RU2778706C2 - Method for transfer of embossed structure to surface of covering means, and combined material used as matrix for embossing - Google Patents

Abstract

FIELD: material processing.

SUBSTANCE: invention relates to the field of production of embossed structures, which are used to impart optical, bionic, and/or tactile properties to material, and concerns a method for the transfer of an embossed structure to the surface of covering means and combined material used as a matrix for embossing. The method for the transfer of the embossed structure to the surface of covering means (B2a) includes stages of: (1-i) application of covering means (B2a) to a part of the surface of substrate (F2); and (2-i) partial embossing of covering means (B2a) partially applied to the surface of substrate (F2) by means of embossing tool (P2) with at least one matrix (p2) for embossing, wherein, after embossing, combined material (F2B2aB1F1) is obtained, or (1-ii) application of covering means (B2a) to a part a partially embossed surface of partially embossed and partially cured coating (B1) used as matrix (p2) for embossing of embossing tool (P2) of combined material (B1F1) from substrate (F1) to obtain combined material (B2aB1F1), and (2-ii) application of substrate (F2) to a part of the surface of combined material (B2aB1F1), formed by (B2a) to obtain combined material (F2B2aB1F1), and (3) partial curing of covering means (B2a) inside resulting combined material (F2B2aB1F1) to obtain combined material (F2B2B1F1), wherein covering means (B2a), during the entire time of partial curing, is in contact with partial combined material (B1F1) used as matrix (p2) for embossing in combined material (F2B2aB1F1), and (4), if necessary, removal of combined material (F2B2) in combined material (F2B2B1F1) with combined material (B1F1) used as matrix (p2) for embossing, wherein stages (1-i) and (2-i), or (1-ii) and (2-ii) are performed using combined material (F1B1) from substrate (F1) used as matrix (p2) for embossing of embossing tool (P2) and at least partially embossed and at least partially cured coating (B1), and covering means (B1a) used for manufacture (B1) of combined material (F1B1) is a radiation-cured covering means with a certain composition, to combined means (F1B1), as well as the use of combined material (F1B1) as matrix (p2) for embossing of embossing tool (P2) for the transfer of the embossed structure to at least part of the surface of covering means (B2a).

EFFECT: invention provides a method for the transfer of embossed structures to a covering means and to substrates with such a covering means with appropriate microstructures and/or nanostructures, which makes possible sufficient accuracy of copying a shape when transferring embossed structures, so that the depth of modulation is not lost during embossing, and which makes it possible to manufacture a matrix for embossing the most suitable for reuse for transfer of embossed structures, or which can be carried out using such a matrix for embossing.

15 cl, 2 dwg, 5 tbl

Description

The present invention relates to a method for transferring an embossed structure to the surface of a cover means (B2a), which includes steps (1-i) and (2-i) or (1-ii) or (2-ii) and steps (3 ) and optionally (4), wherein steps (1-i) and (2-i) or (1-ii) and (2-ii) are performed using the embossing tool (P2) used as the embossing die (p2). of the combined material (F1B1) from the substrate (F1) and at least partially embossed and at least partially cured coating (B1), and the coating agent (B1a) used for the manufacture (B1) of the combined material (F1B1) is curable radiation of a coating agent with a certain composition to a combined agent (F1B1), as well as the use of a combined material (F1B1) as a matrix (p2) for embossing an embossing tool (P2) for transferring an embossed structure to at least a part of the surface of the coating agent (B2a).

State of the art

It is common practice today in engineering in many applications to provide parts on their surface with structures whose structural imprints vary in the micrometer or even nanometer range. Such structures are also called microstructures (structures with imprints in the micrometer range) or nanostructures (structures with imprints in the nanometer range). Such structures are used, for example, to influence the surface of a material with respect to optical, bionic and/or tactile properties. Such structures are also referred to as embossing or embossed structures.

In this case, the commonly used method is the transfer of these structures to the varnish. In this case, the transfer of structures to the lacquer is often achieved by means of an embossing process, in which a matrix, which, on the embossing surface or the transfer surface, contains microstructures and/or nanostructures made in a negative form, which are brought into contact with the lacquer and pressed into it. For further durable performance on the surface of the part and preservation of the structure, the varnish is usually cured directly in place.

WO 90/15873 A1 describes a process in which a radiation-curable lacquer is applied to a film or an embossing tool with a negative desired embossed structure, and then the embossing tool is pressed against the lacquered film or the lacquered embossing tool is pressed against the film. While the radiation-cured lacquer is still between the film and the embossing tool, it is cured, and then, after removal, a film is obtained which is provided with a radiation-cured lacquer that has the desired positive embossed structure. EP 1 135 287 B1 also describes such a method, in which a curable coating agent is applied to the surface of the substrate to be decorated and an appropriate negative pattern embossing matrix is pressed into the uncured coating layer. Finally, the overlay is cured and then the embossing matrix is removed. EP 3178653 A1 discloses an article including a flexible fabric with a textured surface for use in replication molding of curable systems. The fabric may have polymeric layers, which may be made using monofunctional and multifunctional acrylates.

From US Patent Nr. 9,778,564 B2, a printing material is known which, among other things, contains a component that necessarily has a methacrylamide structural element, as well as other components with 2-6 polymerizable groups, which also have alkylene oxide elements. After these materials have been deposited on a substrate, the resulting film can be patterned using a nickel embossing tool during UV curing.

US 2007/0204953 A1 discloses a process for structuring adhesive resins, which involves alternately applying a curable layer of adhesive resin to a substrate, applying a structured pattern to this layer, and then curing the layer, so as to obtain a substrate that is provided with a cured adhesive resin that contains the desired structuring.

WO 2015/154866 Al relates to a process for the manufacture of a surface structured substrate. In this case, a UV-curable coating is first applied and cured to the substrate. This cured coating is then coated with a second UV-curable coating as an embossing varnish, which is embossed and then cured to create a microstructure.

DE 102007062123 A1 describes a process for applying an embossing lacquer, such as, for example, an embossing lacquer that can be crosslinked by means of ultraviolet radiation, to a carrier film, for structuring the embossing lacquer in the micrometer range, and for curing the embossing lacquer deposited on the film to obtain an embossed film whose microstructure is then formed by depositing the metal on the embossed surface, i.e. by plating the film. However, the disadvantage of such copying of the form by subsequent metallization is the resulting undesirable reduction in the quality of copying of the form.

Finally, EP 2146805 B1 describes a method for making a material with a textured surface. The method involves providing the substrate with a curable coating, bringing it into contact with the texturizing medium for the purpose of embossing, and then curing the coating thus embossed and removing it from the texturizing medium. The texturizing medium has a surface layer that includes 20 to 50% acrylic oligomer, 15 to 35% monofunctional monomer, and 20 to 50% multifunctional monomer. WO 2016/090395 A1 and ACS Nano Journal, 2016, 10, pages 4926-4941, describe similar methods, whereby it is specifically stated that 3-fold ethoxylated trimethylol propane triacrylate (TMP(EO ) ₃ TA) to be able to obtain a relatively hard matrix of the texturizing medium. In addition, the coating agent used to obtain the surface layer according to WO 2016/090395 A1 must contain a structural unit which has at least two thionyl groups, such as, for example, trimethylolpropantris(3-mercaptopropionate). However, the use of such thiols in suitable coating compositions is often detrimental, since such formulations do not always have sufficient storage stability and coatings made from them are not sufficiently weather resistant. Added to this is the unpleasant odor caused by the use of thiols, which of course is also undesirable.

The embossing methods known from the prior art, as primarily those described in EP 2146805 B1, WO 2016/090395 A1 and ACS Nano Journal, 2016, 10, pages 4926-4941, are not always suitable enough to transfer embossing, in particular in the micrometer range and/or in the nanometer range, i.e. microstructures and/or nanostructures, in particular, without reducing to an unacceptable extent the accuracy of copying the shape during such a transfer. At the same time, the embossing is not always replicated sufficiently.

Therefore, there is a need for an embossing method that does not have the above disadvantages.

A task

Therefore, the object of the present invention is to develop a method for transferring embossed structures onto a coating agent and onto substrates having such a coating agent, in particular with appropriate microstructures and/or nanostructures, which makes it possible to achieve sufficient shape copying accuracy when transferring the embossed structures, so that when embossing is not the modulation depth is lost, and which, above all, makes it possible to manufacture the most reusable embossing matrix for transferring embossed structures, or which can be carried out using such an embossing matrix. At the same time, the embossed structures to be transferred must be replicated to the highest degree and the method above all must not suffer from disadvantages caused by undesirable or insufficient properties of the coating agent and coatings used, such as, for example, lack of adhesion.

Solution

This problem is solved by means of the items claimed in the claims, as well as the subsequent description of the described preferred embodiments of these items.

Therefore, the first subject of the present invention is a method for transferring an embossed structure to at least a part of the surface of the cover means (B2a), which includes at least steps (1-i) and (2-i) or (1-ii) ) and (2-ii), as well as at least steps (3) and optionally (4), namely:

(1-i) applying the coating agent (B2a) to at least a portion of the surface of the substrate (F2), and

(2-i) at least partial embossing of the coating agent (B2a) at least partially applied to the surface of the substrate (F2) by means of at least one embossing tool (P2) having at least one die (p2) for embossing, and the matrix (p2) for embossing includes at least one combined material (B1F1) from the substrate (F1) and at least partially embossed and at least partially cured coating (B1), and after , at least partially embossed, a combined material (F2B2aB1F1) is obtained,

or

(1-ii) applying the coating agent (B2a) to at least part of the at least partially embossed surface of the embossing tool (P2) used as a matrix (p2) for embossing the combined material (B1F1) from the substrate (F1 ) and at least partially embossed and at least partially cured coating (B1) to form a composite material (B2aB1F1), and

(2-ii) applying the substrate (F2) to at least a part of the surface of the combined material (B2aB1F1) formed by (B2a) to obtain the combined material (F2B2aB1F1),

and

(3) at least partial curing of the coating agent (B2a) inside the composite material (F2B2aB1F1) thus obtained to obtain the composite material (F2B2B1F1), wherein the coating agent (B2a) is in contact with the partial composite material (B1F1) used as a matrix (p2) for embossing in the composite material (F2B2aB1F1), and

(4) if necessary, removing the composite material (F2B2) in the composite material (F2B2B1F1) from the composite material (B1F1) used as an embossing matrix,

moreover, the coating agent (B1a) used for the manufacture of the coating (B1) used as the matrix (p2) for embossing the composite material (B1F1) is a radiation-curable coating agent,

characterized in that the coating agent (B1a) contains at least one component (A) in an amount in the range from 40 to 95% by weight,

at least one additive as component (B) in an amount in the range from 0.01 to 5% by weight,

at least one photoinitiator as component (B) in an amount ranging from 0.01 to 15% by weight, and

at least one component (D) having at least one carbon-carbon double bond in an amount in the range from 0 to 45% by weight,

and (i) components (A), (B), (C) and (D) are respectively different from each other, (ii) the indicated amounts of components (A), (B), (C) and (D) are given respectively in calculated on the total weight of the coating agent (B1a), and (iii) the amounts of all components contained in the coating agent (B1a) are summed up to 100%, and

moreover, the component (A) has at least three different from each other or at least partially identical structural elements according to formula (I)

wherein

the residues R ¹ , respectively, independently of each other, denote an alkylene group C ₂ -C ₈ ,

the residues R ² respectively independently of each other represent H or methyl, and

the parameters m, respectively, independently of each other, denote an integer parameter in the range from 1 to 15, but with the condition that in at least one structural element of formula (I) in component (A), the parameter m is equal to at least 2.

Preferably, the parameter m in at least three different or at least partially identical structural elements of the formula (I) of the component (A) of the coating agent (B1a) is equal to at least 2, respectively.

Surprisingly, it turned out that the method according to the invention makes it possible to transfer embossed structures, in particular microstructures or nanostructures, with a very high shape copying accuracy to the cover medium to be embossed (B2a), so that the modulation depth is not lost during embossing, in particular with high precision. shape copying in the range of structure width from 10 nm to 1000 µm and structure depth in the range from 0.1 nm to 1000 µm. In this regard, first of all, it turned out, in an unexpected way, that the method according to the invention makes it possible with the combination material (F1B1), which is obtained by applying on, preferably, a moving substrate (F1) a radiation-curable coating agent (B1a) and which is used as die (p2) for embossing tool (P2) for embossing, transferring the embossed structure with very high shape copying accuracy and very successful replication.

In addition, surprisingly, it turned out that therefore the method according to the invention can preferably be used in such a way that the coating (B1) of the combined material used (F1B1), which can be obtained by applying a radiation-curable coating agent (B1a) on, preferably, a moving substrate (F1), is distinguished by a high degree of conversion of double bonds. As a result, a good separation of the combined material (F2B2) from the tool (P2) is possible in the optional step (4) of the process according to the invention. In addition, it has surprisingly turned out that the process according to the invention can therefore be used in such an advantageous manner, since the coating (B1) on the substrate (F1) has a very good adhesion and the corresponding combined material (F1B1) can be used very well as a matrix (p2 ) for embossing.

In addition, surprisingly, it turned out that the combined material (F1B1) used in the method according to the invention as a matrix (p2) for embossing an embossing tool (p2) can be reused for transferring embossed structures, such as microstructures and/or nanostructures, before in total, in the form of an endless embossing die, which is preferred for economic reasons. In addition, this combination material (F1B1), preferably available as an endless embossing die (p2), is surprisingly not only reusable and thus reusable, but can also be produced economically and quickly on an industrial scale.

Therefore, another object of the present invention is a composite material (F1B1) of a substrate (F1) and an at least partially embossed and at least partially cured coating (B1) which is produced by at least partial curing by curing radiation deposited on at least part of the surface of the substrate (F1) and at least partially embossed coating agent (B1a), and the coating agent (B1a) is a radiation-curable coating agent (B1a),

characterized in that the coating agent (B1a) contains at least one component (A) in an amount in the range from 40 to 95% by weight,

at least one additive as component (B) in an amount in the range from 0.01 to 5% by weight,

at least one photoinitiator as component (B) in an amount ranging from 0.01 to 15% by weight, and

at least one component (D) having at least one carbon-carbon double bond in an amount in the range from 0 to 45% by weight,

and (i) components (A), (B), (C) and (D) are respectively different from each other, (ii) the indicated amounts of components (A), (B), (C) and (D) are given respectively in calculated on the total weight of the coating agent (B1a), and (iii) the amounts of all components contained in the coating agent (B1a) are summed up to 100%, and

moreover, component (a) has at least three different from each other or at least partially identical structural elements according to formula (I)

wherein

the residues R ¹ , respectively, independently of each other, denote an alkylene group C ₂ -C ₈ ,

the residues R ² respectively independently of each other represent H or methyl, and

the parameters m, respectively, independently of each other, denote an integer parameter in the range from 1 to 15, but with the condition that in at least one structural element of formula (I) in component (a) the parameter is at least 2.

Preferably, the combined material (F1B1) is obtained by carrying out steps (5) to (8) of the method described below.

Surprisingly, it turned out that the at least partially embossed combination material (F1B1) according to the invention can be used not only as a reusable die (p2), but preferably as a reusable endless die (p2) for embossing, in the embossing process , such as the method according to the invention, but also that due to the components contained in the cover material (B1a) used for the production of this composite material, a very good separation of the composite material (F1B1) used as a matrix (p2) from the embossed cover ( B2) or from a suitable composite material, such as including such an embossed coating, such as coating (B2), composite material (F2B2), especially when carrying out the method according to the invention and in it the optional step (4). In addition, it has surprisingly turned out that the coating (B1) of the combination material (F1B1) used, which is obtained by applying the radiation-curable coating agent (B1a) to the substrate (F1), is preferably characterized by a high degree of conversion of double bonds, such as the degree of conversion of double connections>90%. In addition, first of all, it turned out that, first of all, by performing steps (5) to (8) of the method for producing a composite material (F1B1), an embossed cover structure (B1) with high shape copying accuracy and high replication success can be obtained.

In addition, another object of the present invention is the use of the combined material (F1B1) according to the invention as a matrix (p2) for embossing an embossing tool (P2) for transferring an embossed structure to at least part of the surface of the cover means (B2a) or, according to on at least part of the surface of the coating agent (B2a) which is at least partially applied to the substrate (F2).

Detailed description

The term "comprising" in the sense of the present invention, in connection with the coating agents used according to the invention, such as, for example, the coating agent (B1a), and the method according to the invention and its method steps, preferably has the meaning "consisting of". In this case, for example, as regards the coating agent (B1a) used according to the invention, it can - along with components (A) and (B), as well as (C) and, if necessary, (D) - contain one or several other components, which are optionally mentioned below, are contained in the coating agent (B1a) used according to the invention. However, all components can be respectively present in their preferred embodiments named below. With regard to the method according to the invention, it can, in addition to steps (1-i) and (2-i), as well as (3) and optionally (4), have other optional method steps, such as, for example, steps (5)-(8).

Method for transferring an embossed structure according to the invention, comprising at least steps (l-i)-(2-i) or (1-ii) and (2-ii) and also (3) and optionally (4)

The first object of the present invention is, as described above, the method according to the invention for transferring an embossed structure to at least part of the surface of the cover means (B2a). In FIG. 1 shows by way of example steps (1-i) and (2-i), as well as (3) and optionally (4) of the method according to the invention, which can also be understood from the following description of this figure.

Preferably, the process according to the invention is a continuous process.

или понятием "тиснение"

обозначается, по меньшей мере, частичное снабжение покровного средства (В2а), факультативно в качестве части комбинированного материала (F2B2), по меньшей мере на части его поверхности тисненой структурой. При этом тисненой структурой обеспечивают по меньшей мере определенную область покровного средства (В2а). Предпочтительно, тисненой структурой обеспечивают всю поверхность покровного средства (В2а), факультативно в качестве части комбинированного материала (F2B2). Аналогичное является справедливым в связи с понятием "тиснение"

или понятием "тиснение"

в отношении используемого в качестве матрицы (р2) для тиснения и, по меньшей мере, частично тисненого комбинированного материала (B1F1) из субстрата (F1) и, по меньшей мере, частично тисненого и, по меньшей мере, частично отвержденного покрытия (В1), который может быть получен согласно описанным ниже шагам (5)-(8).The embossed structure is transferred or obtained by at least partial embossing of the coating agent (B2a) at least partially applied to the surface of the substrate (F2) according to step (2-i) of the method. Optionally, transfer is possible by steps (1-ii) and (2-ii) of the method. At the same time, the concept of "embossing"

or the concept of "embossing"

the at least partial provision of the cover means (B2a), optionally as part of the combined material (F2B2), is indicated on at least part of its surface with an embossed structure. At the same time, at least a certain area of the cover means (B2a) is provided with an embossed structure. Preferably, the entire surface of the cover means (B2a) is provided with an embossed structure, optionally as part of a combined material (F2B2). The same is true in connection with the concept of "embossing"

or the concept of "embossing"

with respect to the embossing matrix (p2) and at least partially embossed composite material (B1F1) of substrate (F1) and at least partially embossed and at least partially cured coating (B1), which can be obtained according to steps (5) to (8) described below.

The embossed structures of the composite materials (F1B1), (F2B2a) and (F2B2) are preferably based independently of one another on a repeating and/or regular pattern. This can be a continuous embossing structure, such as, for example, a continuous corrugated structure, or several, preferably repeating, single embossing structures. In this case, the respective single embossed structures can, in turn, be based on a corrugated structure, which has more or less pronounced bridges (embossing hills), by means of which the embossing height of the embossed structure is determined. According to the appropriate geometry of the bridges, preferably of a repeating single structure, a plurality of different, preferably repeating, single embossed structures can be obtained in plan view, such as, for example, in the form of a sinuous line, in the form of teeth, hexagonal, in the form of a diamond, in the form of rhombus, parallelogram, honeycomb, circles, dots, star, fines, grid, polygonal, preferably triangular, quadrangular, particularly preferably rectangular and square, pentagonal, hexagonal, heptagonal and octagonal, wire-shaped, elliptical, oval and lattice pattern, and at least two patterns can also be superimposed on each other. The bridges of the single embossed structures may also have a curvature, ie a convex or concave structure.

In this case, the respective embossed structures can be described by their width, such as, for example, the width of the bridges, that is, their structure width, and by the embossing height, that is, by their structure height (or structure depth). In this case, the width of the structure, such as the width of the bridges, can be up to a centimeter long, however, it is preferably in the range from 10 nm to 1 mm. Preferably, the structure height is in the range of 0.1 nm to 1 mm. Preferably, however, the corresponding embossed structure is a microstructure and/or a nanostructure. In this case, the microstructures are structures - both with regard to the width of the structure and the height of the structure - with impressions in the micrometer range. In this case, the nanostructures are structures - both with regard to the width of the structure and the height of the structure - with imprints in the nanometer range. Here, microstructures and nanostructures are structures that have a structure width in the nanometer range and a structure height in the micrometer range, or vice versa. In this case, the concepts of structure height and structure depth are interchangeable.

Preferably, the structure width of the respective embossed structure is in the range of 10 nm to 500 µm, particularly preferably in the range of 25 nm to 400 µm, highly preferably in the range of 50 nm to 250 µm, especially in the range of 100 nm to 100 µm. Preferably, the structure height of the respective embossed structure is in the range of 10 nm to 500 µm, particularly preferably in the range of 25 nm to 400 µm, highly preferably in the range of 50 nm to 300 µm, especially in the range of 100 nm to 200 µm. This is true for the embossed structure of both the composite material (F1B1) and the composite material (F2B2) respectively.

The width of the structure and the height of the structure of the respective embossed structure are then determined by means of mechanical probing of the surface. In this case, the height of the embossing is measured at least 10 places on one line with a uniform distribution over the entire width of the sample, and it should be paid attention to the fact that the groping device does not compress the embossed structure. Structure height determination is a shape copying accuracy determination and is performed by scanning electron microscopy according to the method described below.

Alternative (i) including steps (1-i) and (2i)

The method according to the invention according to alternative (i) includes at least steps (1-i), (2-i) and (3), and optionally (4).

Step (1-i)

Step (1-i) of the method according to the invention involves applying the coating agent (B2a) to at least part of the surface of the substrate (F2). The substrate (F2) is the carrier material for the coating agent to be applied to it (B2a) or the coating to be applied to it (B2).

The substrate (F2) or, if a coated substrate is used, the layer on the surface of the substrate (F2) preferably consists of at least a thermoplastic polymer, in particular one selected from the group consisting of polymethyl methacrylates, polybutyl methacrylates, polyethylene terephthalates, polybutylene terephthalates, polyvinylidene fluorides, polyvinyl chlorides , polyesters, including polycarbonates and polyvinyl acetate, preferably polyesters such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET), polyamides, polyolefins such as polyethylene, polypropylene, polystyrene, as well as polybutadiene, polyacrylonitrile, polyacetal, polyacrylonitrileethylene-propylene-dienestyrene copolymer (A-EPDM), polyesterimides, phenolic resins, urea-formaldehyde resins, melamine resins, acrylic resins, epoxy polyurethane resins including thermoplastic polyurethane (TPU), polyetherketones, polyphenylsulfides, polyethers, polyvinyl alcohols, and mixtures thereof. Particularly preferred substrates or layers on their surface are polyolefins, such as, for example, PP (polypropylene), which can optionally be isotactic, syndiotactic or atactic and optionally unoriented or oriented by uniaxial or biaxial stretching, SAN (styrene- acrylonitrile), PC (polycarbonates), PMMA (polymethyl methacrylates), PBT (polybutylene telephthalates), PA (polyamides), ASA (acrylonitrile-styrene-acrylic ether copolymers) and ABS (acrylonitrile-butadiene styrene copolymer), as well as their physical mixtures. Particularly preferred are PP, SAN, ABS, ASA, as well as mixtures of ABS or ASA with PA or PBT or PC. Highly preferred is PET, ABT, PP, PE and polymethyl methacrylate (PMMA) or modified high impact PMMA. Particularly preferably polyester is used as the material for the substrate (F2), most often preferably PET. Optionally, the substrate (F2) itself - optionally in spite of being coated with at least one of the above polymers - can be made from another material such as glass, ceramic, metal, paper and/or fabric. Preferably, in this case the substrate (F2) is a plate and can be used in a roll-to-plate embossing device.

Preferably, the thickness of the substrate (F2) is between 2 µm and 5 mm. Particularly preferably, the layer thickness is from 25 to 1000 µm, in particular from 50 to 300 µm.

Preferably, the substrate (F2) is a film, particularly preferably a film web, most preferably an endless film web. Preferably, in this case, the substrate (F2) can be used in a roll-to-roll embossing device.

Preferably, the term "endless film" or "endless film web" in the sense of the invention means a film with a length of 100 m to 10 km.

Preferably, the substrate (F2) when performing step (1-i) (and preferably also when performing steps (2-i), (3) and (4) of the method, as well as when performing steps (1-ii), ( 2-ii), (3) and (4) of the method of alternative (ii) is moved, and therefore it is a movable composite material Preferably, the substrate (F2) during step (1-i) and also step (2-ii) is transported by means of a transport device such as, for example, a conveyor.Therefore, the corresponding device used for carrying out step (1-i) as well as step (2-ii) preferably includes such a transport device. step (1-i), the device includes means for applying a preferably radiation-curable coating agent (B2a) to at least a portion of the surface of the substrate (F2). ) devices.

Step (2-i)

Step (2-i) of the method according to the invention provides for at least partial embossing of at least partially applied coating agent (B2a) on the surface of the substrate (F2) by means of at least one having at least one matrix (p2) for embossing tool (P2) for embossing, and the matrix (p2) for embossing includes a combined material (B1F1) from the substrate (F1) and at least partially embossed and at least partially cured coating (B1), and after at least partial embossing, a combined material (F2B2aB1F1) is obtained. Preferably, in step (2-i), the embossing tool (P2), including the embossing die (p2), is at least partially pressed against the applied coating means (B2a) during step (2-i).

Preferably, the embossing die (p2) of the embossing tool (P2) used in step (2-i) is reused and reused for transferring at least one embossed structure, preferably in the method according to the invention, if it necessarily includes step (4). Preferably, by means of step (2-i), the microstructures and/or nanostructures are transferred as an embossed structure onto the coating agent (B2a).

Preferably, in relation to the matrix (p2), that is, in relation to the combined material (F1B1), we are talking about a film web (F1), which has at least partially embossed and at least partially cured coating (B1) . Particularly preferably, the substrate (F1) is an endless film web which has an at least partially embossed and at least partially cured coating (B1), whereby the composite material (F1B1) used as the matrix (p2) for embossing is an endless embossing matrix, especially when the substrate (F2) is also an endless film web.

At least one embossing die (p2) of the embossing tool (P2) used for at least partial embossing according to step (2-i) has a "negative structure" ("negative shape"), i.e. as a mirror image of that embossed structure, which is obtained after performing the optional step (4) of the method according to the invention, the combined material (F2B2) from the substrate (F2) and at least partially embossed and fully cured coating (B2), and a mirror image of the embossed matrix structure ( pi) for embossing tool (P1) for embossing.

The respective device used to carry out step (2-i) includes means for at least partially embossing the coating agent (B2a) at least partially applied to the surface of the substrate (F2) by means of at least one tool (P2) for embossing. In addition, the device used preferably has means for pressing the tool (P2) against the substrate (F2) used, preferably as an endless film seal, after applying the radiation-curable coating agent (B2a) to (F2), which, when viewed in the transport direction The substrate (F2) is preferably positioned downstream of the means for applying the radiation-curable coating agent (B2a).

At least partial embossing according to step (2-i) of the method according to the invention is carried out with an embossing tool (P2). With regard to (P2), it may preferably be an embossing calender, which preferably includes a screening device, particularly preferably a screening roller. Preferably, this calender has rollers that rotate in the opposite direction or in the same direction at a certain distance one above the other in the vertical direction, and the combined material (F2B2a) to be provided with an embossed structure is brought to the rollers and guided through the gap formed between the rollers, the width of the gap being set variable. In this case, the screening device preferably includes a first roll, such as, for example, a metal roll, for example a steel roll or a nickel roll or a quartz-based roll or a roll coated with at least one synthetic material, and a second roll. The first roll functions as an embossing roll (printing roll). Here, the screening device preferably includes a second roll (pressure roll or pressure roll). In this case, the first roller functions as an embossing tool (P2) and contains the negative shape of the embossed structure to be embossed into the surface of the composite material (F2B2a). To this end, the embossing tool (P2) is provided with a combination material (F1B1) as an embossing matrix (p2), which is a negative mold. The creation of the negative shape of the structure to be embossed on the embossing tool (P2) takes place according to the usual methods known to the person skilled in the art, with specific methods being particularly preferred depending on the structure and materials. Preferably, according to the invention, this is realized in that the embossing roller functions as an embossing tool (P2) and includes the composite material (F1B1) used as an embossing matrix (p2) in the form of a coated and at least partially an embossed film, preferably a film web, particularly preferably a moving endless film web. The pressure roller moves the composite material (F2B2a) to be embossed in the opposite direction. At the roll gap point, which is formed by spaced, counter-rotating rolls, embossing occurs according to step (2-i). In this case, the first roll, which drives the composite material (F1B1) functioning as the embossing die (p2), serves to emboss the composite material (F2B2a), which is driven opposite to this embossing roll by the second roll, which presses the composite material to be embossed ( F2B2) to the first embossing roll. As already described above, the structures on the embossing roll, i.e. the structures of the embossing die (p2), can have a continuous structure or can be made in the form of a discontinuous structure (a sequence of individual embossed structures), and a combination of both structures is also possible. The corresponding structures on the embossing roller can have different geometries depending on the intended structure of the combined material. If necessary, step (2-i) can be performed at an elevated temperature, for example at 30-100°C or up to 80°C. In this case, the composite material to be embossed (F2B2a) first passes through the heating rollers, then, if necessary, infrared light is irradiated before the embossing process described above takes place. Then, after embossing, the embossed composite material (F2B2a) is optionally passed through chill rolls for cooling. Optionally, step (2-i) may take place during cooling. In this case, the composite material to be embossed (F2B2a) first passes through the chill rolls before the own embossing process described above takes place.

Preferably, the combined material (F1B1) used in step (2-i) as the matrix (p2) for embossing is the combined material of the film web (F1) and applied and at least partially embossed and at least partially cured coating (B1).

Preferably, the composite material (F1B1) used in step (2-i) as an embossing die (p2) is guided during step (2-i) along the first roll functioning as a tool (P2), and the composite material (F2B2) is guided along a second roll, which is located opposite the first roll and rotates relative to it in the opposite direction or in one direction, preferably, is rotating in the opposite direction.

Preferably, at least partial embossing according to step (2-i) takes place at the height of the gap between the rolls, which is formed by opposed opposite or co-rotating rolls, wherein the at least partially embossed coating (B1) of the combined material (B1F1) faces the cover means (B2a) of the combined material (F2B2). In this case, at least partial embossing is preferably achieved by pressing or pressing the composite material (F1B1) against the composite material (F2B2a).

Used in step (2-i) as a matrix (P2) for embossing, the combined material (B1F1) of the substrate (F1) and at least partially embossed and at least partially cured coating (B1) will hereinafter be referred to as "template substrate" or "template film". If the substrate (F1) is a film (Folie), then the corresponding master film (Masterfilm) is called "master film" ("Masterfolie"). If the substrate (F1) is a foil web, then the corresponding master foil is called a "master foil web". The coating (B1) of the template film will hereinafter be referred to as "at least partially cured template varnish" or "template varnish layer", and the coating agent (B1a) used to make the cured template varnish will be referred to as "template varnish". Preferably, there is no other (varnish) layer between (F1) and (B1) of the combined material (F1B1). However, it is also possible that between (F1) and (B1) of the combined material (F1B1) there is at least an adhesion enhancing layer, which in this case is preferably transparent to UV radiation.

The composite material (F1B1) used as an embossing matrix can optionally be pre-treated with the coating agent (B2a) used before step (2-i). Such pre-treatment comprises, or preferably is, wetting the embossing matrix with the coating agent (B2a).

Step (3)

Step (3) of the method according to the invention involves at least partial curing of the coating agent (B2a) inside the combined material (F2B2aB1F1) obtained after step (2-i) or step (2-ii) to obtain a combined material (F2B2B1F1), moreover the covering means (B2a) during the entire duration of at least partial curing is in contact with the partial combined material (B1F1) used as a matrix (p2) for embossing in the combined material (F2B2aB1F1).

Preferably, steps (2-i) and (3) are performed simultaneously. In this case, at least partial curing according to step (3) during step (2ii) takes place, preferably directly on site.

Therefore, the corresponding device used to carry out step (3) preferably includes at least one radiation source for irradiating the covering means (B2a) with curing radiation. Since the coating agent (B2a) is preferably a UV-curable coating agent, UV radiation is preferably used as the curing radiation. If the coating agent (B2a) is not radiation curable, it is preferably chemically curable. In this case, curing according to step (2) takes place thermally, for example by using a suitable heat emitter. Of course, combined curing, ie thermal curing and UV curing, is also possible.

Suitable radiation sources for radiation curing are, for example, low-pressure mercury emitters, medium-pressure emitters, high-pressure emitters, as well as fluorescent lamps, pulsed emitters, metal halide emitters (halogen lamps), lasers, light emitting diodes and, in addition, devices with an electronic flash, due to which radiation curing without a photoinitiator is possible, or excimer emitters. Curing radiation occurs through the action of high energy radiation, that is, ultraviolet radiation or daylight, or through the clothing of high energy electrons. Typically, a sufficient radiation dose for crosslinking in the case of curing with ultraviolet radiation is in the range from 80 to 3000 mJ/cm ² . Of course, several radiation sources, for example two to four, can also be used for curing. They can emit respectively in different wavelength ranges. Preferably, at least partial curing in step (3) occurs by irradiation through the substrate (F2). In this case, it is preferable that the transparency of the substrate (F2) for the radiation used is matched to the at least one photoinitiator used, which is preferably contained in the coating agent (B2a). Thus, for example, the PET material as substrate (F2), that is, for example, a PET film, is transparent to radiation with a wavelength below 400 nm. 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphosphinate and bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide are taken into account as photoinitiators that form radicals during this radiation. Preferably, therefore, at least one such photoinitiator is present in the coating agent (B2a) in this case.

Optional step (4)

Step (4) of the method according to the invention optionally removes the composite material (F2B2) in the composite material (F2B2B1F1) from the composite material (B1F1) used as a matrix (p2) for embossing. As a result, a combined material (F2B2) can be obtained from the substrate (F2) and the at least partially embossed and at least partially cured coating (B2). Preferably, step (4) is performed.

Alternative (ii)

The method according to the invention in accordance with alternative (ii) includes at least steps (1-ii), (2-ii) and (3), and optionally (4). Steps (3) and (4) have already been described above in connection with alternative (i).

Step (1-ii)

Step (1-ii) of the method according to the invention involves applying the coating agent (B2a) to at least part of the at least partially embossed surface of the embossing tool (P2) used as a matrix (p2) for embossing the combined material (B1F1 ) from the substrate (F1) and at least partially embossed and at least partially cured coating (B1) to obtain a combined material (B2aB1F1).

The composite material (F1B1) used as an embossing matrix can optionally be pre-treated with the coating agent (B2a) used before step (1-ii). Such pre-treatment includes, or preferably is, wetting the embossing matrix with a coating agent (B2a).

Step (2-ii)

Step (2-ii) of the process according to the invention involves applying a substrate (F2) to at least a part of the surface of the combined material (B2aB1F1) formed by (B2a) to obtain a combined material (F2B2aB1F1).

Preferably, the combined material (F1B1) used in step (1-ii) as a matrix (p2) for embossing after coating (B2a) on at least part of the at least partially embossed surface to obtain a combined material (B2aB1F1 ) during step (2-ii) is guided along the first roller (P2) functioning as an embossing tool, and the substrate (F2) used in step (2-ii) is guided along the second roller, which is located opposite the first roller and rotates relative to it in the opposite direction or in one direction, preferably, is counter-rotating.

Preferably, at least partial embossing according to step (2-ii) takes place at the height of the gap between the rolls, which is formed by opposed opposite or co-rotating rolls, the cover means (B2a) of the combined material (B2aB1F1) facing to the substrate (a2). In this case, at least partial embossing is preferably achieved by pressing or pressing the substrate (A2) against the combined material (B2aB1F1).

In FIG. 1 is a schematic side view of a device that can be used to carry out steps (1-i) and (2-i), as well as (3) and optionally (4) of the method according to the invention, and which shows the method according to the invention by way of example. Likewise, the device can in principle be used in a similar way to carry out steps (1-i) and (2-i) as well as (3) and optionally (4) of the method according to the invention. By means of this arrangement, structures such as microstructures and/or nanostructures can advantageously be transferred from the matrix (F1B1, p2) present as template film to the substrate (F2) coated (B2a). Therefore, this device is generally referred to as a transmission device and is provided in FIG. 1 with reference symbol (10).

In the transfer device (10), an embossing area (1) is formed as a central element, in which a printing roll (2) with a roll lining of quartz glass is located. The printing roller (2) is driven. Next to the printing roller (2) is a radiation source in the form of an illuminating device (3) which generates ultraviolet light and, above all, can include a number of ultraviolet LEDs located in the longitudinal direction of the printing roller. As shown in FIG. 1, the lighting device (3) can also be located inside the printing roll. In the area (1) embossing is pressed against the printing roller (2) pressure roller. In the matrix rack (5) of the transfer device (10) there are rolls (6) and (7) of the film web, which can be driven by a motor. Of course, the film web rolls (6) and (7) can be supported in bearings and positioned differently than in the matrix stand (5), for example in a cabinet-like element or also outside the transfer device (10) itself. Shown here in the form of rolls (6) and (7) arranged in a matrix rack of the film web, a template film web (8) is wound, which is an endless matrix for embossing. The patterned film web (8) on the transfer surface is provided with a patterned lacquer layer in which the negative shapes of the microstructures and/or nanostructures to be transferred are embedded in the form of a surface relief. The pattern varnish layer is at least partially cured so that the relief structures therein are stable. The template film web (8) can be obtained by carrying out steps (5) to (8) of the method according to the invention and is thus a composite material (F1B1). The template film web (8) is unwound from the first roll (6) of the film web, is guided through various guide roller systems to the embossing area (1) and passes, as can be seen from FIG. 1 vertically from above into the area between the print roller (2) and the pressure roller (4). There it is guided with a snug fit along the circumference of the printing roll (2) and again fed through the system of guide rollers with web tensioners to the second roll (7) of the film web and wound on it. Forming the substrate (2) to be provided with microstructures and/or nanostructures, the film web (9) proceeds from the roll (11) of the film web and here, through various systems of guide rollers with web tensioners, is brought to the area (1) of embossing, passes there in a stretched state through the section circumference of the pressure roll (4), and from there to the contact area of the pressure roll (4) against the printing roll (2) or to the area formed between these elements of the gap between the rolls. The film web (9) leaves this area in the image according to FIG. 1 vertically downwards and - again guided through a system of guide rollers and web tensioners - is directed to the roll (12) of the film web and is wound on it in the form of a finished processed product. On its way to the area (1) of embossing or to the gap between the rolls between the printing roll (2) and the pressure roll (4), the film web (9) is provided on its facing in the area (1) printing to the printing roller (2) varnish layer. Thus, by means of the varnishing device (27) according to step (1-i) of the process according to the invention, the coating agent (B2a) is applied to the film web used as (F2). Then, in the printing area (1), the film web (9) with its surface provided with a not yet cured lacquer layer is brought together with the surface of the template film web (8) provided with a template layer to carry out step (2-i) of the method according to the invention. In this case, the film web (9) passes over the pressure roll (4), and the template film web (8) passes over the printing roll (2). Both webs, the film web (9) and the master film web (8), are provided with their lacquer layer (at the master film web (8) at least partially cured master varnish layer, which corresponds to the coating (B1), at the film web ( 9) with the uncured lacquer layer which corresponds to the coating agent (B2a) with the surfaces facing each other In the area in which the pressure roller (4) is pressed against the printing roller (2), a negative display of the structures to be transferred, such as microstructures and/or nanostructures , which is formed in the master lacquer layer, is pressed into the uncured lacquer layer, which corresponds to the coating agent (B2a), whereby the structures are transferred. lacquer layer, which corresponds to the coating agent (B2a) of the lacquer layer on the film web (9), while This lacquer layer is in contact with the pattern lacquer layer (8). This is carried out directly during the transfer of structures and directly on site, at least partial curing of the lacquer layer. In this case, the irradiation of the film web (9) or the uncured lacquer layer applied to it occurs through the film material (9) during irradiation from the outside on the printing cylinder (2). Optionally, the irradiation occurs through the quartz glass material of the side surface of the impression cylinder (2) and also through the material of the template film web (8) and the template lacquer layer applied thereon. Accordingly, the film web (8) and the pattern lacquer layer are transparent to the radiation used, in this case ultraviolet light. The side surface of the printing roll (2) is here described as consisting of quartz glass. In principle, the other material is also taken into account in this case, as long as it is permeable to the curing radiation emitted from the inside of the printing roll (2) (which may be other than ultraviolet light). Optionally, instead of the lighting device (3), which provides ultraviolet illumination, for example a thermal heat emitter can also be used if the coating agent (B2a) is a non-radiatively curable coating agent. Following at least partial curing by ultraviolet illumination, optional additional illumination is possible, for example by means of infrared radiation. At the end of this curing process, according to the optional step (4) of the method according to the invention, the film web (9) and the template film web (8) are separated to separate the laminated composite material (F2B2) and the template film (F1B1) respectively. The coated film web (9) thus provided with the desired structure (i.e. composite material (F2B2)) is sent as a finished product to the film web roll (12) and wound on it. If the illumination of the printing roll (2) takes place from the outside by means of an illumination device (3), then the coated film web (9) provided with the desired structure (i.e. composite material (F2B2)) can also be opaque, if the placement is chosen such that the patterned film web (8) (that is, the composite material (F1B1)) and the film web (9) (that is, the composite material (F2B2)) are swapped. Varnishing in the varnishing device (27) according to step (1-i) of the method according to the invention can then take place without limitation of the process on the template film web (8).

Optional steps (5)-(8) of the method according to the invention for the production of composite material (F1B1) used as a matrix (p2) for embossing

Preferably used in step (2-i) and step (1-ii) of the method, the combined material (F1B1) of the substrate (F1) and at least partially embossed and at least partially cured coating (B1) can be obtained through the specific steps (5)-(8) described below. Therefore, steps (5)-(8) of the method according to the invention are carried out to produce the combined material (F1B1) used as the matrix (p2) for embossing. In FIG. 2 shows by way of example steps (5)-(8) of the method according to the invention, which can also be understood from the following description of this figure.

Step (5)

Step (5) of the method according to the invention involves applying a radiation-curable coating agent (B1a) to at least part of the surface of the substrate (F1). The substrate (F1) is the carrier material for the coating agent (B1a) to be applied to it or the coating to be applied to it (B1). The substrate (F1) may be coated). As the material for the substrate (F1) or for the surface layer, the same materials are taken into account that can be used for the manufacture of the substrate (F2) and have already been mentioned above. In this case, it is strongly recommended to refer to the relevant fragments of the description. The substrate (F1) is preferably a film, particularly preferably a film web, most preferably an endless film web. The preferred material for (F1) is polyester, especially PET. Preferably, the thickness of the substrate (F1) is between 2 µm and 5 mm. Particularly preferred is a layer thickness of 25 to 1000 µm, in particular 50 to 300 µm.

Preferably, the substrate (F1) during steps (5) (and preferably also during steps (6), (7) and (8) of the method) is moved and is therefore a moving substrate. Preferably, the substrate (F1) during step (5) is moved by means of a transport device such as a conveyor. Therefore, the respective device used to carry out step (5) preferably includes such a transport device. In addition, the corresponding device used to carry out step (5) includes means for applying a preferably radiation-curable coating agent (B1a) to at least a portion of the surface of the substrate (F1).

Step (8)

или "тиснение"

уже были определены выше. В соответствии с этим ниже в связи с (В1а) или (В1), по меньшей мере, частичное обеспечение покровного средства (В1а) в качестве части комбинированного материала (F1B1a) называется тисненой структурой. При этом тисненой структурой обеспечивают по меньшей мере определенную область покровного средства (В1а). Предпочтительно, тисненой структурой обеспечивают всю поверхность покровного средства (В1а) в качестве части комбинированного материала (F1B1a). Предпочтительно, во время выполнения шага (6) инструмент для тиснения, по меньшей мере, частично прижимают или придавливают к нанесенному покровному средству (В1а).Step (8) of the method according to the invention provides for at least partial embossing of the coating agent (B1a) at least partially applied on the surface of the substrate (F1) by means of a tool (P1) having at least one embossing die (pi) for embossing. In this case, by at least partial embossing, the embossed structure is at least partially transferred to the surface of the coating agent (B1a) deposited on the substrate (F1). The concept of "embossing"

or "embossed"

have already been defined above. Accordingly, in connection with (B1a) or (B1), at least partially providing the cover means (B1a) as part of the combined material (F1B1a) is referred to as an embossed structure below. At the same time, at least a certain area of the cover means (B1a) is provided with an embossed structure. Preferably, the entire surface of the cover means (B1a) is provided with the embossed structure as part of the combined material (F1B1a). Preferably, during step (6), the embossing tool is at least partially pressed or pressed against the applied coating agent (B1a).

Preferably, by means of step (6), microstructures and/or nanostructures are transferred to the cover means (B1a) as an embossed structure.

Therefore, the corresponding device used to carry out step (6) includes means for at least partially embossing the coating means (B1a) at least partially applied to the surface of the substrate (F1) by means of at least one tool (P1) for embossing. In addition, the device used preferably has means for pressing the embossing tool (P1) against the substrate (F1) used, preferably in the form of an endless film web, after applying the radiation-curable coating agent (B1a) to (F1), which, when considered in in the substrate transport direction (F1) is preferably positioned downstream of the means for applying the radiation-curable coating agent (B1a).

At least partial embossing according to step (6) of the method according to the invention is carried out with an embossing tool (P1). With regard to (P1), it may preferably be an embossing calender, which preferably includes a screening device, particularly preferably a screening roller. Preferably, this calender has rollers that rotate in the opposite direction or in the same direction at a certain distance one above the other in the vertical direction, and the combined material (F1B1a) to be provided with an embossed structure is brought to the rollers and guided through the gap formed between the rollers, the width of the gap being set variable. Here, the screening device preferably includes a first roll, such as, for example, a metal roll, such as a steel roll or a nickel roll, and a second roll. The first roller (embossing roller) functions as an embossing tool (P1) and contains the negative shape of the embossed structure to be embossed into the surface of the composite material (F1B1a). This corresponds to the positive structure to be embossed into the composite material (F2B2a) in step (2) of the process. The second roll serves as a pressing or pressure roll. The creation of the positive shape of the structure to be embossed on the embossing tool (P1) takes place according to the usual methods known to the person skilled in the art, with specific methods being particularly preferred depending on the structure and materials. Preferably, this is realized according to the invention in that the embossing roller functions as an embossing tool (P1) and includes an embossing die (pi). The combination material (F1B1a) to be embossed, for example in the form of an at least partially coated (B1a) film web, is conveyed by means of the pressure roller in the opposite direction. At the roll gap point, which is formed by spaced, counter-rotating rolls, embossing occurs according to step (6). In this case, the first roll, which drives the embossing matrix (pi), serves to emboss the combined material (F1B1a), which is driven by the second roll opposite this embossing roll, which presses the combined material (F1B1a) to be provided with an embossed structure against the first embossing roll. If necessary, step (6) can be performed at an elevated temperature, for example at 30-100°C or up to 80°C. In this case, the composite material to be embossed (F1B1a) first passes through the heating rollers, then, if necessary, infrared light is irradiated before the actual embossing process described above takes place. After the embossing, the embossed composite material is then, if necessary, passed through chill rolls for cooling. Optionally, step (6) may take place during cooling. In this case, the composite material to be embossed (F1B1a) first passes through the chill rolls before the own embossing process described above takes place.

As the embossing tool (P1), a conventional impression cylinder can also be used, which has on the surface the negative shape of the embossed structure to be embossed into the surface of the combined material (F1B1a). It can be pressed against the composite material (F1B1a) for at least partial embossing.

At least one die (pi) of the tool (P1) used for at least partial embossing according to step (6) has a "positive structure" ("positive shape"), i.e. an embossed structure which, after step (4) the method according to the invention has obtained a combined material (F2B2) from the substrate (F2) and at least partially embossed and fully cured coating (B2). Preferably, the embossing tool (PI) is a metal embossing tool, particularly preferably nickel. Accordingly, the embossing die (pi) is preferably metallic, particularly preferably nickel, especially nickel which contains small amounts of phosphorus. Optionally, soft materials such as, for example, polydimethylsiloxanes (PDMS) can also be used to make (pi). In addition, rolls can be used that are coated with at least one synthetic material. In addition, the embossing tool (P1) may have a structured lacquer such as a UV lacquer as the embossing matrix. The coating agent (B1a) applied to (F1) after step (6) has the negative shape of the embossed structure to be transferred, such as microstructures and/or nanostructures.

The embossing die of the embossing tool used can optionally be pre-treated with the coating agent (B1a) used before step (6). Such pre-treatment comprises, or preferably is, the wetting of the embossing matrix with the coating agent (B1a).

Step (7)

Step (7) of the method according to the invention provides for at least partial and preferably complete curing of the substrate applied on at least part of the surface (F1) and at least partially embossed coating agent (B1a) to obtain a combined material (F1B1) from the substrate (F1) and at least partially embossed and at least partially cured coating (B1), and the coating agent (B1a) during the entire time of at least partial curing is in contact along with at least one embossing die (pi) and at least one embossing tool (P1).

Preferably, steps (6) and (7) are performed simultaneously. In this case, the curing according to step (7) during step (6) preferably takes place directly on site.

Therefore, the respective device used to carry out step (6) preferably includes at least one radiation source for irradiating the radiation-curable coating agent (Bla) with curing radiation, preferably ultraviolet radiation.

Suitable radiation sources for radiation curing are, for example, low-pressure mercury emitters, medium-pressure emitters, high-pressure emitters, as well as fluorescent lamps, pulsed emitters, metal halide emitters (halogen lamps), lasers, light emitting diodes and, in addition, devices with an electronic flash, due to which radiation curing without a photoinitiator is possible, or excimer emitters. Curing radiation occurs through the action of high energy radiation, that is, ultraviolet radiation or daylight, or through irradiation with high energy electrons. Typically, a sufficient radiation dose for crosslinking in the case of curing with ultraviolet radiation is in the range from 80 to 3000 mJ/cm ² . Of course, several radiation sources, for example two to four, can also be used for curing. They can emit respectively in different wavelength ranges.

Preferably, curing in step (7) occurs by irradiation through the substrate (F1). In this case, it is preferable that the transparency of the substrate (F1) for the radiation used is matched to the at least one photoinitiator used as component (B). Thus, for example, the PET material as substrate (F1), that is, for example, a PET film, is transparent to radiation with a wavelength below 400 nm. 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphosphinate and bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide are taken into account as photoinitiators that form radicals during this radiation.

Step (8)

Step (8) of the method according to the invention involves the removal of the composite material (F1B1) from the embossing tool (P1), resulting in the desired product, namely the composite material (F1B1) used as the matrix (p2) for embossing from the substrate (F1) and at least partially embossed and at least partially cured coating (B1).

In FIG. 2 is a schematic side view of a device that can be used to carry out steps (5) to (8) of the method according to the invention for the production of the combined material (F1B1) used as (p2), i.e. for the production of a template film, and on which, for example the method according to the invention is illustrated with respect to steps (5)-(8). By means of this device, structures such as microstructures and/or nanostructures can be transferred by means of a tool (P1) onto a coated (B1a) substrate (F1) and, after at least partial curing, a combined material (F1B1) used as a template film can be obtained, in fig. 2, designated as the template film web (8), which, as described above in connection with the one shown in FIG. 1 way, can be used as a matrix (p2) for embossing.

Shown in FIG. 2, the template transfer device (30) works according to the transfer principle, according to which, directly from the structured impression cylinder or the impression roller, which here is the template impression cylinder (17), the desired negative structures are pressed into the still uncured film web (8b) applied to the template film. the lacquer layer - corresponding to the combined material (F1B1) - and then it, together with the structures deposited on it, is at least partially cured directly in place by means of a lighting device (3) to obtain a template film web (8) corresponding to the combined material (F1B1) . The film web (8a) used as the substrate (F1) in this method is unwound from the roll (18) of the film web, which contains only the carrier material, therefore, a clean film without the applied pattern varnish, and through a separate system of guide rollers and a web tension system is introduced into zone (1) of the embossing device. There, the film web (8a) passes into the area between the pressure roller (4) and the template impression cylinder (17) and is provided outside the print area in the varnish applicator (27) with a layer of template varnish (corresponding to the coating agent B1a), which has not yet been cured. This application of varnish corresponds to step (5) of the process according to the invention. In the embossing zone (1) in which the template film web (8b) with the not yet cured layer of template varnish moves along the side surface area of the template impression cylinder (17), the microstructures embossed in the template impression cylinder (17) into its side surface and/ or the nanostructures are pressed as a negative image into the pattern lacquer layer of the pattern film web (8b) and transferred. This corresponds to step (8) of the method according to the invention. Then, the master film web (8b) having the uncured coating agent (B1a) is cured according to step (7) of the method according to the invention. At the same time, at least partially, curing is carried out directly on site by irradiation using an irradiation device (3) using ultraviolet irradiation, for example, by means of a device made of ultraviolet light emitting diodes. Then, the template film (8) thus obtained, i.e. the composite material (F1B1) according to step (8) of the method according to the invention, is removed from the side surface of the template impression cylinder (17), and the template film web (8) thus obtained is wound onto a roll. (19) template film. Then the template film roll (19) contains a finished template film web (8) with a layer of template varnish applied to it and negative images of microstructures and/or nanostructures embossed into it. This roll (19) of the master film web can be removed and then used in the transfer device (10) according to FIG. 1 or another transfer device operating on the same principle as the first roll (6) of the film web.

Coating agent used according to the invention (B1A) and (B2A)

Cover agent (B1A)

The coating agent (B1a) is a radiation-curable coating agent. The terms "radiation cured" and "radiation cured" are used interchangeably. By "radiation curing" is meant preferably the radical polymerization of polymerizable compounds under the action of electromagnetic and/or particulate radiation, for example near infrared light in the wavelength range from λ=400-1200 nm, preferably 700-900 nm, and/ or ultraviolet light in the wavelength range λ=100-400 nm, preferably λ=200-400 nm, and particularly preferably λ=250-400 nm, and/or electron irradiation in the range from 150 to 300 keV, and particularly preferably with a dose irradiation of at least 80, preferably 80-3000 mJ/cm ² . Particularly preferably, the curing takes place by means of ultraviolet radiation as a radiation curing. The coating agent (B1a) can be cured by using a suitable radiation source. Therefore, (B1a) is preferably a UV curable coating agent.

The coating agent (B1a) contains:

at least one component (A) in an amount in the range from 40 to 95% by weight, preferably in the range from 45 or >45 to 90% by weight, particularly preferably in the range from 50 or >50, such as, for example, from 55 to 85% by weight, highly preferably in the range from 55 or 80 to 80% by weight,

at least one additive as component (B) in an amount in the range of 0.01 to 5% by weight, preferably in the range of 0.05 to 4.5% by weight, particularly preferably in the range of 0.1 to 4 % by weight, highly preferably in the range of 0.2 or 0.5 to 3% by weight,

at least one photoinitiator as component (B) in an amount in the range of 0.01 to 15% by mass, preferably in the range of 0.1 to 12% by mass, particularly preferably in the range of 0.5 to 10% by mass mass,

at least one component (D) having at least one carbon-carbon double bond in an amount in the range from 0 to 45% by weight, preferably in the range from 0 to 40% by weight, particularly preferably in the range from 0 to 35% by weight, highly preferably in the range from 0 to 30% by weight,

respectively, based on the total weight of the coating agent (B1a).

Therefore, the presence of the component (D) in the coating agent (B1a) used according to the invention is only optional, as is evident from the above lower limit value of 0% by weight. Preferably, the coating agent (B1a) contains component (D) in an amount of 0 to 30% by weight, based on the total weight of the coating agent (B1a).

Components (A), (B), (C) and (D) are respectively different from each other. The quantities of components (A), (B), (C) and (D) mentioned above refer respectively to the total weight of the coating agent (B1a). The quantities of all components contained in the coating agent (C1a), that is, the quantities of components (A), (B), (C) contained in (C1a), as well as optionally (D), as well as other optional components present in it, are summed up to 100 %.

Component (A) has at least three different or at least partially identical structural elements according to formula (I)

wherein

the residues R ¹ , respectively, independently of each other, denote an alkylene group C ₂ -C ₈ ,

the residues R ² respectively independently of each other represent H or methyl, and

the parameters m respectively independently of each other denote an integer parameter in the range of 1 to 15, preferably in the range of 1 to 10, particularly preferably in the range of 1 to 8 or 2 to 8, most preferably in the range of 1 to 6 or from 2 to 6, especially in the range from 1 to 4 or from 2 to 4, but with the proviso that in at least one structural element of the formula (I) the parameter m is at least 2, preferably at least 3.

Preferably, component (A) has at least three identical elements of formula (I).

стоит вместо соответствующего остатка со структурой более высокого уровня компонента (А), то есть, например, связи остатка -[O-R¹]m-O-C(=O)-C(R²)=СН₂ внутри структурного элемента со структурой более высокого уровня компонента (А). При этом связь происходит, предпочтительно, через связь атома кислорода остатка -[O-R¹]_m- с атомом углерода остатка более высокого уровня. Аналогичное справедливо для других структурных элементов формулы (I). Является однозначным, что по меньшей мере все три структурных элемента формулы (I) объединены в одном единственном компоненте - а именно, компоненте (А).At the same time, the symbol

stands in place of the corresponding residue with the structure of the higher level component (A), that is, for example, the relationship of the residue -[OR ¹ ]mOC(=O)-C(R ² )=CH ₂ inside the structural element with the structure of the higher level component ( BUT). In this case, the connection occurs, preferably, through the connection of the oxygen atom of the residue -[OR ¹ ] _m - with the carbon atom of the residue of a higher level. The same is true for other structural elements of formula (I). It is unambiguous that at least all three structural elements of formula (I) are combined in one single component - namely, component (A).

Preferably, component (A) has exactly three building blocks of formula (I). In this case, component (A) has exactly three functional methacrylate groups. Optionally, the building blocks of formula (I) are respectively present more than three times as part of component (A). In this case, component (A) may have, for example, more than three methacrylate functional groups, for example 4, 5 or 8 methacrylate groups.

The aforementioned R ¹ radicals, independently of each other, represent a C ₂ -C ₈ alkylene group, preferably a C ₂ -C ₆ alkylene group, particularly preferably a C ₂ -C ₄ alkylene group, most preferably, respectively independently of one another, an ethylene group and/or a propylene group, most preferably ethylene. First of all, all residues R ¹ denote ethylene. As propylene groups, residues R ¹ are taken into account, which have the structure -CH ₂ -CH ₂ -CH ₂ - or the structure -CH(CH ₃ )-CH ₂ - or the structure -CH ₂ -CH(CH ₃ )-. However, the propylene structure -CH ₂ -CH ₂ -CH ₂ - is particularly preferred.

The parameters m, respectively, independently of each other, denote an integer parameter in the range from 1 to 15. Since the component (A) has at least three structural elements of the formula (I) and in at least one structural element of the formula (I) m is at least 2, component (A) as a whole contains at least four ester groups with the general formula "-OR ¹ -".

Preferably, component (A) has a total of at least five, particularly preferably at least six ester groups with the general formula "-OR ¹ -". Preferably, the number of ester groups with the general formula "-OR ¹ -" in component (A) is in the range of 4 to 18, particularly preferably in the range of 5 to 15, most preferably in the range of 8 to 12.

Preferably, the proportion of ester segments -[OR ¹ ] _m contained in the building blocks of formula (I) of component (A) is generally at least 35% by weight, particularly preferably at least 38% by weight, highly preferably, at least 40% by weight, that is, 42% by weight, in particular at least 45% by weight, respectively, based on the total weight of the component (A).

Preferably, the component (A) has a molecular weight (M _n ) in the range from 300 to 2000 g/mol, particularly preferably from 350 to 1500 g/mol, in particular from 400 to 1000 g/mol.

Particularly preferably, as component (A) a compound with the general formula (IVa) and/or (IVb) is used,

in which, respectively, independently of each other

R ¹ and R ² and m have the meanings mentioned above in connection with the structural elements (I), including the preferred embodiments named above, and

R ³ stands for H, C ₁ -C ₈ -alkyl, OH or OC _1-8 -alkyl, particularly preferably C ₁ -C ₄ -alkyl, OH or OC _1-4 -alkyl, highly preferably C ₁ -C ₄ -alkyl or OH or

R ³ stands for the remainder -[OR ¹ ] _m -OC(=O)-C(R ² )=CH ₂ , where R ¹ , R ² and m have the meanings mentioned above in connection with the structural element (I), including those named above are their preferred embodiments.

Highly preferably, as component (A), at least one compound of the general formula (IVa) is used, in which

the residues R ¹ respectively, independently of each other, denote a C ₂ -C ₈ -alkylene group,

the residues R ² respectively independently of each other denote H or methyl,

the parameters m respectively independently of each other denote an integer parameter in the range of 1 to 15, preferably in the range of 1 to 10, particularly preferably in the range of 1 to 8 or 2 to 8, most preferably in the range of 1 to 6 or from 2 to 6, especially in the range from 1 to 4 or from 2 to 4, but with the proviso that in at least one structural element, preferably in all structural elements, of the formula (I) the parameter m is equal to at least 2.

R ³ stands for C ₁ -C ₈ -alkyl, OH or OC _1-8 -alkyl, particularly preferably stands for C ₁ -C ₄ -alkyl OH or OC _1-4 -alkyl, highly preferably stands for C ₁ -C ₄ -alkyl or OH.

Particularly preferably, as component (A) methacrylates are used in general from 4-fold to 10-fold or from 4-fold to 12-fold alkoxylated, for example ethoxylated, propoxylated or mixed ethoxylated and propoxylated and, above all, exclusively ethoxylated neopentyl glycol, trimethylolpropane, trimethylolethane or pentaerythritol. Most preferred are the corresponding methacrylates which are derived from suitably alkoxylated trimethylol propane. Such products are commercially available and sold under the names Sartomer® SR 499 and Sartomer® SR 502, as well as Sartomer® SR 415 and Sartomer® SR 9035, and Sartomer® SR 501. The term "methacryl" or "methacrylate" includes in the sense of the present invention, both methacrylic and acrylic, or both methacrylate and acrylate.

Preferably, the coating agent (B1a) - with the exception of the optional component (D) - does not contain a component that has only exactly one or only exactly two ethylenically unsaturated groups, such as methacrylic groups. In the case where (B1a) does not contain component (D), (B1a) therefore preferably does not contain a component that has only exactly one or exactly two ethylenically unsaturated groups, such as methacrylic groups.

Component (B) is an additive. The term "additive" is known to the skilled person, for example, from Rompp Lexikon, "Lacke und Druckfarben" (varnishes and printing inks), Thieme Verlag, 1998, page 13. Preferably, at least one rheological additive is used as component (B). Also, this concept is known to the specialist, for example, from Rompp Lexikon, "Lacke und Druckfarben" (varnishes and printing inks), Thieme Verlag, 1998, page 497. auxiliary means ("Rheologiehilfsmittel") are interchangeable. Preferably, the additive used as component (B) is selected from the group consisting of spreading agents, surface active agents such as surfactants, wetting agents and dispersing agents, as well as thickeners, thixotropic agents, emollients and lubricating agents and anti-blocking agents, as well as mixtures of them. These terms are also known to those skilled in the art, for example from Rompp Lexikon, "Lacke und Druckfarben" (varnishes and printing inks), Thieme Verlag, 1998. Spreading aids are components which, by reducing viscosity and/or surface tension, help the coating agents to form flat spreading films. Wetting agents and dispersing agents are components which reduce the surface tension or, in general, the boundary surface tension. Lubrication additives and anti-blocking additives are components that reduce sticking (sticking).

Examples of commercial additives 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.

Preferably, at least one polymethacrylate and/or at least one siloxane, such as at least one oligosiloxane and/or polysilioxane and/or at least a fluorine-containing polymer, such as a fluorine-containing, preferably aliphatic, is used as additive (B). complex polyester. Particularly preferably, component (B) are siloxanes. Highly preferably, silicone methacrylates are used.

For curing with near infrared light and/or ultraviolet light, the coating agent (B1a) contains at least one photoinitiator as component (B). It is decomposed by light with the irradiated wavelength into radicals, which, in turn, can initiate radical polymerization. On the contrary, when curing by means of electron radiation, the presence of such photoinitiators is not required. Preferably, the coating agent (B1a) contains as component (B) at least one photoinitiator which, by means of light of the irradiated wavelength, can be decomposed into radicals, which in turn can initiate radical polymerization.

Photoinitiators, such as ultraviolet photoinitiators, are known to those skilled in the art. Considered are, for example, phosphine oxides, benzophenones, a-hydroxy-alkyl-aryl-ketones, thioxanthones, antriquinones, acetophenones, benzoins and benzoin esters, ketals, imidazoles or phenylglyoxylic acids and mixtures thereof.

Phosphine oxides are, for example, mono- or bisacylphosphine oxides, for example 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoyldiphenylphosphinate or bis(2,6-limethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. Benzophenones are, for example, benzophenone, 4-aminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, Michler's ketone, o-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 2 ,4-dimethylbenzophenone, 4-isopropylbenzophenone, 2-chlorobenzophenone, 2,2'-dichlorobenzophenone, 4-methoxybenzophenone, 4-propoxybenzophenone or 4-butoxybenzophenone, α-hydroxyalkylaryl ketones are, for example, 1-benzoylcyclohexan-1-ol (1-hydroxycyclohexylphenyl ketone ), 2-hydroxy-2,2-dimethylacetophenone (2-hydroxy-2-methyl-1-phenylpropan-1-one), 1-hydroxyacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy -2-methyl-1-propan-1-one) or polymers which contain polymerized 2-hydroxy-2-methyl-1-(4-isopropen-2-yl-phenyl)-propan-1-one. Xanthones and thioxanthones are, for example, 10-thioxanthenone, thioxanthen-9-one, xanthen-9-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dichlorothioxanthone or chlorxanthenone, anthroquinones are, e.g. -butylanthraquinone, 1-chloranthraquinone or 2-amylanthraquinone. Acetophenones are, for example, acetophenone, acetonaphthoquinone, valerophenone, hexanophenone, α-phenylbutyrophenone, p-morpholinepropiophenone, dibenzosuberone, 4-morpholinebenzophenone, p-diacetylbenzene, 4'-methoxyacetophenone, α-tetralone, 9-acetyleneanthrene, 2-acetylphenetrene, 3- acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indanone, 1,3,4-triacetylbenzene, 1-acetonaphthone, 2-acetonaphthone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-methylthio)phenyl]-2-morpholinoproman-1-one, 2,2-dimethoxy-1,2-diphenylethan- 2-one or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one. Benzoins and benzoin ethers are, for example, 4-morpholinedeoxybenzoin, benzoin, benzoinisobutyl ether, benzointrahydropyranyl ether, benzoin methyl ether, benzoinethyl ether, benzoinbutyl ether, benzoinisopropyl ether or 7-H-benzoinmethyl ether. Ketals are, for example, acetophenone dimethyl ketal, 2,2-diethoxyacetophenone or benzyl ketals such as benzyl dimethyl ketal. In addition, suitable photoinitiators are, for example, benzaldehyde, methyl ethyl ketone, 1-naphthaldehyde, triphenylphosphine, tri-o-tolylphosphine or 2,3-butanedione. Typical mixtures include, for example, 2-hydroxy-2-methyl-1-phenylpropan-2-one and 1-hydroxycyclohexylphenyl ketone, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphine oxide and 2-hydroxy-2 -methyl-1-phenylpropan-1-one, benzophenone and 1-hydroxycyclohexylphenylketone, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 1-hydroxycyclohexylphenylketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy- 2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzophenone and 4-methylbenzophenone or 2,4,6-trimethylbenzophenone and 4-methylbenzophenone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Preferred among these photoinitiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphinate, bis-(2,4,6-trimethylbenzoyl)phenylphosphine oxide, benzophenone, 1-benzoylcyclohexan-1-ol, 2-hydroxy- 2,2-dimethylacetophenone and 2,2-dimethoxy-2-phenylacetophenone. Preferably, therefore, at least one such photoinitiator is used as component (B). Component (C) is exposed from components (A), (B) and (D). Commercially available photoinitiators are, for example, the products Irgacure® 184, Irgacure® 500, Irgacure® TPO, Irgacure® TPO-L and Lucirin® TPO, as well as Darocure® 1173 from BASF SE.

As mentioned above, the use of at least one component (D) is only optional. Component (D) has at least preferably a terminal carbon-carbon double bond. Preferably, this is a methacrylic group. Preferably, component (D) has one or two ethylenically unsaturated groups, for example one or two or three or also more methacrylic groups. Two or more different components (D) may also be used.

Examples of components (D) are mono-, di- and/or trifunctional esters of methacrylic acid, such as ethylene glycol dimethacrylate, 1,2-propanediol dimethacrylate, 1,3-propanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, 1,5 -pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,8-octanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol dimethacrylate, 1,2-, 1,3- and 1, 4-циклогександиолдиметакрилат, трициклодекандиметанолдиметакрилат, триметилолпропантриметакрилат, дитриметилолпропанпентаакрилат или дитриметилолпропангексаметакрилат, пентаэритриттриметакрилат или пентаэритриттетраметакрилат, глицериндиметакрилат или глицеринтриметакрилат, а также ди- и полиметакрилаты многоатомных спиртов, таких, как, например, сорбита, маннита, диглицерина, треита, эритрита, адонита (рибита), arabitol (lixit), xylitol, dulcitol (galactitol), maltitol or isomalt, 2-phenoxyethyl methacrylate, ethyl diglycol methacrylate, 4-tert-butylcyclohexyl methacryl at, trimethylolpropane formalmonomethacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, as well as lauryl methacrylate, stearyl methacrylate, isodecyl methacrylate, octyl methacrylate and decyl methacrylate, esters of α,β-ethylenically unsaturated carboxylic acids, preferably methacrylic acid with alcohols from 1 to 20 carbon atoms, preferably optionally hydroxy-substituted 1 to 20 carbon alcohols, for example methyl methacrylic acid, ethyl methacrylic acid, n-butyl methacrylic acid, 2-ethylhexyl methacrylic acid, 2-hydroxymethacrylate, 2- hydroxypropyl methacrylate or 4-hydroxybutyl methacrylate.

Highly preferred components (D) are 1,4-butanediol dimethacrylate and 1,6-hexanediol dimethacrylate, as well as tricyclodecane dimethanol dimethacrylate.

Additionally or optionally, at least one methacrylic acid polyester, methacrylic acid polyether, carbonate methacrylate, epoxy methacrylate, polymethacrylate and/or urethane methacrylate and/or unsaturated polyester resin can be used as component (D).

Urethane methacrylates can be prepared, for example, by reacting a polyisocyanate with hydroxyalkyl methacrylates and optionally chain extenders such as diols, polyols, diamines, polyamines or dithiols or polythiols. Water-dispersible without the addition of emulsifiers, the urethane methacrylates additionally contain ionic and/or non-ionic hydrophilic groups, which are introduced into the urethane, for example, via build-up components such as hydroxycarboxylic acids. Such urethane methactylates as add-on components essentially comprise:

(A) at least one aliphatic, aromatic or cycloaliphatic diisocyanate or polyisocyanate, for example, at least one of those described in relation to two-component polyisocyanate coating masses,

(B) at least one compound with at least one isocyanate-reactive group, preferably the hydroxyl-containing monomer described for polyacrylate polyols, and at least one radically polymerizable unsaturated group, and

(B) optionally at least one compound with at least two isocyanate-reactive groups, for example one of the polyhydric alcohols described above in connection with polyesterols.

Preferably, the urethane methacrylates have an average molecular weight M _n from 200 to 20,000, in particular from 500 to 10,000, particularly preferably from 600 to 3,000 g/mol (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard). Preferably, the urethane methacrylates have a content of 1 to 5, particularly preferably 2 to 4 moles of methacrylate groups per 1000 g of urethane methacrylate.

Epoxy methacrylates can be prepared by reacting epoxides with methacrylic acid. Suitable epoxides are, for example, epoxidized olefins, aromatic glycidyl ethers or aliphatic glycidyl ethers, preferably such aromatic or aliphatic glycidyl ethers. The epoxidized olefins may be, for example, ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, vinyloxirane, styrene oxide or epichlorohydrin, ethylene oxide, propylene oxide, isobutene oxide, vinyloxirane, styrene oxide or epichlorohydrin are preferred, particularly preferably ethylene oxide, propylene oxide or epichlorohydrin, and highly preferred, ethylene oxide and epichlorohydrin. Aromatic glycidyl ethers are, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol B diglycidyl ether, bisphenol S diglycidyl ether, hydroquinone diglycidyl ether, phenol/dicyclopentadiene alkylation products, e.g. -epoxypropoxy)phenyl]octahydro-4,7-methane-5H-indene, tris[4-(2,3-epoxypropoxy)phenyl]methane isomers, phenol-based epoxy novolacs and cresol-based epoxy novolacs. Aliphatic glycidyl ethers are, for example, 1,4-butanediol diglycidyl ether, 1,6-hexadiol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritoltetraglycidyl ether, propylene glycol ether (α,ω-bis(2,3-epoxypropoxy)polyoxypropylene) and hydrogenated bisphenol A (2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane). Preferably, the epoxy methacrylates have an average molecular weight M _n of 200 to 20,000, particularly preferably 200 to 10,000 g/mol, and most preferably 250 to 3,000 g/mol; the content of methacrylic groups is preferably 1 to 5, particularly preferably 2 to 4 per 1000 g of epoxy methacrylate (determined by gel permeation chromatography with polystyrene as standard and tetrahydrofuran as eluent).

Methacrylated polymethacrylates are the corresponding esters of α,β-ethylenically unsaturated carboxylic acids, preferably methacrylic acid, particularly preferably acrylic acid, with polyacrylate polyols obtained by esterification of polymethacrylate polyols with methacrylic acid. The polyacrylate polyols are preferably those described above with respect to the two-component coating compositions. Carbonate methacrylates can be prepared with various functionalities. Preferably, the average molecular weight M _n of carbonate methacrylates is less than 3000 g/mol, particularly preferably less than 1500 g/mol, particularly preferably less than 800 g/mol (determined by gel permeation chromatography with polystyrene as standard, tetrahydrofuran as solvent). Carbonate methacrylates can be obtained in a simple manner by transesterification of carbonic esters with polyhydric, preferably dihydric alcohols (diols, e.g. hexanediol) and subsequent esterification of the free OH groups with methacrylic acid or also by transesterification with methacrylic acid esters, as described for example in EP 0092269 A1. They can also be obtained by reacting phosgene, urea derivatives with polyhydric, eg dihydric, alcohols. Also possible are methacrylates of polycarbonate polyols, such as the reaction product of one of the diols or polyols mentioned and a carbonic ester, as well as a methacrylate containing hydroxyl groups. Suitable carbonic esters are, for example, ethylene carbonate, 1,2-propylene carbonate or 1,3-propylene carbonate, carbonic dimethyl ester, carbonic diethyl ester or carbonic dibutyl ester. Подходящими содержащими гидроксильные группы метакрилатами являются, например, 2-гидроксиэтилметакрилат, 2- или 3-гидроксипропилметакрилат, 1,4-бутандиолмонометакрилат, неопентилгликольмонометакрилат, монометакрилат глицерина и диметакрилат глицерина, монометакрилат триметилолпропана и диметакрилат триметилолпропана, а также монометакрилат пентаэритрита, диметакрилат пентаэритрита и триметакрилат пентаэритрита . Preferably, the carbonate methacrylates are aliphatic carbonate methacrylates.

Unsaturated polyester resins preferably consist of the components:

(A1) maleic acid or its derivatives,

(A2) at least one cyclic dicarboxylic acid or derivatives thereof,

(A3) at least one aliphatic or cycloaliphatic diol.

In this case, derivatives are understood as:

- the corresponding anhydrides in monomeric or also polymeric form,

- monoalkylethers or dialkylethers, preferably monoalkylethers or di-C ₁ -C ₄ -alkylethers, particularly preferably monomethylethers or dimethylethers or the corresponding monoethylethers or diethylethers,

- other monoethers and divinylethers, as well as

- mixed ethers, preferably mixed ethers with different C ₁ -C ₄ -alkyl components, particularly preferably mixed methyl ethyl ethers.

If (B1a) contains component (D), it is preferably at least one urethane methacrylate.

The coating agent (B1a) can have at least one other component (E) different from components (A) to (D), such as, for example, fillers, pigments, thermally activated initiators, such as, for example, potassium peroxodisulphate, dibenzoyl peroxide, cyclohexanone peroxide, azobis-isobutyronitrile, cyclohexylsulfonyl acetyl peroxide, diisopropyl percarbonate, tert-butyl peroctoate or benzpinacol, di-tert-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, tert-butyl perbenzoate, silylated pinacolas containing hydroxyl groups, amine-N-oxides such as 2,2, 6,6-tetramethylpiperidine-N-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidinoxyl, and organic solvents, as well as stabilizers. Preferably, however, (B1a) does not contain organic solvents. Component (E) may be contained in (B1a) in an amount in the range of 0 to 15% by mass, preferably in the range of 0 to 12% by mass, particularly preferably in the range of 0 to 10% by mass, respectively, based on the total the weight of the covering agent (B1a).

Preferably, the solids content of the coating agent (B1a) is ≥80% by mass, particularly preferably ≥90% by mass, highly preferably ≥95% by mass, in particular ≥98 or ≥99% by mass, most often, preferably, 100% by weight, respectively, based on the total weight of the coating agent (B1a). In this case, the content of solids is determined by the method described below.

Preferably, the coating agent (B1a) does not contain thiols, in particular trimethylol propattris(3-mercaptopropionate).

Preferably, the double bond conversion of the at least partially cured coating (B1) obtained from (B1a) is at least 70%, particularly preferably at least 75%, i.e. 80%, highly preferably at least 85%, especially at least 90%.

Cover agent (B2a)

Any kind of coating agent can be used in step (1) of the method according to the invention as a coating agent (B2a). The coating agent (B2a) can be a physically drying, thermally curing, chemically curing and/or radiation curing coating agent (B2a). Preferably, the coating agent (B2a) is a chemically curable, thermally curable and/or radiation curable coating agent, particularly preferably a radiation curable coating agent. Accordingly, at least partial curing according to step (3) preferably takes place by means of radiation curing. The coating agent (B2a) may be identical to the coating agent (B1a). However, preferably, (B2a) is different from (Bla). Preferably, (B2a) is formed from the same, but not the same, components (A) to (D) which are also used for the manufacture of (B1a), and the specified quantities relating to (B1a), however, should not refer to (B2a ).

In this context, physical drying is preferably understood to be the simple evaporation of the solvent(s) to form a coating (B2). While thermal curing, preferably, provides a curing mechanism, which should be determined by a temperature above room temperature (>23°C). This may be, for example, the formation of radicals or ions, preferably radicals, from an initiator which decomposes at elevated temperatures and thus initiates a radical or ionic polymerization. Examples of such thermally activated initiators are those which at 80° C. have a half-life of less than 100 hours. Chemical curing is preferably understood to mean a reaction between at least two different and complementary reactive functional groups, for example in the sense of polycondensation such as the reaction of a -OH group with a -COOH group, or in the sense of polyaddition (reaction of an NCO group with -OH or an amino group).

If the coating agent (B2a) is a physically drying, thermally curing and/or chemically curing coating agent, then at least one conventional and known to the person skilled in the art polymer is used as a binder. Preferably, it then has crosslinkable functional groups. Any conventional crosslinkable group known to the person skilled in the art is taken into account. First of all, crosslinkable functional groups are selected from the group consisting of hydroxyl groups, amino groups, carboxylic acid groups, isocyanates, polyisocyanates and epoxides. Preferably, the polymers are exothermically or endothermically crosslinkable or curable, preferably crosslinkable or curable in the temperature range from -20°C to 250°C or from 18°C to 200°C. Suitable polymers are in particular at least one selected from the group consisting of polyurethanes, polyethers, polyesters, polyamides, polyureas, polyvinyl chlorides, polystyrenes, polycarbonates, polymethacrylates, epoxy resins, phenol-formaldehyde resins, melamine- formaldehyde resins. In this case, the polymers can be primarily OH-functional. In this case, they can be brought together under the general concept of "polyols". Such polyols can be, for example, polyacrylate polyols, ester polyols, ether polyols, polyurethane polyols, polyurea polyols, polyester polyacrylate polyols, polyether urethane polyols, polyurethane polyacrylate polyols, polyurethane-modified alkyd resins, fatty acid-modified polyether polyurethane polyols, as well as mixtures of the named polyols. Polyacrylate polyols, ester polyols and polyether polyols are preferred.

In this case, at least one polymer can be used that cures with the participation of an isocyanate and/or oligomerized isocyanate groups, most preferably at least one corresponding polyurethane and/or at least one corresponding polyurea (for example, the so-called "polyaspartic binder means"). Polyaspartic binders are components which are obtained from the reaction of amino functional compounds, in particular secondary amines, with isocyanates. If at least one polyurethane is used, then especially resins based on polyurethane are suitable, which can be obtained by polyaddition reaction between components containing hydroxyl groups, such as polyols, and at least one polyisocyanate (aromatic and aliphatic isocyanate, diisocyanate, triisocyanate and/or polyisocyanate). This usually requires a stoichiometric reaction of the OH groups of the polyols with the NCO groups of the polyisocyanate. However, the stoichiometric ratio used may also vary as the polyisocyanate may be added to the polyol component in such amounts that "over-crosslinking" or "under-crosslinking" may occur. If epoxy resins are used, i.e. epoxy-based resins, epoxy-based resins are preferably suitable which are made from glycidyl ethers which have epoxy terminal groups and intramolecular hydroxyl groups as functional groups. Preferably, they are reaction products of bisphenol A and epichlorohydrin or bisphenol F with epichlorohydrin and mixtures thereof, which are also used in the presence of reagent diluents. The curing or cross-linking of such epoxy-based resins usually occurs by polymerization of the epoxy groups of the epoxy ring, by means of a polyaddition reaction in the form of addition of other reactive compounds as curing agents in stoichiometric amounts to the epoxy groups, and accordingly, the presence of one active hydrogen equivalent per epoxy group (that one H-active equivalent is required per equivalent of epoxide), or by polycondensation through epoxy groups and hydroxyl groups. Suitable hardeners are, for example, polyamines, in particular (hetero)aliphatic, (hetero)aromatic and (hetero)cycloaliphatic polyamines, polyamidamines, polyamineamides, as well as polycarboxylic acids and their anhydrides.

The term "radiation curing" has already been described in connection with the coating agent (Bla). The coating agent (B2a) can be cured by using a radiation source, preferably by using ultraviolet radiation. Therefore, (B2a) is preferably a UV-curable coating agent.

Preferably, agent (B2a) therefore has unsaturated carbon-carbon double bonds, particularly preferably methacrylic groups. To this end, the coating agent (B2a) may contain each of the above-mentioned in connection with (B1a) and brought together among the components (A) and (D) of the agent (B1a), such as, in particular, polyesters, polyethers, carbonates , epoxides, polymethacrylate and/or urethane methacrylate and/or at least one unsaturated ester resin and/or mono-, di- and/or trifunctional esters of methacrylic acid.

When cured with (near) infrared light and/or ultraviolet light, the coating agent (B2a) preferably contains at least one photoinitiator which, by means of light with an irradiating wavelength, can decompose into radicals, which, in turn, can initiate a radical polymerization. On the contrary, when curing by means of electron radiation, the presence of such photoinitiators is not required. As photoinitiators, the same components and in the same amounts as mentioned above in connection with component (B) of the coating agent (B1a) can be used.

In addition, the coating agent (B2a) may contain at least one other additive. In this case, the same components and in the same quantities as mentioned above in connection with components (B) and (E) of the coating agent (B1a) can be used.

Particularly preferably, as the coating agent (B2a), a coating agent is used which has methacrylic groups. Preferably, this coating agent (B2a) contains at least one urethane methacrylate. Preferably, it also contains at least one photoinitiator.

Combined material (B2B1F1) according to the invention

In addition, another subject of the present invention is a composite material (F1B1) of a substrate (F1) and an at least partially embossed and at least partially cured coating (B1) which is produced by at least partially curing by means of radiation curing applied to at least part of the surface of the substrate (F1) and at least partially embossed coating agent (B1a), and the coating agent (B1a) is a radiation-curable coating agent that contains:

at least one component (A) in an amount in the range from 40 to 95% by weight,

at least one additive as component (B) in an amount in the range from 0.01 to 5% by weight,

at least one photoinitiator as component (B) in an amount ranging from 0.01 to 15% by weight, and

at least one component (D) having at least one carbon-carbon double bond in an amount in the range from 0 to 45% by weight,

and (i) components (A), (B), (C) and (D) are respectively different from each other, (ii) the indicated amounts of components (A), (B), (C) and (D) are given respectively relative to the total weight of the coating agent (B1a), and (iii) the amounts of all components contained in the coating agent (B1a) are summed up to 100%, and

moreover, the component (A) has at least three different from each other or at least partially identical structural elements according to formula (I)

in which the residues R ¹ respectively independently of each other denote an alkylene group C ₂ -C ₈ ,

the residues R ² respectively independently of each other represent H or methyl, and

the parameters m, respectively, independently of each other, denote an integer parameter in the range from 1 to 15, but with the condition that in at least one structural element of formula (I) in component (A), the parameter m is equal to at least 2.

All the preferred embodiments previously described here in connection with the method according to the invention, especially in connection with the coating agents (B1a) used therein, the substrate (F1) as well as the coating (B1), are preferred embodiments with respect to the combined material (F1B1) according to invention.

Preferably, the combined material (F1B1) according to the invention of this is obtained by carrying out the steps (5)-(8) of the method described above. Preferably, the substrate (F1) is a film web, particularly preferably an endless film web.

Application

Another object of the present invention is the use of the combined material (F1B1) as an embossing matrix (p2) of an embossing tool (P2) for transferring an embossed structure to at least part of the surface of the cover means (B2a) or at least to a part the surface of the coating agent (B2a), which is at least partially applied to the substrate (A2), preferably in the method according to the invention.

All the embodiments described hereinbefore in connection with the method according to the invention and the combined material (F1B1) are also preferred embodiments in relation to the named use of the combined material (F1B1) according to the invention.

Preferably, the coating agent (B2a) is in this case a radiation-curable coating agent.

Methods for determining

1. Determination of the non-volatile fraction

The determination of the non-volatile fraction (solids or solids fraction or solids content) takes place according to DIN EN ISO 3251 (Date: June 2008). In this case, 1 g of the sample is weighed in a pre-dried aluminum cup and dried for 60 minutes at 125°C in an oven, cooled in a desiccator and then weighed again. The remainder, based on the total amount of sample used, corresponds to the non-volatile fraction.

2. Determining the accuracy of copying the form

Determination of the copying accuracy of the form is carried out by means of a commercially available scanning force microscope (AFM) using a commercially available cantilever. By means of AFM, for example, the surface topography of a certain grid structure, such as the structure of an embossing tool (P1) with a depth of, for example, 140 nm and a period of, for example, 430 nm, can be compared with the surface topography of a template film (B1F1) after embossing. In this case, the embossing tool is intentionally damaged at a certain location in order to thus determine the starting point. By means of this starting point, respectively identical regions of the comparison and replication pattern can be examined and compared with each other. In this case, the shape copying accuracy determines how exactly a certain reference structure can be transferred, such as, for example, from an embossing tool P1 on a template (B1F1) film. If, for example, the investigated area of the embossing tool (P1) has a grating structure with a depth of 140 nm, this comparison depth is then compared with the corresponding structure height, which is determined on the template film (B1F1). In this case, the percentage change, which in this case corresponds to the accuracy of copying the form, is defined as:

where Ah corresponds to the percentage change, h _m is the structure height of the area of the stencil film used, and h _r is the corresponding structure depth of the examined area of the embossing tool. This percentage change, hence the shape copying accuracy, is also called shrinkage. The smaller the value for Δh, the better the shape copying accuracy.

3. Determination of the expiration time

The expiration time is determined according to DIN EN ISO 2431 (Date: March 2012). In this case, the outflow time is determined by means of a funnel with a nozzle diameter of 4 mm (Nr. 4) at room temperature (20°C).

4. Determination of the degree of conversion of double bonds

The degree of conversion (DB-Umsatz) is determined after the test sample has cured by means of attenuated total internal reflection spectroscopy (ATR-IR-Spektroskopie, ATR-IR spectroscopy). In the ATR-IR spectroscopy method, an infrared spectrum is recorded at the point of contact of a round reflective crystal with a substrate. The contact point has a diameter of about 200 µm, and a germanium crystal is used as the reflective crystal.

An appropriate liquid sample sample is used as the starting material for calculating the degree of conversion of double bonds. The degree of conversion of double bonds is calculated through the decrease in the intensity of the band at 810 cm ^-1 . The ester band at 1730 cm ^-1 is used as the reference band. The percentage conversion of double bonds is calculated using the following formula:

while I _{810 cm -1} is the normalized intensity at 810 cm ^-1 of the cured layer, and I _{Ref-810 cm -1} is the normalized intensity at 810 cm ^-1 of the corresponding liquid sample. The degree of conversion of double bonds >90% is estimated as sufficient.

5. Definition of clutch

Adhesion is determined according to DIN EN ISO 2409 (Date: June 2013) by means of a grid notch test. In this case, the adhesion of the lacquer layer to be examined to the substrate is checked in a double determination. Byk Gardner grating checker with 2 mm notch spacing is used manually. Then Tesa-Band Nr is pressed against the damaged surface. 4651 and removed to remove detached sections. Evaluation occurs by means of parameters ranging from 0 (small separation) to 5 (very strong separation). A mean value of at least 3.5 is considered sufficient.

6. Determining Replication Success

Determination of the success of replication occurs visually, and the percentage of successfully replicated surface is determined. The range is between 0% and 100% of successfully replicated surface. If not 100% of the surface is replicated, this means that a corresponding proportion of the surface could not be removed from the embossing die, i.e. that the coating B1 in the form of B1F1 partially remained adhered to the embossing tool P1 or that the coating B2 partially remained adhered to the template film B1F1.

Examples and Comparison Examples

The following comparative examples serve to clarify the invention, but should not be interpreted as limiting.

Unless otherwise indicated, in the case of data in parts, we are talking about parts by weight and in the case of data in percentage, we are talking about percent by weight.

1. Used raw materials and materials

Hostaphan® GN is a commercially available PET film with a layer thickness of 125 µm.

Laromer® UA 9033 (L UA 9033) - aliphatic urethane acrylate from BASF SE, applicable as component (G)

Hexandioldiacrylat (HDDA) - applicable as component (G)

Sartomer® 395 (SR 395) isodecyl acrylate from Sartomer, applicable as component (D)

Sartomer® 502 (SR 502) - 9-fold ethoxylated TMPTA (trimethylpropane triacrylate) from Sartomer, applicable as component (A)

Sartomer® 499 (SR 499) - 6-fold ethoxylated TMPTA (trimethylpropane triacrylate) from Sartomer, applicable as component (A)

Sartomer® 454 (SR 454) - 3-fold ethoxylated TMPTA, (trimethylpropane triacrylate) from Sartomer, applicable as reference component (A)

TMPTA (trimethylpropane triacrylate) applicable as reference component (A)

GPTA (glyceryl propoxy triacrylate) - 3-fold propoxylated glyceryl triacrylate applicable as reference component (A)

Irgacure® 184 (1-184) - commercially available photoinitiator from BASF SE, applicable as component (B)

Ingacure® TPO-L (1-TPO-L) is a commercially available photoinitiator from BASF SE, applicable as component (B)

Ingacure® TPO (1-TPO) is a commercially available photoinitiator from BASF SE, applicable as component (B)

Tego® Rad 2500 (TR 2500) - lubricant and anti-blocking additive from Evonik (silicone acrylate), applicable as component (B)

Byk-SILCLEAN 3710 (BS 3710) is a surfactant from BYK Chemie GmbH (polyether-modified acrylic-functional polydimethylsiloxane, applicable as component (B).

2. Examples

2.1 Manufacture of the veil (B1a) and the corresponding reference veneer

Were made integumentary means according to the following table 1A and 1B. Coating agents E1a-E7a are agents according to the invention. Coating agents V1a-V5a are comparison samples of the coating agent. The defined flow times at room temperature (20° C.) in the case of manufacturing E1a-E3a and V1a-V5a range from 26 to 172 seconds.

2.2 Fabrication of template films (B1F1) using E1a-E3a and V1a-V5a

Several different pattern films were made using a roll-to-plate embosser with a nickel embossing tool P1 that has the desired positive structure. To do this, one of the coating agents E1a-E3a and V1a-V5a described above was applied respectively to P1 and a PET film (F1) (Hostaphan® GN) was laid on it. The stack thus obtained of the film and the respective coating agent then passes under the pressure roll and, while the embossing device is in contact with the coating agent of the respective stack, the coating agent is at least partially cured by means of an LED UV lamp. This uses an Easytec LED UV lamp with a wavelength of 365 nm and a power of 6 W (100% lamp power, 2 m/min, 2 passes). The at least partially cured coating is then separated from the embossing device together with the film with a negative structure compared to P1, and a structured film (pattern film) is obtained. The template films were then further irradiated with a type A ultraviolet light emitter (Panacol-Elosal UV F-900).

In addition, template films were made using a roll-to-roll embossing machine with a nickel embossing tool P1 that has the desired positive structure. To do this, the coating agent E1a described above is applied to a PET film (Fl) (Hostaphan® GN) and is passed over the embossing tool P1 by means of a pressure roller. Even while the embossing device is in contact with the coating agent, the coating agent is at least partially cured by the LED UV lamp. This uses an Easytec LED UV lamp with a wavelength of 365 nm and a power of 6 W (100% lamp power, 2 m/min, 2 passes). The at least partially cured coating is then separated from the embossing device together with the film with a negative structure compared to P1, and a structured film (pattern film) is obtained. The master film was then further irradiated with a type A ultraviolet light emitter (Panacol-Elosal UV F-900).

2.3 Manufacture of Template Films (B1F1) Using E4a-E7a In addition, template films were produced using a nickel embossing tool P1, which has the desired positive structure. To do this, one of the coating agents E4a to E7a described above was applied respectively to P1 and a PET film (F1) (Hostaphan® GN) was laid on it. The stack thus obtained of the film and the respective coating agent is then, by means of a rubber roll, and while the embossing device is in contact with the coating agent of the respective stack, the coating agent is at least partially cured by means of an LED UV lamp. This uses an Easytec LED UV lamp with a wavelength of 365 nm and a power of 6 W (100% lamp power, 2 m/min, 2 passes). The at least partially cured coating is then separated from the embossing device together with the film with a negative structure compared to P1, and a structured film (pattern film) is obtained.

2.3 Manufactured template films

In the manner described in paragraphs 2.2 and 2.3, different sets of template films (E1F1-E7F1 and V1F1-V5F1,) were obtained, which, depending on the type of positive structure, differed in their embossing. In this case, nickel embossing devices with different positive structures were used, namely:

- with a nanostructure (lattice structure with a period of 430 nm and a depth of 140 nm; an appropriate coating agent is applied with a layer thickness between 5-10 µm on the PET film used),

- with microstructure A (continuous two-dimensional triangular structure with a width of 33 µm and a height of 35 µm; the appropriate coating agent is applied with a layer thickness of 20 µm on the PET film used),

- with microstructure B (continuous two-dimensional triangular structure with a width of 43 µm and a height of 10 µm; the appropriate coating agent is applied with a layer thickness of 20 µm on the PET film used) or

- with microstructure C (two-dimensional triangular structure with a height of 80 µm and a space between the structures of 115 µm; the appropriate coating agent is applied with a layer thickness of 110 µm on the PET film used).

Template films with a nanostructure were used to determine the accuracy of shape copying, the degree of conversion of double bonds and adhesion. Template films with microstructure A were used to determine the success of replication in the case of template films for which one of the coating agents E1a-E3a and V1a-V5a was used (cf. paragraph 2.5 below), and in addition, as described below under paragraph 2.6 , were used as an embossing matrix. Template films with microstructure B were used to determine the success of replication in the case of such template films, for the manufacture of which one of the coating agents E4a-E7a was used (cf. paragraph 2.5 below) and also, as described below under paragraph 2.6, was used as a matrix for embossing. Template film with microstructure C was used, as described below under paragraph 2.7, as an embossing matrix. For the preparation of this template film, the coating agent E1a was used and, accordingly, the template film E1F1 with microstructure C was obtained.

2.4 Template film tests

Table 2 below summarizes the tests carried out. The tests were carried out respectively according to the methods described above. The sign "-" in the table means that the corresponding test was not carried out.

The data show that in the case of V2F1, V3F1 and V5F1, a sufficient degree of conversion of double bonds was not achieved (degree of conversion of double bonds <90). If the double bond conversion is too low, problems can arise when embossing both the coating agent (B1a) and later the coating agent (B2a). In contrast, the E1F1, E2F1 and E3F1 template films showed a double bond conversion rate of at least 90%.

In the case of V1F1 and V4F1 the degree of conversion of double bonds, although >90%, however, with these template films, as with V3F1 and V5V1, sufficient adhesion was not achieved (assessment of the cross-cut test with note 5). If the adhesion of the pattern varnish to the PET film is too low, problems may arise when embossing both the top coat (B1a) and later of the top coat (B2a). On the contrary, all template films E1F1, E2F1 and E3F1 showed good to sufficient adhesive properties.

In addition, the data show that in the case of V2F1, V3F1 and V5F1, only 85% values were obtained when evaluating the replication success, since 15% of the corresponding V2, V3 or V5 coating could not be removed from the embossing tool. In contrast, the E1F1 and E2F1 template films tested showed a replication success rate of 100%.

With the exception of V5F1, all stencil films tested showed sufficient shape copying accuracy, as small shrinkage values were almost always obtained. Only in the case of V5F1 a shrinkage of 29% was obtained, which is unacceptable.

In summary, only the template films E1F1, E2F1 and E3F1 gave good results in all properties tested (double bond conversion, adhesion, shape copying accuracy and replication success).

2.6 Use of template films as an embossing matrix for the production of embossed commercial films

The resulting template films with A or B microstructures were then used as an embossing matrix of an embossing tool. For this, a template film is used in a roll-to-plate embossing machine. The coating agent (B2a) is applied with a wet layer thickness of 20 µm to a corresponding template film. In addition, a PET film (Hostaphan® GN) is brought into contact with the coating agent (B2a) as a substrate (F2). The stack of film and coating agent (B2a) thus obtained then passes under the pressure roller and, while the embossing device is in contact with the coating agent of the corresponding stack, at least partial curing of the coating agent (B2a) takes place by LED ultraviolet lamp. This uses an Easytec LED UV lamp with a wavelength of 365 nm and a power of 6 W (100% lamp power, 2 m/min, 2 passes). The at least partially cured coating B2 together with the film F2 is then supplied with the desired final embossed structure from the embossing matrix, i.e. the used master film, is separated from the embossing tool and a structured product film (B2F2) is obtained. The used coating agent (B2a) is a commercially available radiation-curable coating agent that contains at least one urethane acrylate and at least one photoinitiator, as well as a commercially available additive.

The following table 3a summarizes the results of replication success tests that were carried out on the resulting commercial films, taking into account the template film used for embossing, respectively. The sign "-" in the table means that the corresponding test was not carried out.

The data show that when V1F1 and V3F1 are used as the embossing matrix, only values <100% are obtained when evaluating the replication success, since in this case 15% or 58% of the B 2 coating cannot be removed from the VI or V3 coatings of the corresponding templates. films. In contrast, when using the tested template films E1F1, E2F1 and E4F1-E7F1 as the embossing matrix, a 100% success rate in replicating the B2 coating of the commercial film is achieved.

2.7 Further use of template films for the production of embossed commercial films

As an embossing matrix, the obtained template film with microstructure C (E1F1) is used. The coating agent (B2a) is applied to a template film with a wet layer thickness of 100 µm. In addition, a PET film (Hostaphan® GN) is brought into contact with the coating agent (B2a) as substrate F2 and pressed. The thus obtained stack of film (F1), coating (B1, ie E1), coating agent (B2a) and film (F2) is cured at room temperature (23°C) for 24 hours. The at least partially cured coating (B2a), together with the film (F2) with the desired final embossed structure, is then separated from the embossing matrix, hence from the used master film (E1F1) with microstructure C, and thus a structured commercial film (B2F2) is obtained. ).

The coating agent used (B2a) is a commercially available thermally cured two-component epoxy resin (Epofix from Struers GmBH). The mixing ratio of component 1 and component 2 is 9:1. Component 1 contains at least one bisphenol epichlorohydrin. Component 2 contains at least one polyamine.

The following table 3B summarizes the results of replication success tests that were carried out on the resulting commercial films, taking into account the template film used for embossing, respectively.

With the use of the template film E1F1 as the embossing matrix, a 100% replication success rate of the coating B2 of the commercial film is achieved, namely also when a thermally set coating agent (B1a) is used as the coating agent (B2a).

Claims (51)

1. A method for transferring an embossed structure to at least a portion of the surface of a cover means (B2a), which includes at least steps (1-i) and (2-i) or (1-ii) and (2 -ii), as well as at least steps (3) and optionally (4), namely: (1-i) applying the coating agent (B2a) to at least a portion of the surface of the substrate (F2), and (2-i) at least partial embossing of the coating means (B2a) at least partially applied to the surface of the substrate (F2) by means of at least one embossing tool (P2) having at least one matrix (p2) for embossing, and the matrix (p2) for embossing includes at least one combined material (B1F1) from the substrate (F1) and at least partially embossed and at least partially cured coating (B1), and after, at least partially embossed, a combined material (F2B2aB1F1) is obtained, or (1-ii) applying the coating agent (B2a) to at least part of the at least partially embossed surface of the embossing tool (P2) used as a matrix (p2) for embossing the combined material (B1F1) from the substrate (F1 ) and at least partially embossed and at least partially cured coating (B1) to form a composite material (B2aB1F1), and (2-ii) applying the substrate (F2) to at least a part of the surface formed by (B2a) of the combined material (B2aB1F1) to obtain the combined material (F2B2aB1F1), and (3) at least partial curing of the coating agent (B2a) inside the composite material (F2B2aB1F1) thus obtained to obtain the composite material (F2B2B1F1), the coating agent (B2a) being in the contact with the partial composite material (B1F1) used as a matrix (p2) for embossing in the composite material (F2B2aB1F1), and (4) if necessary, removing the composite material (F2B2) in the composite material (F2B2B1F1) from the composite material (B1F1) used as a matrix (p2) for embossing, moreover, the coating agent (B1a) used for the manufacture of the coating (B1) used as the matrix (p2) for embossing the composite material (B1F1) is a radiation-curable coating agent, characterized in that the coating agent (B1a) contains: at least one component (A) in an amount in the range from 40 to 95% by weight, at least one additive as component (B) in an amount in the range from 0.01 to 5% by weight, at least one photoinitiator as component (B) in an amount ranging from 0.01 to 15% by weight, and at least one component (D) having at least one carbon-carbon double bond in an amount in the range from 0 to 45% by weight, and (i) components (A), (B), (C) and (D) are respectively different from each other, (ii) the indicated amounts of components (A), (B), (C) and (D) are given respectively in calculated on the total weight of the coating agent (B1a), and (iii) the amounts of all components contained in the coating agent (B1a) are summed up to 100%, and moreover, the component (A) has at least three different from each other or at least partially identical structural elements according to formula (I)

wherein the residues R ¹ , respectively, independently of each other, denote an alkylene group C ₂ -C ₈ , the residues R ² respectively independently of each other represent H or methyl, and the parameters m, respectively, independently of each other, denote an integer parameter in the range from 1 to 15, but with the condition that, in at least one structural element of formula (I) in component (A), the parameter m is equal to at least 2. 2. Method according to claim 1, characterized in that the substrate (F2) is preferably a moving film web. 3. Method according to claim 1 or 2, characterized in that by means of step (2-i) or by means of step (1-ii) and step (2-ii) microstructures and/or nanostructures are transferred to the coating agent (B2a) as embossed structure. 4. Method according to one of the preceding claims, characterized in that the embossing die (p2) of the embossing tool (P2) used in step (2-i) and step (1-ii) is reused and reused for transfer, at least one embossed structure when step (4) of the method is carried out. 5. Method according to one of the preceding claims, characterized in that the composite material (B1F1) used as the embossing matrix (p2) in step (2-i) and in step (1-ii) is a film web composite material (F1 ) and deposited on it and at least partially embossed and at least partially cured coating (B1). 6. The method according to one of the preceding claims, characterized in that the combined material (B1F1) used as an embossing die (p2) during step (2-i) is guided over a first roll functioning as an embossing tool (P2), and the combined material (F2B2) is guided along the second roll, which is located opposite the first roll and rotates relative to it in the opposite direction or in the same direction, and used in step (1-ii) as a matrix (p2) for embossing the combined material (B1F1) after applying the coating agent (B2a), at least on a part of its at least partially embossed surface to obtain a combined material (B2aB1F1) during step (2-ii) is sent along functioning as a tool (P2) for embossing the first roll, and the substrate (F2) used in step (2-ii) is guided along the second roll, which is located opposite the first roll and rotates relative to it in the opposite direction. in the opposite direction or in one direction. 7. The method according to claim 6, characterized in that at least partial embossing according to step (2-i) takes place at the height of the gap between the rolls, which is formed by oppositely located oppositely rotating rolls in the opposite or in the same direction, and the at least partially embossed coating (B1) of the composite material (B1F1) faces the coating means (B2a) of the composite material (F2B2), and at least partially embossing according to step (2-ii) takes place at the height of the gap between the rolls , which is formed by counter-rotating or co-rotating rolls arranged opposite each other, the coating means (B2a) of the combined material (B2aB1F1) facing the substrate (F2). 8. The method according to one of the preceding claims, characterized in that the solids content of the coating agent (B1a) is ≥90% by weight, based on the total weight of the coating agent (B1a). 9. The method according to one of the preceding claims, characterized in that in each of at least three structural elements of formula (I) of component (A), the parameter m is at least 2. 10. The method according to one of the preceding paragraphs, characterized in that the proportion contained in the structural units of formula (I) ether segments -O[OR ¹ ] _m - in component (A) is at least 35% by weight, calculated on the total weight of component (A). 11. The method according to one of the preceding claims, characterized in that the combined material (F1B1) used as the matrix (p2) for embossing the embossing tool (P2) is obtained from the substrate (F1) and is at least partially embossed and, at least cured coating (B1) through at least steps (5)-(8), namely: (5) applying a radiation-curable coating agent (B 1a) to at least a portion of the surface of the substrate (F1), (6) at least partial embossing of the coating agent (B 1a) at least partially applied to the surface of the substrate (F1) by means of at least one embossing tool (P1) having at least one matrix (pi) for embossing (7) at least partial curing of the substrate applied on at least part of the surface (F1) and at least partially embossed coating agent (B1a) by radiation curing to obtain a combined material (F1B1) from the substrate (F1) and at least partially embossed and at least partially cured coating (B1), wherein the coating means (B1a) is in contact with at least one matrix ( p1) for embossing at least one embossing tool (P1), and (8) removing the composite material (F1B1) from the embossing tool (P1). 12. Combined material (F1B1) from the substrate (F1), at least partially embossed and at least partially cured coating (B1), which is manufactured by at least partial curing by radiation curing applied, at least at least part of the surface of the substrate (F1) and at least partially embossed coating agent (B1a), wherein the coating agent (B1a) is a radiation-curable coating agent, characterized in that the coating agent (B1a) contains: at least one component (A) in an amount in the range from 40 to 95% by weight, at least one additive as component (B) in an amount in the range from 0.01 to 5% by weight, at least one photoinitiator as component (B) in an amount ranging from 0.01 to 15% by weight, and at least one component (D) having at least one carbon-carbon double bond in an amount in the range from 0 to 45% by weight, and (i) components (A), (B), (C) and (D) are respectively different from each other, (ii) the indicated amounts of components (A), (B), (C) and (D) are given respectively relative to the total weight of the coating agent (B1a), and (iii) the amounts of all components contained in the coating agent (B1a) are summed up to 100%, and moreover, the component (A) has at least three different from each other or at least partially identical structural elements according to formula (I)

in which the residues R ¹ respectively independently of each other denote an alkylene group C ₂ -C ₈ , the residues R ² respectively independently of each other represent H or methyl, and the parameters m, respectively, independently of each other, denote an integer parameter in the range from 1 to 15, but with the condition that, in at least one structural element of formula (I) in component (A), the parameter m is equal to at least 2. 13. Combined material (F1B1) according to claim 12, characterized in that the combined material is obtained by carrying out steps (5) to (8) described in paragraph 11 of the method. 14. Composite material according to claim 12 or 13, characterized in that the substrate (F1) is a preferably moving film web. 15. The use of combined material (F1B1) according to paragraphs. 12-14 as an embossing die (p2) of an embossing tool (P2) for transferring the embossed structure to at least part of the surface of the cover means (B2a) or at least part of the surface of the cover means (B2a), which , at least partially deposited on the substrate (F2).

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