embossed and partially cured coating material, optionally containing a substrate (F1). The term "at least partially cured" in relation to the composition (P1a) for coating means the transformation of the specified composition (P1a) for coating into a ready-to-use state, that is, a state in which the material (M1) containing the specified structured coating (P1) can be used for its intended purpose.

Preferably, throughout the duration of the at least partial curing in step b), the means used in step a-I) or a-II) for applying pressure or compressing the applied coating composition (P1a) against at least one plate (e2 ) for embossing is in contact with the composition (P1a) for coating and/or at least partially cured coating formed from it.

Therefore, steps a-I) or a-II) and b) are preferably carried out simultaneously. In this case, the curing in step b) takes place during step a-I) or a-II), preferably in situ, in particular if the radiation-curable coating composition is used as the coating composition (P1a). Alternatively, and in particular if the coating composition (P1a) used is a thermally curable and/or chemically curable coating composition, steps a-I) or a-II) and b) are carried out in time each after another.

If a substrate (F1) is used in steps a-I) or a-II), then at least partial curing in step b) is preferably effected by irradiation through the substrate (F1). If no substrate is used in step a-II) and a composite material (S1C1) is used as at least one plate (e2) for embossing the embossing device (E2), the irradiation is preferably carried out through the composite material (S1C1) used in as a substrate. In both cases, it is preferred if the permeability of the substrate (F1) or substrate (S1) in the composite material (S1C1) corresponds to the absorption range of at least one photoinitiator preferably present in the coating composition (P1a). In the case where the substrate (F1) is not used in step a-II) and the embossing tool (E2) contains the embossing plate (e2), the irradiation is preferably carried out via the coating composition (P1a).

Therefore, the corresponding apparatus which is used in carrying out step b) preferably comprises at least one radiation source for irradiating the coating composition (P1a) with curing radiation. Since the coating composition (P1a) is preferably a UV curable coating composition, the curing radiation used is preferably UV radiation. If the coating composition (P1a) is not radiation curable, it is preferably chemically curable. In this case, the curing in step b) takes place thermally, for example by using suitable sources of heat radiation. Of course, combined curing is also possible, i.e. thermal curing and UV curing.

Stage c)

According to step c) of the first possible variant of the production of the structured material (M1) obtained in step (1) of the method according to the invention, the at least partially embossed coating material, optionally containing a substrate (F1), is removed from the device (E2) for embossing. After removal from the embosser, the material (M1) containing at least one micro- and/or nano-structured surface (SU1) including a number of micro- and/or nano-sized surface features is preferably obtained in the form of a free film, optionally containing substrate (F1). The material (M1) has on its surface which has been in contact with the embossing plate (e2) at least a partial negative mirror image of the embossing plate (e2) of the embossing tool (E2). The embossing tool (E2) is restored in step c).

Said removal from the embossing tool can, for example, be carried out by peeling off the at least partially embossed coating material, optionally containing a substrate (F1), from the embossing tool (E2) or vice versa. The peeling can either be carried out manually or by using conventional mechanical separation means.

Alternatively, removal from the embosser (E2) may comprise the following steps:

c-1I) applying at least one adhesive layer (AL) to at least part of the unstructured surface of the at least partially embossed coating material

or

c-1II) applying at least one adhesive layer (AL) to a substrate (F1) not in contact with the at least partially embossed coating material, and

c-2) removing, preferably peeling, the material (M1) containing at least one adhesive layer (AL) from the embossing tool (E2) or vice versa.

The adhesive layer (AL), for example, may be a laminate adhesive such as a polyacrylate or a polyacrylate-based adhesive. However, preferably the adhesive layer (AL) is a self-adhesive layer or a multi-layer construction. Such sandwich structures, for example, comprise a polymeric middle layer (PL), also referred to as an inner layer, which is coated with an adhesive (AH) on both surfaces. Each of said adhesives (AH) may be a polyacrylate or a polyacrylate-based adhesive. In principle, any type of polymer can be used to form the polymeric middle layer (PL). Examples of such polymers are poly(meth)acrylates, polyesters such as PET and/or PBT, polyvinylidene fluorides, polyvinyl chlorides, polyamides and/or polyolefins. In particular, a polyester such as PET may be used. The layer thickness of the polymer layer (PL) can be in the range of 5 to 55 µm, preferably 6 to 50 µm, more preferably 7 to 40 µm, in particular 8 to 30 µm. Each adhesive (AN) may initially be coated with a protective film such as silicone paper for ease of handling. However, before it is used as an adhesive layer (AL) in step c-I), one of the two protective films is removed. The other protective film is preferably removed at a later stage of the process according to the invention, more preferably before the composite material (M1C2) is attached to at least one object (A1).

Steps c-1I) or c-1II) and c-2) can either be carried out manually or by means of a mechanism comprising at least one means for moving the adhesive layer (AL), at least one means for applying pressure for applying pressure for attaching adhesive layer (AL) to at least part of the unstructured surface of the at least partially embossed coating material or to the substrate (F1) not in contact with the at least partially embossed coating material, and at least one separating means for removal, preferably delamination, material (M1) from the embossing tool (E2) or vice versa.

The device used in the process for producing material (M1) comprising steps a-I) or a-II), b) and c) according to option 1 preferably corresponds to the device described above in connection with the production of composite material (S1C1 ), that is, a device for embossing from roll to roll. In the case when the substrate (F1) at stage a-II) is not used, the specified device does not contain means for moving the substrate (F1).

Possible Option 2:

In addition to possible variant 1, containing steps a-I) or a-II), b) and c) of the method, the material (M1) obtained in step (1) of the method according to the invention can be obtained by other methods. Preferably, the material (M1) obtained in step (1) is selected from (I) hot stamped resin materials, preferably hot stamped resin films; (II) self-assembled monolayers; (III) materials having at least one micro- and/or nanostructured surface (SU1) obtained by laser and/or photolithography; and (IV) polymeric materials having at least one micro- and/or nanostructured surface (SU1) obtained by external action.

In hot stamping processes, polymeric materials, in particular polymeric films, are heated to temperatures above their glass transition temperature, the corresponding structure is pressed into the thinned polymeric film by means of negative or positive plates, the embossed polymeric film is cooled and removed from the plate. Suitable materials (M1) can also be obtained by microscale thermoforming, in which thermoplastic polymer films are stretched in three dimensions and heated before the plate is applied to the film. Unlike hot stamping methods, the polymer film only softens, but is still in a solid state.

The production of structured materials (M1), in particular folded polymer films, is also possible by applying an external force. In this case, the external influence, for example, can be selected from temperature changes, stretching, releasing and swelling or oxidation. During temperature changes, i.e. heating and cooling, there is a mismatch in the thermal expansion coefficients between the substrate and the polymer layer, which leads to warping of the surface layer and the formation of wrinkles on said surface. The formed folds are usually distributed randomly over the surface. Wrinkles can also be created by mechanical stretch/compression involving uniaxial stretch followed by thin film deposition and/or chemical modification. During stress relaxation, wrinkles form on the surface of the polymer material due to the mismatch of the modulus between the rigid top layer and the polymer substrate. Said folds are usually aligned orthogonally to the deformation axis. Swell wrinkling can be induced by immersing the layered polymeric film in solvent vapor or monomer solution. Wrinkles can also be formed by chemical modification, such as oxidation of the surface of the polymer film.

The material (M1) provided in step 1) of the method according to the invention is preferably obtained in accordance with option 1, i.e. the method described above, which includes steps a-I) or a-II), b) and in).

Material specifications (M1)

The material (M1) obtained in step (1) of the method according to the invention, and preferably obtained in accordance with the possible variant 1 described above, contains at least one micro- and/or nanostructured surface (SU1) comprising a series micro-sized and/or nano-sized surface elements. Said surface (SU1) preferably comprises a repeating and/or regularly spaced pattern, or the patterns are randomly arranged. The structure in each case may be a continuous embossed structure, such as a continuous fluted structure, or alternatively a series of preferably repeating individual embossed structures. The respective individual embossed structures in this case can, in turn, preferably be based on a fluted structure having more or less clearly defined projections which determine the embossing height of the embossed structure. According to the corresponding geometry of the ridges of the preferably repeating individual embossed structure, the top view may show a number of preferably repeating individual embossed structures, each of which is different, for example, preferably wavy, sawtooth, hexagonal, rhombic, rhomboid, parallelogram, honeycomb, round, dotted shapes, star shapes, rope shapes, mesh, polygonal, preferably triangular, quadrangular, more preferably rectangular and square, pentagonal, hexagonal, heptagonal and octagonal shapes, wire-shaped, ellipsoidal, oval shapes, as well as lattice-shaped patterns, moreover, it is possible to superimpose at least two patterns on each other. The protruding parts of the individual embossed structures can also have a curvature, that is to say, have a convex and/or concave structure.

The corresponding embossed structure (SU1) can be described by its width, such as the width of the ridges, in other words by the width of its structure, and by the height of the embossings, in other words by its structure height (or structure depth). The width of the structure, such as the width of the ridges, may be up to one centimeter long, but is preferably in the range of 10 nm to 1 mm. The structure height is preferably in the range of 0.1 nm to 1 mm. Preferably, however, the respective embossed structure is a microstructure and/or a nanostructure.

The size of a particular micro-sized or nano-sized surface element, respectively, is defined as its maximum extent in any direction parallel to the surface, i.e., for example, as the diameter of a cylindrical surface element or the surface diagonal of the base of a pyramidal surface element. In the case of surface features that have a macroscale extent in one or more directions within the surface (or, parallel to the surface), and a micro- or nanoscale extent in one or more other directions within the surface, the term surface feature size refers to micro- and/or or nanoscale extent of such surface features. The length of a particular micro-sized or nano-sized surface element, respectively, is defined as its extension in the direction of the length of the structured surface. Similarly, the width of a particular micro-sized or nano-sized surface element, respectively, is defined as its extent in the direction of the width of the structured surface.

The height of a raised (or raised) surface element is determined by its respective extent, measured from the adjacent bottom surface, on which the corresponding raised surface element is located in a direction perpendicular to such bottom surface. Similarly, the depth of a surface feature extending downward from an adjacent top exposed surface is determined by its respective downward extent, measured from the adjacent top surface from which the recess extends, in a direction perpendicular to such top surface.

The distance between two adjacent surface elements is defined as the distance between two maximum values or two relative maximum values, respectively, between such surface elements in a direction within the structured surface. Structured surfaces having a repeating sequence of surface features in one or more predetermined directions parallel to the surface may be characterized by one or more lengths between the highest points in such directions. In a certain direction, parallel to the surface, the term climactic length refers to the distance between the corresponding points of two adjacent, regularly spaced, adjacent elements of the surface. The foregoing can be illustrated in relation to structured surfaces containing an alternating sequence of surface elements such as grooves and laths, both surface elements, in the first longitudinal direction, on a macroscopic scale, extend essentially parallel to each other, and each of them has micro- and, optionally, a nanoscale cross-section located perpendicular to the specified longitudinal direction). The length between the highest points of such a structured surface perpendicular to the longitudinal direction is the sum of the width of the groove-type surface element and the width of the lath-type surface element in that perpendicular direction.

Each of the micro-sized and/or nano-sized surface elements (SU1) of the material (M1) preferably has a structure width of 10 nm - 500 µm, more preferably 25 nm - 400 µm, even more preferably 50 nm - 250 µm, very preferably 100 nm - 100 µm. The structure height of the respective micro-sized and/or nano-sized surface elements (SU1) of the material (M1) is preferably in the range from 10 nm to 500 µm, more preferably from 25 nm to 400 µm, even more preferably from 50 nm to 300 µm, very preferably from 100 nm to 200 µm.

The structure width and structure height of the respective surface (SU1) are preferably determined by obtaining the surface cross section (SU1) and determining the structure height and structure width of said cross section using optical microscopy.

Stage (2):

In step (2) of the method according to the invention, the coating composition (C2a) is applied to the surface (SU1) of the material (M1). Said coating composition (C2a) then forms, after partial curing in step (3), a protective layer on the structured surface (SU1) of the material (M1). Coating composition (C2a) is also referred to as "protective coating composition (C2a)" for this reason. By analogy, the cured coating composition (C2) obtained after step (3) is referred to as "coating protective layer (C2").

The protective coating composition (C2a) applied in step (2) of the method according to the invention is preferably selected from radiation-curable coating compositions, physically curable coating compositions, chemically curable coating compositions, melts and their mixtures. Surprisingly, a wide range of protective coating compositions (C2a) can be used in step (2), thus making the method according to the invention very flexible and easily adaptable to different needs in terms of curing the protective coating composition (C2a). .

According to a particularly preferred embodiment of step (2), the protective coating composition (C2a) is applied at a thickness which is sufficient to obtain the dry film thickness after curing as indicated below. This ensures effective protection of the structured surface.

The coating composition (C2a) applied in step (2) of the process according to the invention is preferably a liquid or highly viscous composition. This makes it possible to effectively fill the recesses and protrusions of the structured surface (SU1) of the material (M1), thus reducing unwanted air inclusions and preventing the cured protective layer from separating when the protected material (M1C2) is attached to the object (A1). If the coating composition (C2a) is a radiation-curable coating composition and a physically curable coating composition or a chemically curable coating composition, it preferably has a viscosity at 23°C of 1 to 500,000 mPa*s, more preferably 25 - 100,000 mPa*s, even more preferably 50 - 50,000 mPa*s, in particular 80 - 9,000 mPa*s, particularly preferably 90 - 3,000 mPa*s, in particular 100 - 2,000 mPa*s as determined according to DIN 53019-1:2008-09, DIN 53019-2:2001-02, DIN 53019-3:2008-09 and DIN 53019-4:2016-10,

If the composition (C2a) for coating is a melt, for example a TPU melt, it preferably has a glass transition temperature of 20 - -60°C, more preferably of 0 - -45°C, which is determined by dynamic scanning calorimetry (DSC ) according to DIN ISO 11357-2:2014-07 using a heating rate of 10 K/min.

Stage (3):

According to step (3) of the method according to the invention, the protective coating composition (C2a) applied in step (2) to the surface (SU1) of the material (M1) is cured at least partially to obtain a composite material (M1C2 ).

The term "at least partially curing" of the protective coating composition (C2a) is used to denote the transformation of the film formed from such a coating composition into a ready-to-use state, that is, a state in which the material (M1) provided by at least partially cured coating (C2), can be transported, stored and used for its intended purpose. In particular, the cured coating (C2) is no longer soft or tacky, but has been conditioned as a hard coating film that does not experience any subsequent significant changes in its properties, such as hardness or adhesion to the substrate, even under conditions further exposure to curing conditions as described below.

The cured composite coating composition (C2) (M1C2) has a dry film thickness of at least 5 µm. The dry film thickness of the cured layer (C2) of the coating is preferably 5-1,000 µm, more preferably 6-900 µm, even more preferably 7 to 700 µm, in particular 8 to 500 µm, particularly preferably 9 to 400 µm, in particular from 10 to 300 µm, as determined in accordance with DIN EN ISO 2808:2007-05, procedure 12A. The dry film thickness in the sense of the present invention preferably means the film thickness of the dry film over the projections of the micro- and/or nano-sized surface features (SU1). On the one hand, said dry film thickness is sufficient to obtain a fully coated structured surface (SU1), i.e. depressions and projections of the surface SU1) are completely covered with the coating composition (C2). Even though the micro-sized and/or nano-sized surface features (SU1) are completely covered by the protective coating layer (C2), they may not necessarily be completely wettable by said coating layer (C2). This makes it possible to control the adhesion of the protective layer (C2) of the coating to the structured surface and thus also the force required to remove it. On the other hand, said dry film thickness is sufficient to maintain the protective layer when it is removed, so that it can be removed without damaging said layer or structured surface (SU1) and without leaving undesirable residues on the structured surface. This ensures effective protection of the surface (SU1) of the material (M1), since the entire surface is covered with a protective layer (C2) of the coating. Of course, it is also possible to cover micro-sized and/or nano-sized surface elements (SU1) with a coating layer (C2) only partially, i.e. at least part of the protruding surface elements is not covered with a protective layer (C2) of the coating after at least partial curing of the said layer. coatings. This, however, is not preferred in accordance with the present invention.

After at least partial curing, the structured surface of the material (M1), preferably the protruding parts of the surface elements of the structured surface of the material (M1), is preferably completely covered with a protective layer (C2) of the coating. Said protective coating layer results in effective protection of the structured material (M1) during packaging, storage, transport and attachment of the structured material to the object (A1), in particular if pressure and/or shock movements are necessary to ensure a strong attachment to the object. Unlike the use of a hard foil, the use of a liquid coating composition makes it possible to fill the structured surface (SU1) of the material (M1) and thus better control the adhesion to the structured surface (SU1) and also to remove said protective layer more easily. After curing, exposure to shear forces during packaging, storage, transport and attachment does not lead to undesirable separation of the protective layer (C2) or damage to the structured surface (SU1) of the material (M1).

In order to ensure easy and residue-free removal of the at least partially cured protective coating (C2) in step (5) of the process according to the invention, said cured coating (C2) preferably has an elongation at break which is greater than 1%. In particular, the cured coating composition (C2) has an elongation at break of 5-3000%, more preferably 10-1000%, even more preferably 25-500%, particularly preferably 50-200% or 75-175 %, or 100 - 150%, in particular 10 - 100%, measured according to DIN EN ISO 527-1:2012-06 and DIN EN ISO 527-2:2012-06. An additional preferred range is from 5 to 300%.

It has been found to be preferable if the cured coating composition (C2) has a certain glass transition temperature T _g . Thus, the cured coating composition (C2) preferably has a glass transition temperature Tg of _-100-100 °C, preferably -75-75°C, more preferably -50-50°C, even more preferably -35 to 35 °C, particularly preferably -25 to 25°C or -15 to 15°C or -10 to 10°C or 0°C, in particular 25 to 50°C. Dynamic mechanical properties, in including the glass transition temperature T _g , was analyzed by applying stretch oscillations in a non-resonant mode with a frequency of 1 Hz, with an amplitude of 0.005 mm, with a heating rate of 2 K/min, from -50°C to 200°C, in in accordance with DIN EN ISO 6721-4:2019-05. The use of protective coating layers (C2) that have the indicated glass transition temperatures T _g leads to improved separation of the coating layer (C2) from the structure (M1) attached to the object (A1) and thus reduces damage or contamination of the structured surface (SU1 ) material (M1) when peeling off the layer (C2) of the coating in step (5).

The cured coating composition (C2) preferably has a surface energy of 5-80 mJ/cm ² , preferably 10-75 mJ/cm ² , more preferably 15-70 mJ/cm ² , even more preferably 20-65 mJ/cm 2 ² , particularly preferably 30-40 mJ/cm ² , in particular 21 mJ/cm ² or 22 mJ/cm ² , or 23 mJ/cm ² , or 24 mJ/cm ² , or 25 mJ/cm ² , or 26 mJ/ ^cm2 or 27 mJ/ ^cm2 or 28 mJ/cm2 or 29 mJ/cm2 as measured according to DIN EN ^55660-1 :2011-12, DIN EN ^55660-2 :2011 -12 and DIN EN 55660-3:2011-12. The use of cured coating compositions having the specified surface energy results in improved separation of the cured coating layer (C2) from the material (M1) attached to the object (A1), but does not result in unintentional removal of the protective layer (C2) of the coating during packing, storing, transporting or attaching to an object (A1).

Stage (4):

In step (4) of the method according to the invention, the composite material M1C2) is at least partially attached to the object (A1) to form an article (A1M1C2). In the sense of the present invention, the term "partial attachment" also includes the embedding of the composite material (M1C2) in the product (A1). At least partial attachment of the composite material (M1C2) to the object (A1) can be achieved, for example, by applying adhesive layers or by welding. In addition, attachment can also be facilitated by pre-attaching the composite material (M1C2) to the attachment system, which is then attached to the object (A1).

To facilitate a strong attachment to at least one object, the composite material (M1C2) preferably contains at least one adhesive layer attached to the opposite side of the protective coating (C2), i.e. the material (M1) not covered with the coating (C2). If the material (M1) does not yet contain at least one adhesive layer (AL), then said at least one adhesive layer (AL) is preferably attached to the composite material (M1C2) before attaching the said composite material (M1C2) to at least one subject. Suitable materials for the adhesive layer (AL) have already been mentioned above in connection with steps c-1) and c-II). In this case, they refer directly to the corresponding places in the description.

Before attaching the composite material (M1C2) or (ALM1C2) to at least one item (A1), it may be preferable to at least partially remove the coating composition (C2) before at least partially attaching said composite material (M1C2) or ( ALM1C2) to at least one subject (A1). This is especially preferred if it is easier to attach said composite material to the object (A1), in the case where part of the coating (C2) has been removed before attaching to the object (A1). However, the coating composition (C2) is not completely removed before being attached to the object (A1) in order to provide sufficient protection to the surface (SU1) of the structured material (M1).

If the size of the composite material (M1C2) or (ALM1C2) does not correspond to the size of the surface of the object (A1) to be structured with the material (M1), then the specified composite material (M1C2) or (ALM1C2), before attaching to at least one object, can be cut to desired size. This is particularly advantageous if objects (A1) of different sizes are to be covered with the structured material (M1), or to improve the adhesion of the structured material if larger areas are to be covered. Thanks to the protective layer (C2), the material (M1) can be cut without undesirable damage to the structured surface (SU1). With regard to this embodiment, it is also possible, before attaching the adhesive layer (AL) to the unstructured side of the material (M1), first cut the composite material (M1C2) to the desired size, and then apply the cut composite material (ALM1C2) to the object (A1).

Suitable items (A1) may be made from a variety of materials including metal, plastic, reinforced materials, glass, rubber, cloth, leather, paper, wood, and mixtures thereof. Preferably, at least one item (A1) is selected from the group consisting of surfaces in contact with liquids and gases, such as aircraft, ships and cars, rotor blades, drilling platforms, pipelines, lighting systems, display devices, photovoltaic modules , structural elements and decorative elements.

Stage (5):

According to step (5) of the method according to the invention, the protective layer (C2) of the coating is at least partially, preferably completely, removed from the article (A1M1C2) to obtain a structured article (A1M1). Said protective layer (C2) of the coating can be easily removed from the article (A1) without damaging the structured surface (SU1) and without significant residue, preferably without leaving any residue, on the structured surface (SU1).

The result after completion of step (5) of the method according to the invention is a structured product (A1M1). Since the structured surface is not damaged during the attachment of the structured material to the product, and the strong attachment of large areas of the structured material (M1) is much easier, the structured product (A1M1) obtained by the method according to the invention contains a repeating and/or regularly spaced high quality pattern.

Composite material (M1C2) according to the invention: The composite material (M1C2) according to the invention comprises at least one material (M1) which is protected by at least a partially cured coating layer (C2) and is preferably obtained after step (3) method according to the invention described above. In order to facilitate the attachment of the composite material (M1C2) to the surface of the product (A1), the object may contain an adhesive layer (AL), as disclosed above in connection with step (4) of the method according to the invention, on the surface of the material (M1) not in contact with the layer (C2) of the coating.

The material (M1) contains at least one micro- and/or nano-structured surface (SU1) including a number of micro- and/or nano-sized surface features, and is therefore structured. Said material structure (M1) is protected by an at least partially cured coating composition (C2) which is applied to the material (M1) and then partially cured. Said coating composition (C2) is insoluble in water and does not exhibit material surface features (M1) on the outer surface of the at least partially cured coating composition (C2). The term "water-insoluble" refers to partially cured coating layers which cannot be completely removed, i.e. without leaving behind detectable residues on the surface of the material (M1), by immersing the object (M1C2) in an aqueous solution, preferably water, at temperatures , constituting 4-35°C. The term "shows no material surface features (M1) on the outer surface of the at least partially cured coating composition (C2)" means in the context of the present invention that the at least partially cured coating layer (C2) has a dry film thickness sufficiently large so that the structure of the material (M1) is not transferred to the surface of the layer (C2) of the coating. Thus, the at least partially cured coating layer (C2) has a sufficiently high dry film thickness to completely cover all projections and recesses of the material (M1). Therefore, it is preferred that the surface of the at least partially cured coating layer (C2) be substantially flat. This allows the composite material (M1C2) according to the invention to be easily stacked during storage and transport, and the composite material (M1C2) or (ALM1C2) according to the invention to be easily attached to the objects (A1).

With regard to suitable materials (M1), partially cured coating layers (C2) and additional layers present, reference is made to materials (M1), coating compositions (C2a), partially cured coating layers (C2) and adhesive layers (AL), described in connection with the method according to the invention.

Everything that has been said about the process according to the invention, in particular regarding the structured material (M1) and the coating composition (C2), applies mutatis mutandis to other preferred embodiments of the subject matter (M1C2) of the present invention.

The invention is described in particular with the help of the following embodiments:

Embodiment 1: A method for manufacturing a structured article (A1M1), said method comprising the following steps:

(1) obtaining a material (M1) containing at least one micro- and/or nanostructured surface (SU1) including a number of micro- and/or nano-sized surface features;

(2) coating the surface (SU1) of the material (M1) with at least one coating composition (C2a);

(3) at least partially curing the coating composition (C2a) on the surfaces (SU1) of the material (M1), to obtain a composite material (M1C2), wherein the dry film thickness of the at least partially cured composition (C2) for coating the composite material (M1C2) is at least 5 microns;

(4) at least partially attaching a composite material (M1C2) to at least one item (A1) to obtain an article (A1M1C2); and

(5) at least partially removing the at least partially cured coating composition (C2) from the article (A1M1C2) to obtain a structured article (A1M1).

Embodiment 2: The method according to Embodiment 1, wherein the material (M1) provided in step (1) is obtained by

a-I) applying the coating composition (P1a) to the substrate (F1), obtaining a composite material (F1P1a), and at least partially embossing the coating composition (P1a) using at least one device (E2) for embossing containing at least one cliché (e2) for embossing

or

a-II) applying composition (P1a) for coating at least part of the at least partially embossed surface of at least one embossing device (E2) containing at least one cliché (e2) for embossing and optionally applying substrates (F1),

and

b) at least partially curing the coating composition (P1a) to obtain an at least partially embossed coating material, optionally containing a substrate (F1), wherein the coating composition (P1a) is in contact with the device (E2) for embossing during curing, and

c) removing the at least partially embossed coating material, optionally containing a substrate (F1), from the embossing tool (E2) to obtain material (M1).

Embodiment 3: The method according to Embodiment 2, wherein the composite material (S1C1) comprising a micro- and/or nano-structured surface including a number of micro- and/or nano-sized elements of the surface of the polymeric material (C1) and a substrate (S1) , are used as at least one cliché (e2) for embossing at least one embossing tool (E2).

Embodiment 4: The method according to Embodiments 2 or 3, wherein the substrate (S1) is selected from the group consisting of polymethyl(meth)acrylates, polybutyl(meth)acrylates, polyethylene terephthalates, polybutylene terephthalates, polyvinylidene fluorides, polyvinyl chlorides, polyesters, polycarbonates, polyvinyl acetate, polyamides, polyolefins, polyacrylonitrile, polyacetal, copolymers of polyacrylonitrile, ethylene, propylene, diene, styrene (A-EPDM), polyetherimides, phenolic resins, urea resins, melamine resins, alkyd resins, epoxy resins, polyurethanes, polyetherketones, polyphenylene sulfides, simple polyesters, polyvinyl alcohols and mixtures thereof, preferably polyethylene terephthalate, poly(butylene terephthalate), polypropylene, polyethylene polymethyl methacrylate (PMMA) or high impact PMMA.

Embodiment 5: Method according to one of Embodiments 2-4, wherein the thickness of the substrate (S1) is 2 µm - 5 mm, preferably 25 - 1000 µm, very preferably 50 - 300 µm.

Embodiment 6: The method according to one of Embodiments 2-5, wherein the coating composition (C1a) contains

a) at least one crosslinkable polymer and/or oligomer,

b) at least one reactive diluent,

c) at least one photoinitiator and

d) optionally at least one additive.

Embodiment 7: The method according to one of Embodiments 2-6, wherein the coating composition (C1a) comprises, based on the total weight of (C1a):

a) 10-35% by weight of exactly one urethane (meth) acrylate oligomer or silicone (meth) acrylate oligomer containing an average of 2 unsaturated groups,

b) 55-80% by weight of hexanediol diacrylate and/or (meth)acrylates, obtained from 6-fold ethoxylated trimethylolpropane,

c) 0.5-10% by weight of ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate and/or 1-benzoylcyclohexan-1-ol and

d) 0.2 or 0.5-3% by weight of a lubricating additive and/or anti-blocking additive.

Embodiment 8: The method according to Embodiment 2, wherein the embossing tool (E2) comprising at least one embossing plate (e2) is selected from metal embossing tools, more preferably embossing tools made of steel, steel plated with a metal layer, such as a copper layer or a nickel layer, optionally containing small amounts of phosphorus, or a roll coated with a nickel casing, which optionally contains small amounts of phosphorus, very preferably from a roll coated with a nickel layer, optionally, containing small amounts of phosphorus.

Embodiment 9: The method according to one of embodiments 2-8, wherein at least partial embossing in step a-1) takes place at the level of the roll gap, which is formed by two opposite rolls rotating in opposite directions or in the same direction. same direction, and

at least one embossing die (e2) of at least one embossing tool (E2) faces the composition (P1a) for coating the composite material (F1P1a) or

- a composition (P1a) for coating at least a portion of an at least partially embossed surface of at least one embossing tool (E2) containing at least one embossing plate (e2), while facing the substrate (F1) .

Embodiment 10: The method according to one of Embodiments 2 to 9, wherein the coating composition (P1a) is preferably a physically curable, thermally curable, chemically curable and/or radiation curable coating composition, more preferably chemically , a thermally curable and/or radiation curable coating composition, very preferably a radiation curable coating composition.

Embodiment 11: The method according to one of Embodiments 2-10, wherein the coating composition (P1a) comprises

a) at least one compound that has an average of at least two unsaturated groups,

b) optionally at least one photoinitiator and

c) optionally at least one additive.

Embodiment 12: The method according to Embodiment 11, wherein the coating composition (P1a) contains at least one compound a) in a total amount of 70-99% by mass, preferably 80-97% by mass, more preferably 85-92% by weight, based on the total weight of the coating composition (P1a).

Embodiment 13: The method according to Embodiment 11 or 12, wherein the coating composition (P1a) contains at least one photoinitiator in a total amount of 0.1-15% by weight, preferably 0.5-10% by weight. by weight, very preferably 1-8% by weight, based on the total weight of the coating composition (P1a).

Embodiment 14: The method according to one of Embodiments 11-13, wherein the coating composition (P1a) contains at least one additive in a total amount of 0.1-10% by weight, preferably 0.3-8 % by weight, very preferably 0.7-4% by weight, based on the total weight of the coating composition (P1a).

Embodiment 15: The method according to one of Embodiments 2-14, wherein the coating composition (P1a) has a solids content of 90-100% by weight based on the total weight of the coating composition (P1a) as determined according to DIN EN ISO 3251:2008-06 at 130°C for 60 min.

Embodiment 16: The method according to one of Embodiments 2-15, wherein the substrate (F1) is selected from (I) polymeric substrates such as polymethyl(meth)acrylates, polybutyl(meth)acrylates, polyethylene terephthalates, polybutylene terephthalates, polyvinylidene fluorides, polyvinyl chlorides , polyesters, polycarbonates, polyvinyl acetate, polyamides, polyolefins, polyacrylonitrile, polyacetal, copolymers of polyacrylonitrile, ethylene, propylene, diene, styrene (A-EPDM), polyetherimides, phenolic resins, urea resins, melamine resins, alkyd resins, epoxy resins, polyurethanes , polyetherketones, polyphenylene sulfides, polyethers, polyvinyl alcohols and mixtures thereof; (II) polymer substrates coated on one side with a double-sided adhesive tape, optionally containing a protective film, or a self-adhesive layer; and (III) self-adhesive backings; preferably polyethylene terephthalate, poly(butylene terephthalate), polypropylene, polyethylene, polymethyl methacrylate (PMMA) or high impact PMMA.

Embodiment 17: The method according to one of Embodiments 2-16, wherein the thickness of the substrate (F1) is 2 µm - 5 mm, preferably 25-1000 µm, very preferably 50-300 µm.

Embodiment 18: The method according to one of Embodiments 2-17, wherein the substrate (F1) is a film, preferably a roll of film, very preferably a continuous roll of film.

Embodiment 19: The method according to one of Embodiments 2-18, wherein the removal of the at least partially embossed coating material, optionally containing a substrate (F1), is carried out by peeling.

Embodiment 20: The method according to one of Embodiments 2-19, wherein removing the at least partially embossed coating material, optionally containing a substrate (F1), comprises the steps of:

c-1I) applying at least one adhesive layer (AL) to at least part of the unstructured surface of the at least partially embossed coating material

or

c-1II) applying at least one adhesive layer (AL) to a substrate (F1) not in contact with at least partially embossed coating material

and

c-2) removing, preferably peeling, the material (M1) containing at least one adhesive layer (AL) from the embossing tool (E2), or vice versa.

Embodiment 21: The method according to Embodiment 1, wherein the material (M1) provided in step (1) is selected from (I) hot stamped resin materials, preferably hot stamped resin films; (II) self-assembled monolayers; (III) materials that have at least one micro- and/or nanostructured surface (SU1) obtained by laser and/or photolithography; and (iv) polymeric materials which have at least one micro- and/or nano-structured surface (SU1) obtained by external action.

Embodiment 22: The method according to one of the previous embodiments, wherein each of the micro-sized and/or nano-sized surface features (SU1) of the material (M1) has a structure width of 10 nm - 500 µm, preferably 25 nm - 400 µm, more preferably 50 nm - 250 µm, very preferably 100 nm - 100 µm.

Embodiment 23: The method according to one of the previous embodiments, wherein each of the micro-sized and/or nano-sized surface features (SU1) of the material (M1) has a structure height of 10 nm - 500 µm, preferably 25 nm - 400 µm, more preferably 50 nm-300 µm, very preferably 100 nm-200 µm.

Embodiment 24: The method according to one of the previous embodiments, wherein the coating composition (C2a) is selected from a radiation-curable coating composition, a physically curable coating composition, a chemically curable coating composition, melts and their mixtures.

Embodiment 25: The method according to one of the previous embodiments, wherein the coating composition (C2a) has a viscosity at 23°C of 1 to 500,000 mPa*s, preferably 25 to 100,000 mPa*s, more preferably 50 - 50,000 mPa*s, even more preferably 80 - 9,000 mPa*s, particularly preferably 90 -3,000 mPa*s, in particular 100 - 2,000 mPa*s, as determined according to DIN 53019-1 :2008-09, DIN 53019-2:2001-02, DIN 53019-3:2008-09 and DIN 53019-4:2016-10,

Embodiment 26: The method according to one of embodiments 1 to 24, wherein the coating composition (C2a) has a glass transition temperature of 20 to -60°C, preferably 0 to -45°C, which is determined by dynamic scanning calorimetry (DSC) in accordance with DIN EN ISO 11357-2:2014-07, with a heating rate of 10 K/min.

Embodiment 27: The method according to one of the previous embodiments, wherein the cured coating composition (C2) has a dry film thickness of 5-1,000 µm, preferably 6-900 µm, more preferably 7-700 µm, even more preferably 8 to 500 µm, particularly preferably 9 to 400 µm, in particular 10 to 300 µm.

Embodiment 28: The method according to one of the previous embodiments, wherein the cured coating composition C2) has an elongation at break of more than 1%, preferably 5-3000%, more preferably 10-1000%, even more preferably 25-500%, particularly preferably 50-200% or 75-175% or 100-150%, in particular 10-100% measured according to DIN EN ISO 527-1:2012-06 and DIN EN ISO 527-2:2012-06.

Embodiment 29: The method according to one of the previous embodiments, wherein the cured coating composition (C2) has a glass transition temperature Tg of _-100-100 °C, preferably -75-75°C, more preferably -50-50 °C, even more preferably -35 to 35°C, particularly preferably -25 to 25°C or -15 to 15°C or -10 to 10°C, in particular 0°C, measured by fluctuations stretching in non-resonant mode, with a frequency of 1 Hz and with an amplitude of 0.005 mm and a heating rate of 2 K/min, in accordance with DIN EN ISO 6721-4:2013-05.

Embodiment 30: The method according to one of the previous embodiments, wherein the cured coating composition (C2) has a surface energy of 5-80 mJ/cm ² , preferably 10-75 mJ/cm ² , more preferably 15-70 mJ/cm ² , even more preferably 20-65 mJ/cm ² , particularly preferably 30-40 mJ/cm ² , in particular 21 mJ/cm ² , or 22 mJ/cm ² or 23 mJ/cm ² , or 24 mJ / cm ² , or 25 MJ / cm ² , or 26 MJ / cm ² , or 27 MJ / cm ² , or 28 MJ / cm ² , or 29 MJ / cm ² , which was measured in accordance with DIN 55660- 1:2011-12, DIN 55660-2:2011-12 and DIN 55660-3:2011-12.

Embodiment 31: The method according to one of Embodiments 1-19 and 21-30, wherein at least one adhesive layer (AL) is attached to a composite material (M1C2) before said composite material (M1C2) is attached to at least one subject.

Embodiment 32: The method according to one of the previous embodiments, wherein the cured coating composition (C2) is at least partially removed from the composite material (M1C2) or (ALM1C2) at least before partial bonding of the composite material ( M1C2) or (ALM1C2) to at least one subject (A1).

Embodiment 33: The method according to one of the previous embodiments, wherein the composite material (M1C2) or (ALM1C2) is trimmed to a desired size, before said composite material (M1C2) or (ALM1C2) is at least partially attached to at least one subject (A1).

Embodiment 34: The method according to one of the previous embodiments, wherein the item (A1) is selected from the group consisting of surfaces in contact with liquids and gases, such as airplanes, ships and cars, rotor blades, drilling platforms, pipelines , lighting systems, display devices, photovoltaic modules, structural elements and decorative elements.

Embodiment 35: Composite material (M1C2) containing:

- at least one material (M1) containing at least one micro- and/or nanostructured surface (SU1), including a number of micro-sized and/or nano-sized surface elements, and

- at least one partially cured coating composition (C2), wherein at least one partially cured coating composition is insoluble in water, and wherein the at least partially cured coating layer (C2) does not exhibit surface features of the material (M1 ) on the outer surface of the at least partially cured coating composition (C2).

Examples

The present invention will now be explained in more detail using working examples, however, the present invention is in no way limited to these working examples. Moreover, the terms "parts", "%" and "ratio" in the examples mean "parts by weight", "wt.%" and "weight ratio", respectively, unless otherwise indicated.

1) Methods of determination:

1.1 Solids content (solids, non-volatile fraction) The non-volatile fraction (solids or solids content) is determined in accordance with DIN EN ISO 3251 (date: June 2008). The method involves weighing 1 g of the sample into an aluminum boat, which was dried before, and drying the sample in an oven at a temperature of 125°C for 60 minutes, cooling it in a desiccator, after which it is weighed again. The remainder, in relation to the total amount of sample used, corresponds to the non-volatile fraction.

1.2. Determination of the success of coating removal (C2)

Coating removal success (C2) is determined by peeling the coating (C2) from the composite (M1C2) and visually evaluating the peeled layer (C2) of the coating as well as the structured article (M1). If the coating layer (C2) can be completely removed and the product (M1) has no visible damage, then the peeling performance of the coating layer (C2) is rated as "GOOD". If the coating layer C2) has been damaged after being peeled off, then the film stability of the coating layer (C2) is rated as "GOOD". If the coating layer (C2) cannot be removed or the product (M1) is damaged during peeling, then the peeling performance of the coating layer (C2) is rated as "poor". If the coating layer (C2) was damaged during peeling off, then the film stability of the coating layer (C2) is rated as "poor".

1.3. Determination of coating residues (C2) on the structured surface after removing the coating (C2):

Coating residues (C2) remaining on the structured surface (SU1) were determined by scanning electron microscopy. Images of the structured article (M1) were recorded at up to 1000x magnification before applying the protective coating (C2a) and after removing the cured layer (C2) of the coating. If the structured surface (SU1) at 1000x magnification showed no visible additional residue and/or abrasions after removal of the cured layer (C2) of the coating, compared to the surface (SU1) before application of the protective coating (C2a), then the rating is "None". If the structured surface (SU1) at 1000x magnification showed visible additional residue and/or abrasions after the cured (C2) coating was removed, compared to the surface (SU1) before the protective coating (C2a) was applied, then the rating is "Yes".

1.4. Determination of dry film thickness over structured surface (SU1):

Dry film thickness over structured surface (SU1) was determined using an ElektroPhysik MiniTest® 2100 microprocessor coating thickness gauge in combination with an F1.6 probe (measurement error: ±(1%+1 µm)) according to DIN EN ISO 2808 (date: May 2007), procedure 12A. In the absence of a ferromagnetic substrate, measurements were made by placing the samples on a flat ferromagnetic plate. The thickness of the protected composite material (M1C2) was measured and compared with the thickness of the material (M1). The thickness of the material (M1) was determined by measuring the thickness on the projections of the material (M1). The dry film thickness over the structured surface (SU1) was defined as the difference in thickness between the composite material (M1C2) and the material (M1).

1.5. Flexibility Definition

The flexibility of the respective composite material (M1C2) was determined by bending it through 180°. If during and/or after bending no visible cracks and/or damage are observed within the protective coating (C2), then the rating is "GOOD". If visible cracks and/or damage are observed in the protective cover (C2) during and/or after bending, then the rating is "unsatisfactory".

2) Production of structured articles (M1-1) - (M1-4) (step (1) of the method according to the invention)

2.1. Compositions (P1a-1) - (P1a-4) for coating

To obtain different structured materials (M1-1) - (M1-4), the following coating compositions (P1a-1) - (P1a-4) were used:

Composition (P1a) for coating contains the following components - based on the total weight (P1a) -

- 13.8% by weight Laromer UA 9033 (aliphatic urethane acrylate containing an average of 2 unsaturated groups, 70% solution in trimethylol propane formal acrylate; commercially available from BASF SE),

- 64.2% by weight SR 499 ((trimethylolpropane triacrylate) 6-fold ethoxylated; commercially available from the Sartomer Arkema Group),

- 13.8% by weight hexanediol diacrylate (HDDA),

- 1.0% by weight of Tego Rad 2500 (silicone acrylate, a lubricating and anti-blocking agent commercially available from Evonik),

- 3.6% by weight of Irgacure TPO-L (ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate, a commercially available photoinitiator from BASF SE) and

-3.6% by weight of Irgacure 184 (1-benzoylcyclohexan-1-ol, commercially available photoinitiator from BASF SE).

A coating composition (P1a-2) is commercially available, a radiation-curable coating composition containing at least one urethane (meth)acrylate, at least a polyfunctional ethylenically unsaturated monomer (i.e., a reactive diluent), at least one photoinitiator, and supplements available on the market.

A coating composition (Pla-3) is commercially available, a radiation curable coating composition containing at least one urethane (meth)acrylate, at least a polyfunctional ethylenically unsaturated monomer (i.e., a reactive diluent), at least one photoinitiator, at least one pigment; and commercially available additives.

A coating composition (Pla-4) is commercially available, a radiation-curable coating composition containing at least one urethane (meth)acrylate, at least a polyfunctional ethylenically unsaturated monomer (i.e., a reactive diluent), at least one photoinitiator, and at least one UV absorber.

2.2. Fabrication of structured articles (M1-1) - (M1-5) by using compositions (P1a-1) 0 (P1a-4) for coating

2.2.1 Structured product (M1-1):

The structured article (M1-1) was produced by using a roll-to-roll embossing machine having a gap formed by an embossing tool (E2) having a nickel plate (e2) having a tile structure (continuous two-dimensional triangular structure with a width of 43 µm and a height of 10 µm), and an additional roller located opposite the embossing tool. After applying the coating composition (P1a-1) of paragraph 2.1 above with a layer thickness of 20 µm to a PET film (Hostaphan® GN, layer thickness 125 µm), (F1), the resulting film package (F1 ) and the composition (P1a-1) for coating (that is, the composite material (F1P1a-1) is passed through the gap formed by the embossing tool (E2) and the additional roller, and while the plate (e2) of the tool (E2) the embossing composition is still in contact with the coating composition (Pla-1) for coating said package, the coating composition (Pla-1) is at least partially cured with a UV LED lamp. case is a UV LED lamp from Heraeus company, with a wavelength of 365 nm, 13 W/cm ² (lamp power 100%, 5 m/min.) Then the composite material (F1P1-1) is separated from the embossing tool, in resulting in material (M1-1).

The material (M1-1) is then subjected to subsequent irradiation with a UVA lamp (Panacol-Elosal UV F-900), resulting in a material (M1-1) having a microstructured surface (SU1) comprising a number of micro-sized surface features in the form of the form of tiles.

2.2.2 Structured products (M1-2) - (M1-5):

Structured articles (M1-2) to (M1-5) as described in paragraph 2.2.1 were made by using embossers (E2) which have embossing dies (e2) with different negative structures as indicated below. Table 1 gives a brief description of the manufactured structured products (M1-1) - (M1-5).

Plate microstructures (e2) for embossing fixture (E2) for embossing:

- microstructure A has a negative riblet structure with a depth of 42 µm,

- microstructure B has a negative riblet structure with a depth of 60 microns,

- microstructure B has a negative conical structure with a depth of 85 µm, and

- microstructure G has a negative pyramidal structure with a depth of 65 microns.

3) Application and curing of the protective coating (C2a) (steps (2) and (3) of the method according to the invention)

3.1. The composition of the compositions (C2a) for coating

As protective coating compositions (C2a), the following coating compositions (C2a-1) - (C2a-3) were used (all amounts are based on the total weight of the respective coating composition)

UV Curable Coating Composition (C2a-1):

- 77.5% by weight CN 966H90 (aliphatic polyester based on urethane diacrylate oligomer blended with 10% 2(2-ethoxyethoxy)ethyl acrylate; commercially available from Sartomer Arkema Group),

- 16.7% by weight hexanediol diacrylate (HDDA)

- 2.9% by weight of Irgacure TPO-L (ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate, a commercially available photoinitiator from BASF SE) and

- 2.9% by weight of Irgacure 184 (1-benzoylcyclohexan-1-ol, a commercially available photoinitiator from BASF SE).

Physically curable coating composition (C2a-2):

100% by weight Daotan-TW-1236/40WANEP (an aqueous dispersion of polycarbonate-based aliphatic polyurethane, 40% in water/1-ethyl-2-pyrrolidone; commercially available from Allnex Belgium S.A.)

Melt (C2a-3):

100% by weight Elastollan 1185-A10 (thermoplastic polyester-polyurethane elastomer; commercially available from BASF SE, T _g -40°C (as determined according to DIN EN ISO 11357-2:2014-07, heating rate 10 K/ min)).

3.2. Application and Curing of the Coating Compositions (C2a) The respective articles (M1-1) to (M1-5) were coated with the respective coating compositions (C2a) in accordance with paragraph 3.1, with the wet thickness of the layers as indicated in the Table 2:

At least partial curing of the respective protective coatings (C2a-1) to (C2a-3) was carried out as follows:

Curing of the UV curable coating composition (C2a-1) was carried out by using a roll-to-plate type device. For this purpose, coating composition (C2a-1) was applied with a wet film thickness of about 350 µm, and covered with a protective layer (unprimed PET film, ^Hostaphan® , layer thickness 125 µm). The resulting film package is pressed against the plate with a rubber roller while the coating composition (C2a-1) is at least partially cured with a UV LED lamp. The lamp is a UV LED lamp, 365, from Heraeus (lamp power 100%, 10 W/cm ² , 5 m/min, distance between lamp and coating composition (C2a-1) 5 cm).

The physically curable coating composition (C2a-2) is cured for 30 minutes at 80°C.

The TPU melt coating composition (C2a-3) was applied to the structured material (M1-1) by using a roll-to-roll device. For this purpose, the TPU was extruded at a nozzle temperature of 200° C. and pressed directly against the structured material (M1-1) in the area of the roll nip formed by the opposite rolls of said roll-to-roll type device. Curing took place by passive cooling of the resulting composite material (M1-1C2a-3) to room temperature as it passed through the device.

After curing, the thickness of the dry film over the raised parts of the structural elements of the surface (SU1), flexibility and film stability were evaluated as described above. The resulting values are listed in Table 3:

After curing, the respective coating composition (C2) completely covers the protrusions and recesses of the structured surface (SU1) of each material (M1). In addition, the presence of the protective coating (C2) does not impair the flexibility and stability of the film of the respective composite material (M1C1). Thus, the use of a protective coating layer does not adversely affect the ability to handle the protected structured material (M1).

4) Attaching the appropriate compositions (M1C2-1) - (M1C2-2) to the object (A1) and peeling the protective layer (C2) from the coating

A double-sided adhesive tape (ATP S-4705 WSA 120P bonding film; polyacrylate) was attached to the opposite side of the coating composition (C2-1), (C2-2) or (C2-3) of Composite Materials No. 1 t-14, received in paragraph 3.2. For this purpose, the silicone paper was first peeled off from one adhesive side, and parallel to the peeling direction of the silicone paper, the adhesive film, with its opening adhesive side, was transferred to the side opposite the protective layer (C2) of the corresponding composite material (M1C2), pressing the adhesive film against M1 rubber roller. Then, in the same way, the silicone paper is peeled off from the other side, and, parallel to the peeling direction of the silicone paper, the adhesive film is pressed against the surface of the steel plate (which corresponds to the item (A1)), while using a rubber roller. Appropriate protective coatings (C2-1) - (C2-3) are removed from the resulting composite material (A1M1C2) manually. The peel performance as well as the resulting structured surface (SU1) of the material (M1) attached to the object (A1) was evaluated as described above. The following results were obtained.

From Table 4, it can be seen that a structured surface (SU1) including a range of micro- and/or nano-sized surface features can be effectively protected by the use of a liquid coating composition that is at least partially cured. Sufficient protection of the structured surface (SU1) was obtained regardless of the type of coating composition (C2a) and material (M1), which makes the method according to the invention flexible with respect to the protective coating composition (C2a) and structured material (M1) . The protective layer (C2) of the coating can be easily removed by manual peeling, without tearing, without leaving any residue on the structured surface (SU1) and without damaging the structured surface.

Claims (38)

1. A method for manufacturing a structured product (A1M1), while this method includes the following steps: (1) obtaining a material (M1) containing at least one micro- and/or nanostructured surface (SU1), including a number of micro-sized and/or nano-sized surface elements; (2) coating the surface (SU1) of the material (M1) with at least one coating composition (C2a); (3) at least partially curing the coating composition (C2a) on the surfaces (SU1) of the material (M1), to obtain a composite material (M1C2), wherein the dry film thickness of the at least partially cured composition (C2) for coating the composite material (M1C2) is at least 5 microns; (4) at least partially attaching a composite material (M1C2) to at least one item (A1) to obtain an article (A1M1C2); and (5) at least partially removing the at least partially cured coating composition (C2) from the article (A1M1C2) to obtain a structured article (A1M1). 2. The method according to claim 1, wherein the material (M1) provided in step (1) is obtained by a-I) applying the coating composition (P1a) to the substrate (F1), obtaining a composite material (F1P1a), and at least partially embossing the coating composition (P1a) using at least one device (E2) for embossing containing at least one cliché (e2) for embossing or a-ii) applying the coating composition (P1a) to at least a portion of the at least partially embossed surface of at least one embossing tool (E2) comprising at least one embossing plate (e2), and optionally undercoating (F1) and b) at least partially curing the coating composition (P1a), to obtain at least partially embossed coating material, optionally containing a substrate (F1), wherein the coating composition (P1a) is in contact with the embossing tool (E2) during curing, and c) removing the at least partially embossed coating material, optionally containing a substrate (F1), from the embossing tool (E2) to obtain material (M1). 3. The method of claim 2, wherein the coating composition (P1a) is preferably a physically drying, thermally curing, chemically curing and/or radiation curing coating composition, more preferably chemically, thermally curing and/or weather curing. radiation-curable coating composition, very preferably a radiation-curable coating composition. 4. Method according to claim 2 or 3, wherein the coating composition (P1a) contains a) at least one compound having an average of at least two unsaturated groups, b) optionally at least one photoinitiator and c) optionally at least one additive. 5. The method according to one of paragraphs. 2-4, wherein the removal of the at least partially embossed coating material, optionally containing a substrate (F1), is effected by peeling. 6. The method according to one of paragraphs. 2-5, wherein the removal of the at least partially embossed coating material, optionally containing a substrate (F1), comprises the following steps: c-1I) applying at least one adhesive layer (AL) to at least part of the unstructured surface of the at least partially embossed coating material or c-1II) applying at least one adhesive layer (AL) to a substrate (F1) not in contact with at least partially embossed coating material and c-2) removing, preferably peeling, the material (M1) containing at least one adhesive layer (AL) from the embossing tool (E2), or vice versa. 7. Method according to one of the preceding claims, wherein each of the micro-sized and/or nano-sized surface elements (SU1) of the material (M1) has a structure width of 10 nm - 500 µm, preferably 25 nm - 400 µm, more preferably 50 nm - 250 µm, very preferably 100 nm - 100 µm. 8. The method according to one of the preceding paragraphs, wherein each of the micro-sized and/or nano-sized surface elements (SU1) of the material (M1) has a structure height of 10 nm - 500 μm, preferably 25 nm - 400 μm, more preferably 50 nm - 300 µm, very preferably 100 nm - 200 µm. 9. A process according to one of the preceding claims, wherein the coating composition (C2a) is selected from a UV curable coating composition, a physically drying coating composition, a thermally curable coating composition, melts and mixtures thereof, preferably from UV a curable coating composition, a physically drying coating composition, and a thermally curable coating composition. 10. The method according to one of the previous paragraphs, and the coating composition (C2a) has a viscosity at 23° C. which is 1-500,000 mPa*s, preferably 25-100,000 mPa*s, more preferably 50-50,000 mPa*s, even more preferably 80-9000 mPa*s , particularly preferably 90-3000 mPa*s, in particular 100-2000 mPa*s, as determined in accordance with DIN 53019-1:2008-09, DIN 53019-2:2001-02, DIN 53019-3:2008 -09 and DIN 53019-4:2016-10. 11. Method according to one of the preceding claims, wherein the coating composition (C2) has a dry film thickness of 5-1000 µm, preferably 6-900 µm, more preferably 7 to 700 µm, even more preferably 8 to 500 µm , particularly preferably from 9 to 400 µm, in particular from 10 to 300 µm. 12. The method according to one of the preceding claims, wherein the cured coating composition (C2) has an elongation at break of more than 1%, preferably 5-3000%, more preferably 10-1000%, even more preferably 25-500%, particularly preferably 50-200% or 75-175% or 100-150%, in particular 10-100%, measured according to DIN EN ISO 527-1:2012-06 and DIN EN ISO 527 -2:2012-06. 13. Method according to one of the preceding claims, wherein the cured coating composition (C2) has a glass transition temperature Tg of _-100-100 °C, preferably -75-75°C, more preferably -50-50°C, even more preferably -35-35°C, particularly preferably -25 to 25°C, or -15 to 15°C, or -10 to 10°C, or 0°C, in particular 25 to 50° C measured by stretching oscillations in non-resonant mode with a frequency of 1 Hz, an amplitude of 0.005 mm and a heating rate of 2 K/min, in accordance with DIN EN ISO 6721-4:2013-05. 14. A method according to one of the preceding claims, wherein the cured coating composition (C2) has a surface energy of 5-80 mJ/cm ² , preferably 10-75 mJ/cm ² , more preferably 15-70 mJ/cm ² , even more preferably 20-65 mJ/cm ² , particularly preferably 30-40 mJ/cm ² , in particular 21 mJ/cm ² , or 22 mJ/cm ² , or 23 mJ/cm ² , or 24 mJ/cm ² , or 25 MJ/cm ² , or 26 MJ/cm ² , or 27 MJ/cm ² , or 28 MJ/cm ² , or 29 MJ/cm ² , which is measured according to DIN EN ISO 527-1:2012 -06 and DIN EN ISO 527-2:2012-06. 15. Composite material (M1C2) as an intermediate product in the manufacture of a structured product (A1M1), containing: - at least one material (M1) consisting of a substrate (F1) and at least partially cured coating material containing at least one micro- and/or nanostructured surface (SU1), including a number of micro-sized and/ or nanoscale surface features and - at least one partially cured coating composition (C2), wherein at least one partially cured coating composition is insoluble in water, and wherein the at least partially cured coating layer (C2) does not exhibit surface features of the material (M1 ) on the outer surface of the at least partially cured coating composition (C2), wherein the dry film thickness of the at least partially cured coating composition (C2) is at least 5 µm and the at least partially cured composition (C2) for coating is exfoliating from a material (M1) containing at least one micro- and / or nanostructured surface (SU1), including a number of micro-sized and / or nano-sized surface elements, characterized in that the composite material comprises an adhesive layer (AL) on the surface of the material (M1) not in contact with the at least partially cured coating composition (C2).