Method for transferring an embossed structure to a coated surface, and composite material usable as an embossing mold.

Abstract

The present invention provides a coating composition and a method for transferring an embossed structure onto a substrate or substrate coated with the coating composition. [Solution] The present invention relates to a method for transferring an embossed structure to at least a portion of the surface of a coating composition using a composite comprising a substrate and a coating that is at least partially embossed and at least partially cured. The coating composition is a radiation-curable coating composition comprising the following (a) to (d), and the composite is preferably used as an embossing mold for an embossing tool. (a) 5 to 45% by mass of at least one crosslinkable polymer and / or oligomer, (b) at least one reactive diluent in an amount of 40 to 95% by mass, (c) At least one photopolymerization initiator in 0.01 to 15% by mass, (d) At least one additive in 0-5% by mass.

Description

[Technical Field]

[0001] Field of Invention The present invention relates to a method for transferring an embossed structure to at least a portion of the surface of a coating composition (C2a) using a composite (S1C1) comprising a substrate or base material (S1) and a coating (C1) that is at least partially embossed and at least partially cured, in the following steps (1), (2-i) and (3-i) or (2-ii) and (3-ii), further at least in step (4), and optionally in step (5-i) or (5-ii). The coating composition (C1a) is a radiation-curable coating composition having the configuration defined herein, and the composite (S1C1) is preferably used as an embossing mold (e2) for an embossing tool (E2).

[0002] prior art In many industrial applications, it has become common practice to give workpiece surfaces structures with structural features ranging from micrometers to nanometers. Such structures are also called microstructures or fine structures (structures with features in the micrometer range) or nanostructures (structures with features in the nanometer range). These structures are used, for example, to influence the optical, biomechanical, and / or tactile properties of a material surface. Such structures are also known as embossing, embossed structures, or structured surfaces.

[0003] A common method for creating surfaces with such structures is to transfer these structures onto a coating material. This transfer is often achieved by embossing, in which a mold containing the microstructures and / or nanostructures to be formed in negative form is brought into contact with the coating material and pressed onto it. The coating material is then typically cured in situ to obtain a permanently formed structure.

[0004] WO90 / 15673A1 describes a method of applying a radiation-curable coating material to a film or to an embossed mold having a desired negative embossed structure, and then printing an embossing tool onto a foil, i.e., a foil with the coating material. Curing occurs while the radiation-curable coating agent remains between the foil and the embossing tool, and then, after the embossing tool is removed, a film with the radiation-curable coating material constituting the desired positive feature structure is obtained. European Patent EP1135267B1 also describes a method of this kind, in which a curable coating material is applied to the surface of a decorative substrate, and a corresponding embossed mold having a negative pattern is pressed into the uncured coating layer. The coating layer is then cured, and then the embossing mold is removed. EP3178653A1 discloses an article comprising a flexible cloth having a textured surface for use in casting a curable system. The fabric may have a polymer layer that can be manufactured using monofunctional and polyfunctional acrylates.

[0005] U.S. Patent No. 9,778,564B2 discloses an imprint material comprising a component that necessarily has (meth)acrylamide structural units and a further component having 2 to 6 polymerizable groups and also having alkylene oxide units. This material can be applied to a substrate, and a pattern can be applied to the resulting film using a nickel embossing tool during the curing process by irradiating the film with UV ultraviolet light.

[0006] US2007 / 0204953A1 discloses a method for patterning an adhesive resin, which provides a series of steps including applying a curable layer of the adhesive resin to a substrate, applying a structured pattern to the layer, and then continuously curing the layer to obtain a substrate having a cured adhesive resin having a desired pattern.

[0007] WO2015 / 154866A1 relates to a method for producing a substrate having a structured surface. In this method, first, a first ultraviolet (UV) curable coating is applied to the substrate and cured. On this cured coating, a second ultraviolet (UV) curable coating is applied as an embossing varnish, a microstructure is formed by embossing, and then cured.

[0008] DE102007062123A1 describes a method in which an embossing varnish, such as a UV-crosslinkable embossing varnish, is applied to a carrier film, the embossing varnish is structured in the micrometer range, the embossing varnish applied to the film is cured to obtain an embossed film, and its microstructure is then modeled by depositing metal onto the embossed surface, in other words, by metallizing the film. However, this type of modeling by subsequent metallization is undesirable because it has the drawback of resulting in a decrease in the quality of the model.

[0009] EP2146805B1 describes a method for producing a material having a textured surface. This method involves preparing a substrate with a curable coating, contacting the coating with a texturing medium and embossing it, then curing the thus embossed coating, and peeling the coating from the texturing medium. The texturing medium consists of a surface layer containing 20% ​​to 50% acrylic oligomers, 15% to 35% monofunctional monomers, and 20% to 50% polyfunctional monomers. Similar methods are described in WO2016 / 090395A1 and ACS Nano Journal, 2016, Vol. 10, pp. 4926-4941, which in each case clearly teach that a large amount of triple-ethoxylated trimethylolpropane triacrylate (TMP(EO)3TA) should be used to generate a relatively hard mold of the texturing medium in order to produce the surface layer of the texturing medium. According to WO2016 / 090395A1, the coating composition used in the manufacture of the surface layer must also contain structural units having at least two thiol groups, such as trimethylolpropanetris(3-mercaptopropionate). However, the use of such thiols in the corresponding coating material composition is often disadvantageous, as such compositions do not necessarily have sufficient storage stability, and the coatings produced from them lack sufficient weather resistance. Furthermore, there is the issue of odor due to the use of thiols, which is also, of course, undesirable.

[0010] KR2009 / 0068490A relates to a method for transferring embossed structures with fine patterns of several tens of nanometers using a polymer mold. In this case, the polymer mold consists of i) an acrylate selected from silicone (meth)acrylate and fluorine (meth)acrylate, ii) a specific polyfunctional urethane (meth)acrylate, iii) an ultraviolet-curable monomer, and (iv) a photopolymerization initiator. Methods for producing these are also disclosed, which are free from swelling by organic solvents, have improved release properties of the polymer mold from the substrate, and exhibit superior flexibility, mechanical strength, and durability compared to molds made from PDMS (polydimethylsiloxane).

[0011] Finally, WO2019185832A1 and WO2019185833A1 describe a method for transferring an embossed structure onto the surface (B2a) of a coating composition according to a specific process using a composite (F1B1) comprising a substrate (S1) and an embossed and cured coating (B1). In this method, the coating composition (B1a) used in the manufacture (B1) of the composite (F1B1) is a radiation-curable coating composition of a defined configuration. The method also relates to the use of the composite (F1B1) as an embossing die (p2) of an embossing tool (P2) for transferring an embossed structure onto at least a portion of the surface of the coating composition (B2a).

[0012] However, the embossing methods known from the prior art, for example, the methods described in particular in EP2146805B1, WO2016 / 090395A1, and ACS Nano Journal, volume 10, pages 4926 - 4941, 2016, are not necessarily fully capable of embossing, especially in the micrometer range and / or the nanometer range, that is, the transfer of microstructures and / or nanostructures, and it cannot be definitely stated that the forming accuracy does not decrease to an unacceptable extent, especially when transferred in such a way. At the same time, the reproducibility of embossing is not necessarily sufficient, or, as in WO2019185832A1 and WO2019185833A1, if the composite used as the embossing mold is aged for a specific time and the embossing mold and the coated object that has been embossed and cured are not directly separated after curing, high reproducibility cannot be obtained, and they cannot be separated without being damaged.

[0013] Therefore, there is a need for an embossing method that does not have the above-mentioned drawbacks.

Prior Art Documents

Patent Documents

[0014]

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Patent Document 7

Patent Document 8

Patent Document 9

[0015] the purpose Therefore, an object of the present invention is to provide a coating composition and a method for transferring an embossed structure to a substrate or substrate having the coating composition, more particularly a method of the same kind that enables the transfer of corresponding microstructures and / or nanostructures, and enables sufficient molding accuracy and a high success rate in transferring embossed structures even on large-area substrates, such that the embossing does not involve a loss of modulation depth, and in particular, a method that enables the manufacture of highly reusable embossing molds for transferring embossed structures and / or a method that can be carried out using such embossing molds. At the same time, it is characterized by no defects caused by undesirable or inappropriate properties of the coating and coating composition used, such as poor adhesion (in particular, including dewetting of the embossed coating composition due to surface energy mismatch, which leads to reduced mold filling and loss of adjustment, resulting in insufficient adhesion in terms of the repulsion of the embossed coating composition from the mold), and the separation between the embossed mold and the embossed and cured coating is good, regardless of the elapsed time after the embossing mold is manufactured and the embossing mold and the embossing coating composition are brought into contact. It is possible to replicate the transferred embossed structure to a considerably high degree. Furthermore, it improves molding accuracy across the entire width of the embossing mold. [Means for solving the problem]

[0016] technical solution This problem is solved by the subject matter described in the claims and by preferred embodiments of that subject matter described below.

[0017] Therefore, the first subject of the present invention is a method for transferring an embossed structure to at least a portion of the surface of a coating composition (C2a) using a composite (S1C1), the method comprising at least steps (1), (2-i) and (3-i) or (2-ii) and (3-ii), and further at least step (4), and optionally step (5-i) or (5-ii), specifically, (1) A step of preparing a composite (S1C1) consisting of a substrate (S1) and a coating (C1) that is at least partially embossed and at least partially cured, and (2-i) A step of preparing a composite (S2C2a) by applying at least one coating composition (C2a) to at least a portion of the surface of a substrate (S2), (3-i) A step of preparing a composite (S1C1C2aS2) by applying the composite (S1C1) to at least a portion of the coating composition (C2a) of the composite (S2C2a), or (2-ii) A step of preparing a composite (S1C1C2a) by applying at least one coating composition (C2a) to at least a portion of the surface of a composite (S1C1) that is at least partially embossed and at least partially cured, and then using the composite (S1C1) to at least partially emboss the coating composition (C2a), (3-ii) Optionally, a step of applying a substrate (S2) to at least a portion of the surface of the composite (S1C1C2a) formed by the coating composition (C2a) to obtain a composite (S1C1C2aS2), and (4) A step of preparing a composite (S1C1C2) or (S1C1C2S2) by at least partially curing a coating composition (C2a) that has been optionally applied to a substrate (S2), wherein the coating composition (C2a) is in contact with the composite (S1C1) throughout the period of at least partial curing. and (5-i) Optionally, remove the complex (C2S2) within the complex (S1C1) from the complex (S1C1) to restore the complex (S1C1) prepared in step (1). or (5-ii) Optionally, a step to remove the coating (C2) within the composite (S1C1) from the composite (S1C1) to restore the composite (S1C1) prepared in step (1). Includes, Here, the coating composition (C1a) used to produce the at least partially embossed and at least partially cured coating (C1) of the composite (S1C1) used in step (1) and restored in step (5-i) or step (5-ii) is a radiation-curable coating composition. (a) at least one crosslinkable polymer and / or oligomer in an amount of 1 to 45% by mass, (b) at least one reactive diluent in an amount of 40 to 95% by mass, (c) At least one photopolymerization initiator in 0.01 to 15% by mass, (d) At least one additive in 0-5% by mass Includes, Here, (i) the total amounts of components (a), (b), (c), and (d) are based on the total mass of the coating composition (C1a), and (ii) the total amount of all components present in the coating composition (C1a) is 100% by mass. Here, at least one crosslinkable polymer and / or oligomer (a) comprises at least one silicone (meth)acrylate oligomer in a total amount of at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass, and very preferably 100% by mass, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a). This method is characterized by the following features.

[0018] The method of the present invention is remarkably capable of transferring embossed microstructures and / or nanostructures, particularly in the range of structural widths from 10 nm to 1000 μm and structural depths from 1 nm to 1000 μm, to a coating composition to be embossed, regardless of the elapsed time since the composite (S1C1) was manufactured and the coating composition (C2a) was applied to it, and regardless of the elapsed time between the embossing and curing processes of the coating composition (C2a) applied to such a composite (S1C1) which can be advantageously used as an embossing mold, without losing high quality during replication due to less mold filling, and the composite (S1C1) can preferably be used as an embossing mold (e2) for an embossing tool (E2) having improved layer thickness uniformity across the width of the embossing mold, and it has been found that pressure can be applied more uniformly to the composite (S1C1).

[0019] In this regard, and remarkably, the method of the present invention has been found to enable the transfer of an embossed structure across the entire width of the mold with very high molding accuracy and a high level of successful replication, using a composite (S1C1). This composite (S1C1) is obtained by coating a radiation-curable coating composition (C1a) preferably onto a transfer substrate (S1), and can be suitably used as an embossing mold (e2) for an embossing tool (E2).

[0020] Even more surprisingly, the method of the present invention has been found to be highly advantageous. This is because the coating (C1) on the substrate (S1) is characterized by excellent adhesion and excellent separation behavior, independent of the age of the composite (S1C1) and the time elapsed since embossing and curing treatment of the coating composition (C2), and therefore the corresponding composite (S1C1) can be used very effectively as an embossed type (e2).

[0021] Furthermore, surprisingly, the composite (S1C1) usable as the embossing mold (e2) of the embossing tool (E2) in the method of the present invention is reusable, particularly in the form of a continuous embossing mold, for transferring embossed structures such as microstructures and / or nanostructures, which has proven advantageous for economic reasons. Moreover, surprisingly, this composite (S1C1), preferably existing in the form of a continuous embossing mold (e2), is not only reusable and therefore versatile, but can also be manufactured cheaply and quickly on a large industrial scale.

[0022] Therefore, a further subject of the present invention is a composite (S1C1) comprising a substrate (S1) and a coating (C1) that is at least partially embossed and at least partially cured, wherein the composite (S1C1) can be manufactured by radiation curing a coating composition (C1a) that is applied to at least a portion of the surface of the substrate (S1) and is at least partially embossed.

[0023] Here, the coating composition (C1a) is a radiation-curable coating composition, (a) at least one crosslinkable polymer and / or oligomer in an amount of 1 to 45% by mass, (b) at least one reactive diluent in an amount of 40 to 95% by mass, (c) At least one photopolymerization initiator in 0.01 to 15% by mass, (d) At least one additive in 0-5% by mass Includes, Here, (i) the total amounts of components (a), (b), (c), and (d) are based on the total mass of the coating composition (C1a), and (ii) the total amount of all components present in the coating composition (C1a) is 100% by mass. Here, at least one crosslinkable polymer and / or oligomer (a) comprises at least one silicone (meth)acrylate oligomer in a total amount of at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass, and very preferably 100% by mass, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a).

[0024] Preferably, this composite (S1C1) can be obtained by carrying out the method steps (6) to (9) described in more detail below.

[0025] Surprisingly, the at least partially embossed composite (S1C1) of the present invention can not only be used as a reusable embossing mold (e2), preferably as a reusable continuous embossing mold (e2), in embossing methods such as the method of the present invention, but it has also been found that the presence of components in the radiation-curable coating composition (C1a) used to manufacture the composite (S1C1) makes it possible to achieve very effective separation between the composite (S1C1) that can be used as an embossing mold (e2) within the embossing tool (E2) and the corresponding composite such as the embossed coating (C2) and / or the composite having an embossed coating (S2C2). In particular, it has been found that when carrying out the method of the present invention, very high-quality separation can be achieved in any step (5-i) or (5-ii) therein, regardless of the time elapsed since the manufacture of the composite (S1C1) that can be used as an embossing mold and the application of the coating composition, or the time elapsed since the embossing and curing process of the resulting coating (C2). Furthermore, a detailed examination of the method steps (6) to (9) for manufacturing the composite (S1C1) revealed that the embossed structure of the coating (C1) can be replicated with a high success rate by full mold filling across the entire width of the mold with a uniform layer thickness, thereby replicating the features of the embossed mold and achieving high replication quality.

[0026] A further subject of the present invention is the use of the composite (S1C1) of the present invention as an embossing mold (e2) of an embossing tool (E2) for transferring an embossed structure, preferably having a microstructured and / or nanostructured surface, onto at least a portion of the surface of a coating composition (C2a) optionally applied to a substrate (S2). [Brief explanation of the drawing]

[0027] [Figure 1]A schematic side view of an apparatus used to illustrate the method of the present invention is shown, which can be used to carry out steps (1), (2-i), and (3-i), as well as (4) and optionally step (5-i). [Figure 2] A schematic side view is shown of an apparatus that can be used to carry out steps (6) to (9) of the method of the present invention for producing a composite (S1C1) that is advantageously used as an embossing mold (e2), that is, for producing a master film. [Modes for carrying out the invention]

[0028] Detailed explanation When referring to official standards in connection with the present invention, this means the version of the standard accepted as of the filing date, or, if no accepted version exists as of the filing date, the most recent accepted version.

[0029] In the context of this invention, the term "at least" is understood to include the specified number (1) and more, for example, in relation to a coating composition (C1a) comprising at least one crosslinkable polymer and / or oligomer, where the coating composition (C1a) is said to contain 1, 2, 3, or 4 different or identical crosslinkable polymers and / or oligomers. The mathematical symbol for the interpretation of the word "at least" is similar to "≧". The same applies to the interpretation of the term "at least" when used in combination with a given numerical range, such as "at least 25% by mass", which in the context of this invention should be interpreted as meaning 25% by mass to 100% by mass. The term "less than" such as "less than 75% by mass" is interpreted as a range from 0% by mass to 75% by mass, rather than including the specified number ("75"). The mathematical symbol for the interpretation of the word "less than" is similar to "<".

[0030] In describing the present invention, for convenience, the terms "polymer (polymer, polymer)" and "resin" are used interchangeably to encompass resins, oligomers, and polymers (polymer, polymer).

[0031] The term "poly(meth)acrylate" refers to both polyacrylate and polymethacrylate. Therefore, poly(meth)acrylate may be composed of acrylate and / or methacrylate, and may further contain ethylenically unsaturated monomers such as styrene or acrylic acid. In the sense of this invention, the term "(meth)acryloyl" includes methacryloyl compounds, acryloyl compounds, and mixtures thereof.

[0032] In the present invention, C1-C4 alkyl refers to methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, preferably methyl, ethyl, and n-butyl, more preferably methyl and ethyl, and most preferably methyl.

[0033] In the sense of the present invention relating to the coating composition used by, for example, a coating component (C1a) and the method and process steps of the present invention, the term "comprising" preferably means "consisting of". For example, with respect to the coating composition (C1a) used by the present invention, in addition to components (a), (b), and (c), and optionally (d), it is also possible to further include in the composition one or more other components specified below and optionally present in the coating composition (C1a) used by the present invention. All components may be present in their respective preferred embodiments specified below. With respect to the method of the present invention, in addition to steps (1), (2-i), and (3-i), or (2-ii), and (3-ii), and at least step (4), and optionally step (5-i) or (5-ii), there may be further optional process steps such as steps (6) to (9).

[0034] A method of the present invention for transferring an embossed structure, comprising at least steps (1), (2-i) and (3-i) or (2-ii) and (3-ii), further at least step (4), and optionally step (5-i) or (5-ii). The first subject of the present invention is a method for transferring an embossed structure to at least a portion of the surface of a coating composition (C2a) using a composite (S1C1). This method comprises at least steps (1), (2-i) and (3-i), or (2-ii) and (3-ii), as described below, further at least step (4), and optionally step (5-i) or (5-ii).

[0035] The method of the present invention is preferably a continuous method.

[0036] The embossed structure is transferred or maintained by at least partially embossing the coating composition (C2a) applied at least partially to the surface of the substrate (S2) according to method steps (2-i) and (3-i). Alternatively, transfer by method steps (2-ii) and (3-ii) is also possible. The term "embossing" means providing an embossed structure at least partially on at least a portion of the surface of the coating composition (C2a), which is optionally part of the composite (S2C2a). In this case, the embossed structure is provided on at least a certain area of ​​the coating composition (C2a). Preferably, the embossed structure is provided on the entire surface of the coating composition (C2a), which is optionally part of the composite (S2C2a). A similar annotation applies to the term “embossed” with respect to a composite (S1C1) that is at least partially embossed, which can preferably be used as an embossing mold (e2) for an embossing tool (E2), and which consists of a substrate (S1) and a coating (C1) that is at least partially embossed and at least partially cured, and can be manufactured according to steps (6) to (9) described below.

[0037] Process (1) In step (1) of the method of the present invention, a composite (S1C1) is prepared, consisting of a substrate (S1) and a coating (C1) that is at least partially cured and at least partially embossed.

[0038] Each of the embossed structures of composite (S1C1), embossed mold (e1), and composites (S2C2a) and (S2C2) described in the following steps is preferably based on repeating patterns and / or regularly arranged patterns, independently of each other in each case, or is completely randomized. The structure in each case may be a continuous embossed structure such as a continuous groove structure, or it may be a plurality of preferably repeating individual embossed structures. In this case, each individual embossed structure may preferably be based on a groove structure having more or less strong and prominent ridges (embossed height) that define the embossed height of the embossed structure. Preferably, according to the shape of each edge of the repeating individual embossed structure, the plan view can show a variety of, preferably repeating individual embossed structures, each of which is different, for example, preferably curved, sawtooth, hexagonal, diamond, rhombus, parallelogram, honeycomb, circular, dot, star, rope, mesh, polygonal, preferably triangular, quadrilateral, more preferably rectangular and square, pentagonal, hexagonal, heptagonal and octagonal, wire-like, elliptical, elliptical and grid patterns, and at least two patterns can be superimposed on each other. Also, the edges of the individual embossed structures may have curved portions, i.e., convex and / or concave structures.

[0039] The embossed coating (C1) preferably includes at least one microstructured and / or nanostructured surface having microscale and / or nanoscale surface elements. Each embossed, microscale and / or nanoscale surface element can be described by its width, such as the width of a ridge, in other words, its structural width, and by the height of the embossing, in other words, its structural height (or structural depth). The structural width, such as the width of a ridge, may have a length of up to 1 centimeter, but is preferably in the range of 10 nm to 1 mm. The structural height is preferably in the range of 0.1 nm to 1 mm. However, each embossed structure preferably has a microstructure and / or nanostructure.

[0040] The size of a particular microscale or nanoscale surface element is defined as its maximum extension in any direction parallel to the surface, i.e., for example, the diameter of a cylindrical surface element or the diagonal of the base of a pyramidal surface element. For a surface element that has a macroscale extension in one or more directions within the surface (or parallel to the surface) and a microscale or nanoscale extension in one or more other directions within the surface, the term size of the surface element means the microscale and / or nanoscale extensions of such surface element. The length of each particular microscale or nanoscale surface element is defined as its extension in the longitudinal direction of the structured surface. Similarly, the width of a particular microscale or nanoscale surface element is defined as its extension in the width direction of the structured surface.

[0041] The height of a protruding surface element (or raised surface element) is defined by the respective extensions measured perpendicular to the adjacent bottom surface on which the protruding surface element is located. Similarly, the depth of a surface element extending downward from an adjacent top surface is defined by the respective downward extensions measured perpendicular to the adjacent top surface on which the recess extends.

[0042] The distance between two adjacent surface elements is defined, in a direction within the structured surface, as the distance between two maximum values ​​or two local maximums between such surface elements. A structured surface in which surface elements are regularly arranged in one or more predetermined directions parallel to the surface can be characterized by one or more pitch lengths in that direction. In a direction parallel to the surface, pitch length is a term that describes the distance between corresponding points of two adjacent, regularly repeating surface elements. This can describe a structured surface consisting of alternatingly arranged channel-type and rail-type surface elements, both of which extend macroscopically, essentially parallel to each other, in a first longitudinal direction, and each having a microscale cross-section perpendicular to that longitudinal direction and optionally a nanoscale cross-section. The pitch length perpendicular to the longitudinal direction of such a structured surface is the sum of the widths of the channel-type surface elements and the rail-type surface elements in that perpendicular direction.

[0043] Each microstructure and / or nanostructure surface transferred by embossing preferably comprises microscale and / or nanoscale surface elements having a structural width favorably located in the range of 10 nm to 1000 μm, preferably 10 nm to 500 μm, more preferably 25 nm to 400 μm, very preferably 50 nm to 250 μm, and more preferably 100 nm to 100 μm, and a structural height favorably located in the range of 10 nm to 1000 μm, preferably 10 nm to 500 μm, more preferably 25 nm to 400 μm, very preferably 50 nm to 300 μm, and more preferably 100 nm to 200 μm. These dimensions apply to the composite (S1C1), the embossed structures of both the composite (C2S2) and the coating (C2), and logically, to the embossing mold (e1) in any step (7).

[0044] The structural width and structural height of each surface having microstructured and / or nanostructured surface elements are preferably determined by preparing a cross-section of the surface and measuring the structural height and structural width of this cross-section using an optical and / or scanning electron microscope.

[0045] The composite (S1C1) prepared in step (1) of the method of the present invention can be fabricated by various processes, for example, by lithography methods such as nanoimprint lithography, laser lithography, and photolithography. It is preferable to fabricate the composite (S1C1) by steps (6) to (9), which will be specified in detail later.

[0046] In steps (3-i) and (2-ii), the composite (S1C1), which is preferably used as an embossing mold (e2) and consists of a substrate (S1) and a coating (C1) that is at least partially embossed and at least partially hardened, is also referred to in the present invention as a "master substrate" or "master film". When the substrate (S1) is a film, the corresponding master film is referred to as a "master foil". Hereinafter, the coating (C1) of the master film is also referred to as a "master coating that is at least partially hardened" or a "master coating film", and the coating composition (C1a) used in the manufacture of the hardened master coating is also referred to as a "master coating". It is preferable that there is no further (coating) layer between (S1) and (C1) of the composite (S1C1). However, it is possible for at least one adhesion promoter layer to be present between (S1) and (C1) of the composite (S1C1), in which case it is preferable that this layer be transparent to UV radiation.

[0047] Processes (2-i) and (3-i) Following step (1), the first alternative involves preparing a composite (S2C2a) by at least partially applying the coating composition (C2a) to the substrate (S2), and then preparing a composite (S1C1C2S2) by at least partially embossing the coating composition (C2a) of the composite (S2C2a) using the composite (S1C1). This first alternative to the method of the present invention is described here by steps (2-i) and (3-i).

[0048] Process (2-i) Step (2-i) of the method of the present invention is a step of preparing a composite (S2C2a) by applying a radiation-curable coating composition (C2a) to at least a portion of the surface of a substrate (S2).

[0049] The substrate (S2) represents the coating composition (C2a) or the carrier material for the coating (C2) applied thereon. The substrate (S2), or, when using a coated substrate, the layer located on the surface of the substrate (S2) and in contact with the coating composition (C2a), is preferably made of at least one thermoplastic polymer. More specifically, the selection is made from the group consisting of polyesters including polymethyl (meth)acrylate, polybutyl (meth)acrylate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyvinylidene fluoride, polyvinyl chloride, polycarbonate, and polyvinyl acetate, preferably polyesters such as PBT and PET, polyamides, polyolefins (such as polyethylene, polypropylene, polystyrene, and even polybutadiene), polyacrylonitrile, polyacetal, polyacrylonitrile-ethylene-propylene-diene-styrene copolymer (A-EPDM), polyimide (PI), polyetherimide (PEI), cellulose triacetate (TAC), phenolic resins, urea resins, melamine resins, alkyd resins, epoxy resins, polyurethanes such as thermoplastic polyurethane (TPU), polyether ketones, polyphenylene sulfide, polyethers, polyvinyl alcohol, and mixtures thereof. Particularly preferred substrates or layers on their surface are polyolefins such as PP (polypropylene), which may alternatively be isotactic, syndiotactic, or atactic, and may alternatively be unoriented or oriented by uniaxial or biaxial stretching, such as SAN (styrene-acrylonitrile copolymer), PC (polycarbonate), PMMA (polymethyl methacrylate), PBT (poly(butylene terephthalate)), PA (polyamide), ASA (acrylonitrile-styrene-acrylic ester copolymer), and ABS (acrylonitrile-butadiene-styrene copolymer), and further physical mixtures (blends) thereof. Particularly preferred are PP, SAN, ABS, ASA, and blends of ABS or ASA with PA or PBT or PC. Particularly preferred are PET, PBT, PP, PE, polymethyl methacrylate (PMMA), or impact-modified PMMA.Particularly preferred is polyester used as the material for the substrate (S2), most preferably PET. Alternatively, the substrate (S2) itself (optionally, even if at least one layer of the aforementioned polymer is applied) may be made from a different material such as glass, ceramic, metal, paper and / or fabric. In that case, the substrate (S2) is preferably a plate and can be used, for example, in a roll-to-plate (R2P) embossing machine.

[0050] The coating composition (C2a) is advantageous to be irradiated with radiation via the substrate (S2) or the composite (S1C1), preferably via the substrate (S2). Therefore, it is preferable that the radiation transmittance of the substrate (S2) is harmonized with the maximum absorption value, or at least within the absorption region, of the at least one photoinitiator used in the coating composition (C2a). A further layer, for example, an adhesion-promoting layer which is preferably transparent to UV irradiation, can be present between (S2) and (C2a) of the composite (S2C2a). However, it is advantageous that there is no further layer between (S2) and (C2a) in the composite (S2C2a). Alternatively, when the coating composition (C2a) is irradiated with radiation via the composite (S1C1), the substrate (S2) may also be impermeable to the radiation applied, such as ultraviolet radiation. Furthermore, the base material (S2) can be selected from (i) a single-sided or double-sided adhesive tape including a release liner, or (ii) a polymer base material covered on one side with a self-adhesive layer, or a self-adhesive polymer base material.

[0051] The thickness of the substrate (S2) is preferably 2 μm or more and 5 mm or less. Particularly preferred is a layer thickness of 25 to 1000 μm, and more specifically, 50 to 300 μm.

[0052] The base material (S2) is preferably a film, more preferably a film web, and very preferably a continuous film web. In this case, the base material (S2) can preferably be used in a roll-to-roll (R2R) embossing apparatus or a plate-to-roll (P2R) embossing apparatus.

[0053] In relation to the present invention, the terms "continuous film" or "continuous film web" preferably refer to a film having a length of 100m to 10km.

[0054] When carrying out step (2-i) (preferably when carrying out steps (3-i), (4) and (5-i) of the method of the present invention, and also when carrying out steps (2-ii), (3-ii), (4) and (5-i) or (5-ii) of the method of the present invention), the substrate (S2) is in motion, so it is preferable that the substrate be a movable substrate. During the carrying out of steps (2-i) and (3-ii), it is preferable that the substrate (S2) is moved by a conveying device such as a belt conveyor. Therefore, it is preferable that the applicable apparatus used to carry out steps (2-i) and (3-ii) is equipped with such a conveying device. The applicable apparatus used to carry out step (2-i) preferably further comprises means for applying the radiation-curable coating composition (C2a) to at least a portion of the surface of the substrate (S2). The same applies to the applicable apparatus for carrying out step (3-ii) and any steps (6) to (9).

[0055] The coating composition (C2a) prepared in steps (2-i) and (2-ii) of the method of the present invention may be any type of coating composition, as will be further described later. It is advantageous to apply the coating composition (C2a) applied in steps (2-i) and (2-ii) with a dry film thickness of at least 0.5 μm, preferably at least 1 μm to 1000 μm, and more preferably at least 5 μm to 1000 μm.

[0056] The coating composition (C2a) applied in steps (2-i) and (2-ii) is preferably applied with a dry film thickness of at least 0.5 μm, preferably 5 to 1000 μm, more preferably 6 to 900 μm, even more preferably 7 to 700 μm, particularly preferably 8 to 500 μm, particularly preferably 9 to 400 μm, and especially 10 to 300 μm. The dry film thickness is determined according to DIN EN ISO2808:2007-05, procedure 12A. In relation to the present invention, dry film thickness preferably refers to the thickness of the dry film on the protrusions of the embossed structure having microscale and / or nanoscale surface elements on the surface of the coating (C2) or a similar coating (C1).

[0057] Process (3-i) In step (3-i) of the method of the present invention, the coating composition (C2a) applied at least partially to the surface of the substrate (S2) is subjected to at least partial embossing using the composite (S1C1). Here, it is preferable to use the composite (S1C1) as the embossing mold (e2) of the embossing tool (E2). The composite (S1C1) consists of the substrate (S1) and a coating (C1) that is at least partially embossed and at least partially cured, and the composite (S1C1C2aS2) is prepared as a result of at least partial embossing. Preferably, the composite (S1C1) used as the embossing mold (e2) may be pre-wetted with the coating composition (C2a) before the composite (S1C1) is brought into contact with the coating composition (C2a) to be embossed.

[0058] At least partial embossing transfers an embossed structure at least partially to the surface of the coating composition (C2a) applied to the substrate (S2). The term “emboss” means a step in which at least a portion of the surface of the coating composition (C2a) after steps (3-i) and (4) exhibits an embossed structure as part of the composite (S2C2). In this case, at least a certain area of ​​the coating composition (C2a) of the composite (S2C2) is provided with an embossed structure. Preferably, the entire surface of the coating composition (C2a) of the composite (S2C2) is provided with an embossed structure. Similar annotations apply to the term “emboss” with respect to steps (2-ii) and (4) of the method of the present invention, and to any steps (7) and (8) for preparing the composite (S1C1). An embossed feature or structure within the coating composition (C2a) (or, with respect to preparing the composite (S1C1), the coating composition (C1a)) is thereby a mirror image of an embossed structured surface. In the method of the present invention, the embossed structure of the composite (S1C1) is transferred to the coating composition (C2a) or the coating (C2) after at least partial curing, where the composite (S1C1) is preferably used as an embossing mold (e2) for the embossing tool (E2). Therefore, the structure embossed in the coating composition (C2a) is a mirror image of the embossed structure on at least one surface of the composite (S1C1), which comprises the substrate (S1) and the coating composition (C1) that is at least partially cured and at least partially embossed. Thus, the image of the embossed surface of the coating composition (C2a) that is at least partially embossed and the coating composition (C2) that is at least partially cured and at least partially embossed may correspond to the image of the embossing mold (e1), where the embossing mold (e1) was used to emboss the coating composition (C1a) of the composite (S1C1), as will be further described below.

[0059] In step (3-i), it is preferable to transfer microstructures and / or nanostructures as embossed structures onto the coating composition (C2a).

[0060] A corresponding apparatus preferably used to carry out step (3-i) (and similarly for steps (2-ii) and (3-ii) of the method) comprises means for at least partially embossing a coating composition (C2a) at least partially applied to the surface of a substrate (S2) with at least one embossing tool (E2) having at least one embossing mold (e2). The apparatus preferably used further comprises means for pressing the embossing mold (e2) of the embossing tool (E2), and thus the composite (S1C1), onto the substrate (S2), which is preferably used in the form of a continuous film web, after the radiation-curable coating composition (C2a) has been applied to (S2), wherein the means is preferably located downstream of the means for applying the radiation-curable coating composition (C2a) as viewed from the transport direction of the substrate (S2).

[0061] If necessary, step (3-i) may be performed at a high temperature of 30°C to 100°C or up to 80°C. In this case, the composite (S2C2a) is first passed through a heating roll mechanism, followed optionally by infrared irradiation. Then, the actual embossing procedure is performed, i.e., it is cured while in contact with the embossing tool (E1). After embossing and curing, the embossed composite (S2C2) is optionally passed through a cooling roll mechanism to be cooled. Alternatively, it is also possible to cure while cooling. In this case, the composite for embossing (S2C2a) is first passed through a cooling roll mechanism before performing the actual embossing procedure described above. Alternatively, instead of using a separate heating or curing roll mechanism, the embossing tool (E2) can be heated or cooled.

[0062] Therefore, the apparatus that can be preferably used to emboss the coating composition (C2a) applied to the substrate (S2) is preferably the following means, namely, (a) Conveying means for transporting the base material (S2), preferably a conveyor belt, (b) Preferably means of applying a radiation-curable coating composition (C2a) to at least a portion of the surface of a mobile substrate (S2), (c) An embossing tool (E2) wherein at least one embossing mold (e2) is preferably located downstream of a means (C2a) for applying a radiation-curable coating composition, with respect to the transport direction of the substrate (S2), and optionally comprising means for pressing the embossing mold (e2) of the embossing tool (E2) onto the substrate (S2), (d) Any heating means, preferably a heating roll mechanism combined with an infrared (IR) radiation means, (e) Any cooling means, preferably a cooling roll mechanism, and (f) Means for irradiating with radiation, preferably ultraviolet (UV) light. It is equipped with.

[0063] The embossing tool (E2) may preferably be an embossing calender equipped with a grid coating mechanism, more preferably a grid roll mechanism. This calender preferably has counter-rotating rolls arranged vertically at a constant interval in the height direction, to which the composite (S2C2a) to be embossed is fed onto the rolls and guided through the roll nip to be formed, and the nip width can be variably adjusted. The grid roll mechanism here preferably comprises a first roll such as a steel roll, a steel roll covered with a metal layer such as a copper layer or a nickel layer optionally containing a small amount of phosphorus, or a metal roll such as a roll covered with a nickel sleeve optionally containing a small amount of phosphorus, or other quartz rolls. However, alternatively, a soft material such as rubber or polydimethylsiloxane (PDMS) may also be used as the first roll, or as a roll covered with at least one soft material such as rubber or PDMS. Furthermore, a roll coated with at least one plastic may also be used. Furthermore, the grid roll mechanism includes a second roll, which is preferably a steel pressing roll or a roll coated with at least one type of plastic, rubber, or a soft material such as PDMS. The second roll functions as an impression roll or a press roll. The composite to be embossed (S2C2a) is, for example, in the form of a film web at least partially coated with a coating composition (C2a), and is moved in the opposite direction to the first roll by the second roll or press roll. Embossing is performed in the roll nip section, which is formed by counter-rotating rolls arranged at a certain distance from each other, according to step (3-i). The first roll, which carries the composite (S1C1) as an embossing mold (e2), plays the role of embossing the composite (S2C2a) guided by the second roll opposite this embossing roll, and the second roll presses the composite (S2C2a) to have an embossed structure against the first embossing roll.In this step, in step (3-i) or (2-ii) of this method, a mirror image of the embossed structure on the surface of the coating (C1) of the composite (S1C1) is transferred to the surface of the coating composition (C2a) of the composite (S2C2a).

[0064] The embossing tool (e2), including the embossing mold (e2), is preferably pressed at least partially onto the applied coating composition (C2a) during the execution of step (3-i).

[0065] The composite (S1C1) can be used as a reusable continuous embossing mold (e2) for an embossing tool (E2), and the composite can very effectively separate the composite (S1C1) from a coating (C2) that is at least partially cured and at least partially embossed, which is optionally applied to a substrate (S2) having a structured surface, within the method of the present invention if the method of the present invention necessarily includes step (5-i) or (5-ii). Step (3-i) preferably involves transferring a microstructure and / or nanostructure of the previously described dimensions in relation to the composite (S1C1) prepared in step (1).

[0066] The embossed type (e2), in other words, the composite (S1C1), preferably comprises a film web as a base material (S1) having a coating (C1) that is at least partially embossed and at least partially cured. Particularly preferably, the base material (S1) is a continuous film web having a coating (C1) that is at least partially embossed and at least partially cured, and thus the composite (S1C1) used as the embossed type (e2) is a continuous embossed type, which is particularly preferred when the base material (S2) is also a continuous film web.

[0067] Processes (2-ii) and (3-ii) Following step (1), instead of steps (2-i) and (3-i), the coating composition (C2a) may first be applied at least partially to the composite (S1C1), thereby at least partially embossing, and then optionally the substrate (S2) may be applied at least partially to the surface formed by the coating composition (C2a). This second option of the method of the present invention is described here by steps (2-ii) and (3-ii) in comparison to the first option of the method of the present invention, which consists of steps (2-i) and (3-i).

[0068] Process (2-ii) Step (2-ii) of the method of the present invention involves at least partially embossing a composite (S1C1), applying at least one coating composition (C2a) to at least a portion of the surface that has been at least partially cured, and then using the composite (S1C1) to at least partially emboss the coating composition (C2a) to prepare a composite (S1C1C2a).

[0069] The composite (S1C1), which can preferably be used as the embossing mold (e2) of the embossing tool (E2), may optionally be pre-wetted before applying the coating composition (C2a).

[0070] The coating composition (C2a) prepared in steps (2-i) and (2-ii) of the method of the present invention may be any type of coating composition, and as will be described later, it is preferably a radiation-curable coating composition. The coating composition (C2a) applied in steps (2-i) and (2-ii) is advantageous to be applied with a dry layer thickness of at least 0.5 μm, preferably at least 1 μm, more preferably at least 5 μm, and up to 1,000 μm.

[0071] In step (2-ii), a desirable (mirror image) of the composite (S1C1) on the substrate (S1) is transferred from the composite (S1C1) to the coating composition (C2a), and further to the coating (C2) after step (4), by applying the preferred radiation-curable coating composition (C2a) to at least a portion of the partially embossed surface of the composite (S1C1). Thus, the composite (S1C1) not only functions as a carrier material for (C2a) or (C2), but also functions as an embossing mold, preferably as an embossing mold (e2) for the embossing tool (E2).

[0072] The partial embossing in step (2-ii) is preferably performed by pressing and pressing the applied coating composition (C2a) onto a composite (S1C1) which is advantageously used as the embossing mold (e2) of the embossing tool (E2). The application of this pressure can be achieved, for example, by means such as a roll or a grid roll mechanism comprising at least one roll after the coating composition (C2a) has been applied. The pressure typically applied is in the range of 1 to 10 bar, preferably 2 to 8 bar, and more preferably 3 to 7 bar. The grid roll mechanism here preferably comprises metal rolls such as a steel roll, a steel roll covered with a metal layer such as a copper layer or a nickel layer optionally containing a small amount of phosphorus, or a roll covered with a nickel sleeve optionally containing a small amount of phosphorus, or a quartz-based roll or a roll coated with at least one plastic such as PDMS, rubber or silicone. Optionally, the applied coating composition (C2a) can be temporarily backed with foil to provide advantageous protection from oxygen and mechanical influences at least during embossing and curing in steps (2-ii) to (4), but also during step (5). Removing the temporary foil, preferably with a thickness of 5 μm to 250 μm, provides the composite (S1C1C2). Suitable materials for the temporary foil are selected from the same materials that can be used in the manufacture of the substrate (S2) described above. The relevant section is explicitly cited here. Alternatively, the foil can be selected from materials commonly observed as release liners, or from cellulose triacetate (TAC). The temporary foil is preferably made of PET or TAC.

[0073] Process (3-ii) Step (3-ii) of the method of the present invention involves optionally attaching a substrate (S2) to at least a portion of the surface of the composite (S1C1C2a) formed by the coating composition (C2a) to obtain a composite (S1C1C2aS2).

[0074] The composite (S1C1) advantageously used as an embossing mold (e2) in step (2-ii) is preferably guided by a first roll that functions as part of the embossing tool (E2) during the execution of step (3-ii) after applying a coating composition (C2a) to at least a portion of its partially embossed surface to obtain a composite (S1C1C2a), and the substrate (S2) used in step (3-ii) is preferably guided via a second roll. The second roll is opposite to the first roll and can rotate in the opposite direction or in the same direction as the first roll (co-rotary), preferably in the opposite direction.

[0075] The at least partial embossing by step (3-ii) is preferably carried out with the coating composition (C2a) of the composite (S1C1C2a) facing the substrate (S2) at the level of the roll nip formed by two opposing rolls rotating in opposite or the same direction. In this case, the at least partial embossing is preferably achieved by applying pressure or pressing the substrate (S2) to the composite (S1C1C2a) by, for example, a second roll or press roll.

[0076] The corresponding apparatus described above, which is preferentially used to carry out steps (2-i) and (3-i) of this method, can also be used in a similar manner to carry out steps (2-ii) and (3-ii) of this method.

[0077] Process (4) Following steps (2-i) and (3-i) as a first option of the method of the present invention, or following steps (2-ii) and (3-ii) as a second option of the method of the present invention, step (4) of the method of the present invention is to apply at least partially embossed coating composition (C2a) to a substrate (S2) obtained after step (3-i) or (3-ii), and to at least partially cure it to prepare a composite (S1C1C2) or (S1C1C2S2). Here, during the at least partially curing period, the coating composition (C2a) is in contact with the composite (S1C1), which is preferably used as the embossed type (e2).

[0078] In step (4), the applied coating composition (C2a) is cured at least partially to produce a partially embossed and partially cured coating material, optionally comprising a substrate (S2). The term “at least partially cured” with respect to the coating composition (C2a) is understood to mean a transformation of the coating composition (C2a) into a certain state, namely, that at least a portion of the coating composition changes into a film, as a result of which the formed coating (C2) can be further processed or treated, for example, in a post-exposure process to increase the double bond conversion ratio, or the coating (C2) can be removed as part of a composite (S2C2) or as a standalone film (C2).

[0079] Preferably, during the partially curing period in step (4), the means used in steps (2-i) and (3-i) or steps (2-ii) and (3-ii) for pressurizing or pressing the applied coating composition (C2a) toward at least one composite (S1C1) which is preferably used as an embossing mold (e2) are in contact with the coating composition (C2a) and / or with at least the partially cured coating (C2) formed from the coating composition.

[0080] Step (3-i) or steps (2-ii) and (3-ii), and step (4) are preferably carried out simultaneously. In this case, at least partial curing by step (4) is preferably carried out in situ during the execution of step (3-i).

[0081] Therefore, the corresponding apparatus preferably used in carrying out step (4) is preferably equipped with at least one radiation source for irradiating the coating composition (C2a) with curing radiation. Since the coating composition (C2a) is preferably an ultraviolet-curable coating composition, the curing radiation used is preferably ultraviolet light. If the coating composition (C2a) is not radiation-curable, it is preferably chemically curable. In that case, curing in step (4) is performed thermally, for example, by using a suitable thermal radiation source. Of course, it is also possible to combine curing methods, and it is possible to use thermal curing and ultraviolet (UV) curing in combination.

[0082] Suitable radiation sources for radioactive curing include low-pressure, medium-pressure, and high-pressure mercury emitters, as well as fluorescent tubes, pulse emitters, metal halide emitters (halogen lamps), lasers, LEDs, and electron flash devices or excimer emitters that enable radioactive curing without photoinitiators. Radioactive curing is performed by exposure to high-energy radiation, i.e., ultraviolet (UV) irradiation, exposure to sunlight, or irradiation with high-energy electrons. In the case of ultraviolet (UV) curing, the irradiation dose required for crosslinking is usually 80-3000 mJ / cm². 2 This is within the range. Of course, it is also possible to harden using two or more radiation sources; for example, two to four radiation sources can be used. In addition, these light sources may each emit light in different wavelength ranges.

[0083] At least partial curing in step (4) is preferably carried out by irradiation through the substrate (S2) and / or composite (S1C1). Irradiation is preferably carried out through the composite (S1C1). If there is no substrate in step (3-ii) and the composite (S1C1) is advantageously used as at least one embossing mold (e2) of the embossing tool (E2), irradiation is preferably carried out through the composite (S1C1) used as the substrate. In any case, it is advantageous that the permeability of the substrate (S2), or the substrate (S2) made of a self-adhesive polymer substrate, and / or the further layer between the substrate (S2) and the coating composition (C2a), or the substrate (S1) in the composite (S1C1), which has a single-sided or double-sided adhesive tape with (i) optionally having a release liner on one side, or (ii) a self-adhesive layer, is in harmony with the absorption maximum or at least absorption range of the at least one photopolymerization initiator used, which is preferably present in the coating composition (C2a). Therefore, for example, the PET material used as the substrate (S2), and thus, for example, the PET film, is transparent to radiation having a wavelength of less than 400 nm. Examples of photopolymerization initiators that generate radicals with such radiation include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphine, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide. Therefore, in this case, it is preferable that at least one such photopolymerization initiator is present in the coating composition (C2a).

[0084] Any step (5-i) or (5-ii) Following step (4), either step (5-i) or (5-ii) is performed depending on the presence or absence of the substrate (S2). For this reason, in the first option of the method of the present invention as defined by steps (2-i) and (3-i), the presence of the substrate (S2) is essential. Therefore, only the arbitrary step (5-i) is applicable. In the second option of the method of the present invention as defined by steps (2-ii) and (3-ii), the arbitrary step (5-i) is applicable if the arbitrary substrate (S2) in step (3-ii) is attached to at least a portion of the surface formed by the coating composition (C2a). However, if the arbitrary substrate (S2) is not attached in step (3-ii), only step (5-ii) is applicable.

[0085] Steps (5-i) and (5-ii) in the method of the present invention preferably involve optionally removing the embossed coating (C2) optionally attached to the substrate (S2) from the composite (S1C1) used as an embossing mold (e2) to produce a composite (S2C2) consisting of the substrate (S2) and a coating (C2) that is at least partially embossed and at least partially cured, or, if no substrate (S2) is present, producing a self-supporting coating (C2), and involve restoring the composite (S1C1) prepared in step (1) of this method. Step (5-i) or (5-ii) is preferentially carried out.

[0086] When removing the composite (S1C1), which is preferably used as an embossed mold (e2), as described above, it is possible, for example, to peel off the composite (S1C1) a coating (C2) that has been at least partially embossed and at least partially cured, which has been optionally attached to a substrate (S2), or vice versa. The peeling can be done manually or using a commonly known mechanical peeling method.

[0087] Alternatively, the removal from the complex (S1C1) may include the following steps:

[0088] 5-ia) A step of preparing a composite (S1C1C2S2AL) by applying at least one adhesive layer (AL) to the surface of a substrate (S2) that is not in contact with at least partially embossed coating (C2), 5-ib) Optionally, a step of attaching the composite (S1C1C2S2AL) at least partially to an object (O1), 5-ic) A step of removing, preferably peeling off, a composite (S1C1) from a composite (C2S2AL) that has been optionally attached at least partially to an object (O1), or 5-ii-a) A step of preparing a composite (S1C1C2AL) by applying at least one adhesive layer (AL) to at least a portion of the unstructured surface of a coating (C2) that is at least partially embossed, 5-ii-b) Optionally, a step of attaching the composite (S1C1C2AL) at least partially to an object (O1), 5-ii-c) Optionally, a step of removing, preferably peeling off, a composite (S1C1) from a composite (C2S2AL) that is at least partially attached to an object (O1).

[0089] The adhesive layer (AL) can be, for example, a laminating adhesive such as polyacrylate or a polyacrylate-based adhesive. However, the adhesive layer (AL) is preferably a self-adhesive layer structure or a multilayer structure. Such a self-adhesive layer can be applied by general methods such as laminating or spraying the adhesive. The multilayer structure consists of, for example, an intermediate polymer layer (PL), also called an inliner, on both surfaces coated with adhesive (AH). The adhesive (AH) may be polyacrylate or a polyacrylate-based adhesive. In principle, any type of polymer can be used to prepare the intermediate polymer layer (PL). Specific examples of such polymers include the polymers already described as the base material (S2). The relevant paragraph is explicitly cited here. Suitable intermediate polymer layers (PL) are poly(meth)acrylate, polyesters such as PET and / or PBT, polyvinylidene fluoride, polyvinyl chloride, polyamide and / or polyolefin. In particular, polyesters such as PET can be used. The thickness of the polymer layer (PL) can be in the range of 5 to 55 μm, preferably 6 to 50 μm, more preferably 7 to 40 μm, and particularly 8 to 30 μm. Each adhesive (AH) may initially be covered with a release liner such as silicone paper to improve handling. However, one of the two release liners is removed before being used as the adhesive layer (AL) in step 5-i) or step (5-ii). The other release liner is preferably removed in a later step of the process of the present invention, more preferably before the composite (S1C1C2) or (S1C1C2S2) is at least partially attached to at least one object (O1). Therefore, before separating the composite (S1C1) from the composite (C2S2) having a coating (C2) or adhesive layer (AL), these composites are attached to an object (O1), and only then is the composite (S1C1) removed, preferably by peeling it off from the coating (C2) or from the composite (C2S2) that is at least partially attached to the object (O1) via the adhesive layer (AL).A suitable object (O1) can be made from a variety of materials, including metals, plastics, reinforcing materials, glass, rubber, cloth, leather, paper, wood, and mixtures thereof. Preferably, at least one object (O1) is selected from the group consisting of surfaces in contact with liquids and gases, such as airplanes, ships and automobiles, rotor blades, drilling platforms, pipelines, lighting systems, displays, photovoltaic modules, structural elements and decorative elements.

[0090] Steps 5-ia) and 5-ib), or 5-ii-a) and 5-ii-b), may be performed manually or by machine. The machine may include at least one conveying means for the adhesive layer (AL), at least one pressurizing means for applying pressure to fix the adhesive layer (AL) to at least one portion of the unstructured surface of the partially embossed coating (C2), or to the surface of the substrate (S2) that is not in contact with the partially embossed coating (C2), and at least one splitting means for removing, preferably peeling, or vice versa, the coating (C2) or the composite (S2C2) from a composite (S1C1) which can be advantageously used as an embossing mold (e2) for an embossing tool (E2).

[0091] The procedure for removing at least partially embossed and at least partially cured coatings (C2) or composites (S2C2) from a composite (S1C1) is preferably carried out easily without damaging the structured and embossed surface and without leaving any significant residue on the surface of the coating (C1) of the composite (S1C1), preferably without leaving any residue at all.

[0092] Figure 1 schematically shows a side view of an apparatus used to illustrate the method of the present invention, which can be used to carry out steps (1), (2-i), and (3-i), further (4), and optionally step (5-i). This apparatus can also be used in essentially similar ways to carry out steps (1), (2-ii), and (3ii), further (4), and optionally (5-i) or (5-ii) of the method of the present invention. This apparatus makes it possible to transfer structures such as microstructures and / or nanostructures from an embossing mold (S1C1, e2) existing as a master film onto a substrate (S2) coated with (C2a). Therefore, this apparatus is also commonly called a transport apparatus and is indicated by reference numeral (10) in Figure 1.

[0093] The core of the transfer apparatus (10) is the embossing area (1), where a press roll (2) having a roll jacket made of fused silica is positioned. The press roll (2) is rotationally driven. Positioned alongside the press roll (2) is a radiation source in the form of a lighting unit (3), which generates ultraviolet (UV) light and may be equipped with UV-LEDs arranged in a row along the length of the press roll (2). Alternatively, as shown in Figure 1, the lighting unit (3) may be positioned inside the press roll (2). In the embossing area (1), a press roll (4) is positioned to be pressed against the press roll (2). The mold (5) of the transfer apparatus (10) has two film web rollers (6) and (7) positioned on it, which can be rotated by motor drive. Of course, the film web rollers (6) and (7) can also be mounted and positioned in places other than the mold (5), for example, on the cabinet elements outside the actual transfer apparatus (10). Here, the master film web (8), which will form a continuous embossed shape, is wound onto the film web rollers (6) and (7), which are shown as being positioned within the mold. The transfer surface of the master film web (8) is provided with a master coating layer (C1) on which the negative shape of the microstructures and / or nanostructures to be transferred is formed as a surface relief. The relief structure within the master coating layer (C1) is stable because it is at least partially cured. The master film web (8) can be obtained by carrying out steps (6) to (9) of the method of the present invention and thus constitutes a composite (S1C1). The master film web (8) is supplied to the embossing region (1) away from the first film web roller (6) via various deflection roller systems and travels vertically from above in the region between the press roll (2) and the pressing roll (4), as is clear from Figure 1. In that region, the master film web is guided in a tightly taut state in contact with the entire outer circumference of the press roll (2), then moves away from the press roll (2) again and is supplied again to the second film web roller (7) via the deflection roller system with web tensioner, where it is wound up.A film web (9) forming a substrate (S2) to which a structure such as a microstructure and / or nanostructure is to be imparted starts from a film web roller (11) and is brought to the embossing region (1) via a variety of deflection roller systems, which again include a web tightening device. In this region, it moves taut over the peripheral area of ​​the press roll (4) and from there enters the contact area of ​​the press roll (4) on the press roll (2) or the area of ​​the roll nip formed between these elements. The film web (9) moves away from this region, vertically downward in Figure 1, and is guided to the film web roller (12) (again guided by the deflection roller system and web tightening device), where it is wound up as a complete processed product. Along its path to the embossing region (1) or on the roll nip between the press roll (2) and the press roll (4), the film web (9) is coated by a coating application unit (27) on its surface facing the press roll (2) in the press region (1). In this case, the coating application unit (27) is located outside the press area (1). Therefore, the coating application unit (27) applies the coating composition (C2a) to the film web (9) to be used as (S2) according to step (2-i) of the method of the present invention. In the press area (1), the film web (9) is then joined together with the surface of the master film web (8), which has a master coating layer, by its surface having an uncured coating layer. In this case, the film web (9) moves via the pressure roller (4) and the master film web (8) moves via the press roll (2). Both the film web (9) and the master film web (8) face each other with their respective coating layers (in the case of the master film web (8), at least a partially cured master coating layer corresponding to coating (C1); in the case of the film web (9), an uncured coating layer corresponding to coating composition (C2a)) on their surfaces.In the region where the pressing roll (4) is pressed against the press roll (2), a negative image of the transfer structure, such as microstructures and / or nanostructures formed on the master coating layer (C1), is imprinted onto the uncured coating layer corresponding to the coating composition (C2a), and as a result, these structures are transferred. Simultaneously, the illumination unit (2) performs UV irradiation, and thus performs at least partial curing of the uncured coating layer corresponding to the coating composition (C2a) on the film web (9) (as long as this coating layer remains in contact with the master coating layer (8)). Thus, at least partial curing of the coating layer occurs directly and in situ during the transfer of the structure. Irradiation of the film web (9) or the uncured coating layer applied thereon is performed here through the film material (9) when irradiating the press cylinder (2) from the outside. Alternatively, irradiation can be performed through the fused silica material on the outer surface of the press cylinder (2), or through the master film web (8) and the master coating layer applied thereon. Therefore, the master film web (8) and the master coating layer are designed to be transparent to the radiation used, in this case to UV light. Here, we assume that the outer surface of the press roll (2) is made of fused silica. However, any other material is also suitable here in principle, as long as it is transparent to curing radiation (which may not be ultraviolet) emitted from inside the press roll (2). Alternatively, instead of the illumination device (3) that supplies ultraviolet (UV) light, a thermal radiator can be used, for example, if the coating composition (C2a) is a non-radiation-curable coating composition. A possible follow-up to at least partial curing by ultraviolet (UV) illumination is post-exposure with infrared (IR) radiation, for example. At the end of this curing operation by any step (5-i) of the method of the present invention, the film web (9) and the master film web (8) are separated from each other, now with a parting between the structured layer composite (S2C2) and the master film (S1C1).Thus, the coated film web (9) with the desired structure (i.e., composite (S2C2)) is supplied as a finished product to the film web roller (12) and wound onto the roller. Furthermore, if the press roll (2) is illuminated from the outside by an illumination device (3), the coated film web (9) (i.e., composite (S2C2)) with the desired structure can be made opaque by selecting an arrangement that switches between the master film web (8) (i.e., composite (S1C1)) and the film web (9) (i.e., composite (S2C2)). Subsequently, coating of the coating application unit (27) according to step (2i) of the method of the present invention can be performed without operational restrictions on the master film web (8).

[0094] Manufacturing of the complex (S1C1) The composite (S1C1) provided in step (1) of the method of the present invention can be manufactured by various processes, such as lithography methods including nanoimprint lithography, laser lithography, and photolithography. Preferably, the composite (S1C1) is prepared by steps (6) to (9) as defined in more detail below. Therefore, steps (6) to (9) of the method of the present invention are carried out to manufacture a composite (S1C1) that can be used as an embossing mold (e2) for an embossing tool (E2). Figure 2 provides an illustrative description of steps (6) to (9) of the method of the present invention, as will be apparent from the following description of this figure.

[0095] Optional steps (6) to (9) of the present invention for producing the complex (S1C1) According to a preferred embodiment of the present invention, the composite (S1C1) prepared in step (1) of the method, comprising a substrate (S1) and a coating (C1) that is at least partially embossed and at least partially cured, is prepared by transferring the repeating pattern and / or regularly arranged pattern of the embossing mold (e1) of an embossing tool (E1) to a coating composition (C1a), at least partially curing the coating composition, and removing the structured and at least partially cured coating composition (i.e., composite (S1C1)) from the embossing tool. Therefore, the preferred composite (S1C1) prepared in step (1) is, (6) Apply the radiation-curable coating composition (C1a) to at least a portion of the surface of the substrate (S1) to prepare a composite (S1C1a); (7) At least partially embossing a coating composition (C1a) applied to the surface of a substrate (S1) with at least one embossing tool (e1) having at least one embossing mold (e1); (8) At least partially curing a partially embossed coating composition (C1a) that has been applied at least partially to a substrate (S1) (which is in contact with at least one embossing mold (e1) of an embossing tool (E1) for at least a period of partial curing); (9) Remove the composite (S1C1) from the embossing mold (e1) of the embossing tool (E1) to prepare a composite (S1C1) that is at least partially embossed and at least partially cured, or vice versa; It is obtained by doing so.

[0096] Process (6) Step (6) of the method of the present invention is to apply a radiation-curable coating composition (C1a) to at least a portion of the surface of a substrate (S1). The substrate (S1) constitutes a carrier material for the coating composition (C1a) or the coating (C1), respectively. Suitable materials for the substrate (S1) or its surface layer include the same materials that can also be used in the manufacture of the substrate (S2) described above. Hereinafter, the relevant section is explicitly cited. Further layers, for example, preferably an adhesion-promoting layer that transmits ultraviolet light, may be present between (S1) and (C1) of the composite (S1C1). However, it is advantageous for the composite (S1C1) not to have any further layers between (S1) and (C1). The substrate (S1) is preferably a film web, preferably a moving film web or a continuous film web, and more preferably a continuous moving film web. In that case, the substrate (S1) can preferably be used in a roll-to-roll (R2R) embossing apparatus. A suitable material for the substrate (S1) is polyester, and more specifically polyethylene terephthalate (PET). The thickness of the substrate (S1) is preferably 2 μm or more and 5 mm or less. Particularly preferred is a layer thickness of 25 to 1000 μm, and more specifically, 50 to 300 μm.

[0097] The coating composition (C1a) prepared in any step (6) of the method of the present invention is a radiation-curable coating composition, as detailed below. It is advantageous to apply the coating composition (C1a) in step (6) with a dry layer thickness of at least 0.5 μm, preferably at least 1 μm, and more preferably at least 5 μm to 1,000 μm.

[0098] During step (6) (and preferably during steps (7), (8), and (9) of this method), the substrate (S1) is preferably in motion and is therefore a mobile substrate. During step (6), the substrate (S1) is preferably moved by a transport means such as a belt conveyor. Therefore, the corresponding apparatus used to carry out step (6) is preferably equipped with this type of transport means. The corresponding apparatus used to carry out step (6) is preferably further equipped with means for applying the radiation-curable coating composition (C1a) to at least a portion of the surface of the substrate (S1).

[0099] Process (7) Step (7) of the method of the present invention is to at least partially emboss a coating composition (C1a) applied at least partially to the surface of a substrate (S1) with at least one embossing tool having at least one embossing mold (e1) that is optionally pre-wetted with the coating composition (C1a). The embossing mold (e1) may be a polymer embossing mold (e1) or a metal embossing mold (e1), and is preferably a metal embossing mold (e1). Optionally, after manufacturing a first composite (S1C1), this first, so-called previous composite (S1C1) can be used as the embossing mold (e1). This at least partial embossing transfers an embossed structure at least partially to the surface of the coating composition (C1a) applied to the substrate (S1). The term "embossing" has been defined above, and the relevant paragraph is explicitly cited.

[0100] In step (7), it is preferable that the microstructure and / or nanostructure are transferred onto the coating composition (C1a) as an embossed structure with the dimensions such as the structural width and structural height described above. These previously mentioned sections are explicitly referenced here.

[0101] Accordingly, the corresponding apparatus used to carry out step (7) includes means for at least partially embossing the coating composition (C1a) applied at least partially to the surface of the substrate (S1) with at least one embossing tool (E1). A preferred apparatus further comprises means for pressing the embossing mold (e1) as part of the embossing mold (E1) onto the substrate (S1), which is preferably used in the form of a continuous film web, after the application of the radiation-curable coating composition (C1a) to (S1). This means is preferably positioned downstream of the means for applying the radiation-curable coating composition (C1a) when viewed from the transport direction of the substrate (S1).

[0102] The at least partial embossing according to step (7) of the method of the present invention is carried out by an embossing tool (E1). The embossing tool (E1) is preferably an embossing calender equipped with a grid coating mechanism, more preferably a grid roll mechanism. The calender preferably has counter-rotating rolls arranged vertically at a constant interval in the height direction, and the composite (S1C1a) to be given an embossed structure is fed to the rolls and guided into the roll nip to be formed. The width of this nip can be variably adjusted. The grid roll mechanism here preferably comprises a first roll, such as a steel roll, a steel roll covered with a metal layer such as a copper layer or a nickel layer optionally containing a small amount of phosphorus, or a metal roll covered with a nickel sleeve optionally containing a small amount of phosphorus, and a second roll. The first roll (embossing roll), which is part of the embossing tool (E1), includes an embossing mold (e1) having a mirror image of the embossed structure to be embossed on the surface of the composite (S1C1a). Therefore, the image of the embossed mold (e1) corresponds to the image obtained by embossing the coating composition (C2a) in step (3-i) or (2-ii) using the composite (S1C1), which is preferably used as the embossed mold (e2). The second roll functions as an impression roll or a press roll. Embossing is performed at the roll nip portion formed by counter-rotating rolls arranged at a certain distance from each other. The embossing tool (E1) that can be used may also preferably be a conventional press cylinder consisting of a metal roll, such as a steel roll, a copper layer, or a steel roll covered with a metal layer such as a nickel layer optionally containing a small amount of phosphorus, which can convey a mirror image of the embossed structure to be embossed on the surface of the composite (S1C1a) and press it against the composite (S1C1a) for at least partial embossing. The mirror image consists of the surface of a microstructure and / or nanostructure, which consists of microscale and / or nanoscale surface elements, as described in step (1) above. I will explicitly quote the relevant passage here.A mirror image of the structure to be embossed is produced on the embossing tool (E1) according to a method conventionally known to those skilled in the art. Depending on the structure and material, a particular method may be particularly advantageous. The composite to be embossed (S1C1a) is, for example, in the form of a film web at least partially coated with a coating composition (C1a), and is moved in the opposite direction to the first roll by a second roll or pressing roll. Embossing is performed according to step (7) at a roll nip section formed by counter-rotating rolls positioned at a certain distance from each other. The first roll that carries the embossing mold (e1) plays the role of embossing the composite (S1C1a) guided by the second roll opposite to this embossing roll, and the second roll presses the composite (S1C1a) to which the embossed structure is to be formed against the first embossing roll. The embossing tool (E1) is preferably a metal embossing tool, more preferably made of steel, or a steel roll covered with a metal layer such as a copper layer or a nickel layer optionally containing a small amount of phosphorus, or a roll covered with a nickel sleeve optionally containing a small amount of phosphorus. Therefore, the embossing mold (e1) is preferably made of metal, more preferably steel, copper, or nickel, more preferably nickel containing a small amount of phosphorus. However, instead, the embossing mold (e1) may be made of a material such as silicone (i.e., polydimethylsiloxane (PDMS)), or a pre-fabricated composite (S1C1) may be used as the embossing mold (e1), and the pattern originally created in the first embossing process may be multiplied onto the first composite (S1C1). Furthermore, a roll coated with at least one type of plastic may also be used. Moreover, the embossing tool (E1) may have a structured coating such as a UV coating as the embossing mold (e1).

[0103] If necessary, step (7) can be carried out at a high temperature, such as 30°C to 100°C or 80°C. In this case, the composite (S1C1a) first passes through a heating roll mechanism and then optionally is irradiated with infrared light before the actual embossing procedure, i.e., hardening while in contact with the embossing tool (E1), takes place. After embossing and hardening, the embossed composite (S1C1) is optionally cooled by passing through a cooling roll mechanism. Alternatively, it is possible to harden while cooling. In this case, the composite (S1C1a) for embossing first passes through a cooling roll mechanism before the actual embossing procedure described above takes place. It is also possible to heat or cool the embossing tool (E2) instead of using a separate heating or hardening roll mechanism.

[0104] Process (8) In step (8) of the method of the present invention, a coating composition (C1a) that is at least partially applied to a substrate (S1) is at least partially cured. The substrate (S1) is in contact with at least one embossing mold (e1) of an embossing tool (E1) throughout the at least partially curing period.

[0105] Steps (7) and (8) are preferably performed simultaneously. In this case, the curing in step (8) is preferably performed in place during the execution of step (7).

[0106] Therefore, the corresponding apparatus used to carry out step (8) preferably comprises at least one radiation source for irradiating the radiation-curable coating composition (C1a) with curing radiation, preferably UV radiation.

[0107] Specific examples of suitable radiation sources for radioactive curing were previously explained in relation to the curing of coating composition (C2a). The relevant section is explicitly cited below.

[0108] The curing in step (8) is preferably carried out by irradiation through the substrate (S1). In this case, it is advantageous that the permeability of the substrate (S1) to the radiation used is in harmony with the permeability of at least one photopolymerization initiator contained in the coating composition (C1a). Therefore, for example, the PET material used as the substrate (S1), and by extension the PET film, is permeable to radiation having a wavelength of less than 400 nm. Examples of photopolymerization initiators that generate radicals with such radiation include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphine, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0109] Process (9) Step (9) of the method of the present invention is to remove the composite (S1C1) from the embossing tool (E1) thereby producing a desired product, namely a composite (S1C1) that can be used as an embossing mold (e2) and is composed of a substrate (S1) and a coating (C1) that is at least partially embossed and at least partially cured.

[0110] Optionally, the composite (S1C1) or master film can be post-exposed with a suitable radiation source, such as a UVA lamp, after separation from the embossing mold (e1), thereby increasing or maximizing double bond conversions on the surface of the coating (C1) of the composite (S1C1) and decreasing or minimizing covalent crosslinking with the coating composition (C2a). Any of the aforementioned radiation sources are suitable here; please refer clearly to those preceding paragraphs.

[0111] The surface of the composite (S1C1) of the coating (C1) which is at least partially cured and at least partially embossed is preferably a microstructured and / or nanostructured surface.

[0112] Figure 2 schematically shows a side view of an apparatus that can be used to carry out steps (6) to (9) of the method of the present invention for producing a composite (S1C1) that is advantageously used as an embossing mold (e2), i.e., for producing a master film, and is used to illustrate the method of the present invention in relation to steps (6) to (9). In this apparatus, an embossing tool (E1) can be used to transfer structures such as microstructures and / or nanostructures onto a substrate (S1) coated with (C1a), and after at least partial curing, a composite (S1C1) - referred to as a master film web (8) in Figure 2 - that can be used as a master film. This composite can be used as the embossing mold (e2) described above in the method described in relation to Figure 1.

[0113] The master transfer apparatus (30) shown in Figure 2 operates according to a transfer principle in which a desired negative structure is directly embossed onto an uncured coating layer applied to a master film web (8b) corresponding to a composite (S1C1a) from a structured press cylinder or press roll (here, a master press cylinder (17)). This coating layer is cured, at least partially, along with the structure applied thereon. The curing is performed on-site by an illumination unit (3) to obtain a master film web (8) (corresponding to the composite (S1C1)). In this method, the film web (8a) used as the substrate (S1) is drawn from a film web roller (18) containing only the carrier material, in other words, a pure film without the master coating (C1a) applied, guided through various deflection roller systems and web tensioning systems, and introduced into the embossing area (1) of the apparatus. There, the film web (8a) travels from a coating application means (27) which is provided with an uncured master coating layer (corresponding to the coating composition (C1a)) to the press region between the pressing roll (4) and the master press cylinder (17). This application corresponds to step (6) of the method of the present invention. In the embossed region (1) on a portion of the outer surface of the master press cylinder (17) where the master film web (8b), which has an uncured master coating layer (C1a), travels, microscale and / or nanoscale surface elements of the microstructured and / or nanostructured surface embossed on the outer surface of the master press cylinder (17) are introduced and transferred as a negative image into the master coating layer of the master film web (8b). This corresponds to step (7) of the method of the present invention. The master film web (8b) with the uncured coating composition (C1a) is then cured at least partially according to step (8) of the method of the present invention. Curing is performed in place here by irradiation with the lighting unit (3), for example by UV radiation from a unit formed with a UV-LED.Next, the obtained master film (8), in other words, the composite (S1C1), is removed from the outer surface of the master press cylinder (17) according to step (9) of the method of the present invention, and the thus completed master film web (8) is wound onto a film web roller (19). The film web roller (19) contains the completed master film web (8), which is coated with a master coating layer and embossed with a microstructure and / or nanostructure negative image. After removal, this film web roller (19) can be used as the first film web roller (6) of the transfer device (10) shown in Figure 1 or other transfer devices operating on the same principle.

[0114] Coating compositions (C1a) and (C2a) used in the present invention Coating composition (C1a) The coating composition (C1a) is a radiation-curable coating composition. Here, the terms "radiation-curable" and "radiation-curable" have the same meaning. The term "radiation-curable" preferably refers to the radical polymerization of a polymerizable compound by electromagnetic radiation and / or particulate radiation. Specific examples of radiation include visible light to (N)IR light in the wavelength range of λ=400~1200nm, preferably 700~900nm, and / or ultraviolet (UV) light in the wavelength range of λ=100~400nm, preferably λ=200~400nm, more preferably λ=250~400nm, and / or electron beams in the range of 150~300keV, more preferably at least 80 mJ / cm². 2 Preferably, the concentration is 80-3000 mJ / cm². 2 Some are irradiated with radiation doses. Radiation curing is carried out using ultraviolet (UV) light in particular. The coating composition (C1a) can be cured by using an appropriate radiation source. Therefore, (C1a) is preferably an ultraviolet (UV) curable coating composition.

[0115] The coating composition (C1a) is (a) 5 to 45% by mass of at least one crosslinkable polymer and / or oligomer, (b) at least one reactive diluent in an amount of 40 to 95% by mass, (c) At least one photopolymerization initiator in 0.01 to 15% by mass, (d) At least one additive in 0-5% by mass It is preferable that it contains [the specified ingredient].

[0116] Here, (i) the total amounts of components (a), (b), (c), and (d) are based on the total mass of the coating composition (C1a), and (ii) the total amount of all components present in the coating composition (C1a) is 100% by mass. Here, at least one crosslinkable polymer and / or oligomer (a) comprises at least one silicone (meth)acrylate oligomer in a total amount of at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass, and very preferably 100% by mass, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a).

[0117] The coating composition (C1a) comprises at least one crosslinkable polymer and / or oligomer in a total amount of 5 to 45% by mass, preferably 8 to 40% by mass, and more preferably 9 to 35% by mass, based on the total mass of the coating composition (C1a), wherein at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass, and very preferably 100% by mass, of the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a), at least one silicone (meth)acrylate oligomer.

[0118] The term "oligomer" refers to a relatively low molecular weight compound consisting of a small number of monomer units, typically less than 2 to 10. These monomer units may be structurally identical or similar, or they may be distinct from one another. Oligomer compounds are usually liquid at room temperature (23°C) and atmospheric pressure, and their dynamic viscosity, as measured according to DIN EN ISO 2555 (Brookfield method), is preferably less than 500 Pa*s, more preferably less than 200 Pa*s, at 23°C. The term "crosslinkable" refers to a polymer or oligomer having, on average, at least one, preferably at least two, retaining unsaturated groups capable of forming free radicals for crosslinking reactions. Crosslinkable oligomers and / or polymer compounds are preferably soluble in one or more reactive diluents.

[0119] The preparation of silicone (meth)acrylate oligomers or polymers useful in the present invention can typically be carried out by a condensation reaction between (meth)acrylic acid and a hydroxy-functional silicone (e.g., α,ω-polydimethylsilicone diol). Due to their silicone backbone, silicone acrylates improve the elasticity and elongation of structured surfaces, but tend to impair tensile strength and robustness. Due to their low surface energy, highly functional silicone (meth)acrylates are often used. Specific examples of useful silicone (meth)acrylates include those marketed under the trade name SARTOMER (e.g., SARTOMER CN9800) by Sartomer Co., those marketed under the trade name EBECRYL (e.g., EBECRYL350, EBECRYL1360) by UCB Radcure Inc., and methacrylate salts marketed under the trade name X-22 (e.g., X-22-164, X-22-164A) by Shin-Etsu Silicones Europe BV.

[0120] The coating composition (C1a) particularly preferably contains, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a), at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass, and very preferably 100% by mass, at least one type of silicone (meth)acrylate oligomer, preferably strictly one type of silicone (meth)acrylate oligomer, more preferably strictly one type of silicone (meth)acrylate oligomer having an average of 2 to 3 unsaturated groups.

[0121] Following the silicone (meth)acrylate, other crosslinkable polymers and / or oligomers optionally present in the coating composition (C1a) can be selected from (meth)acrylic oligomers or polymer compounds, urethane (meth)acrylate, vinyl (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, poly(meth)acrylate, polyether (meth)acrylate, olefin (meth)acrylate, (meth)acrylic oil, and mixtures thereof, with urethane (meth)acrylate oligomers being a preferred example. The coating composition (C1a) contains, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a), in an amount of 0 to 75% by mass, preferably 0 to 50% by mass, more preferably 0 to 10% by mass, and very preferably 0% by mass of the other crosslinkable polymers and / or oligomers. In other words, it is highly preferable that the coating composition (C1a) does not contain any other crosslinkable polymers and / or oligomers after the at least one silicone (meth)acrylate.

[0122] Urethane (meth)acrylates can be obtained, for example, by the reaction of polyisocyanate with a hydroxyalkyl (meth)acrylate and optionally with a chain extender such as a diol, polyol, diamine, polyamine, dithiol, or polythiol. Urethane (meth)acrylates that are dispersible in water without the addition of emulsifiers further possess ionic and / or nonionic hydrophilic groups, which are introduced into the urethane by synthetic components such as hydroxycarboxylic acids. Such urethane (meth)acrylates essentially consist of the following synthetic components: (a) at least one organoliphatic, aromatic, or alicyclic di- or polyisocyanate, (b) at least one compound having at least one isocyanate-reactive group, preferably a monomer having a hydroxyl group, and having at least one radically polymerizable unsaturated group, (c) Optionally, at least one compound having at least two isocyanate-reactive groups, such as a polyhydric alcohol. Includes.

[0123] The number-average molar mass Mn of urethane (meth)acrylate is preferably 200 to 20,000, more particularly 500 to 10,000, and very preferably 600 to 3,000 g / mol (determined by gel permeation chromatography with tetrahydrofuran as the eluent and polystyrene as the standard). The urethane (meth)acrylate contains preferably 1 to 5, more preferably 2 to 4 moles of (meth)acrylic groups per 1,000 g of urethane (meth)acrylate.

[0124] Epoxide (meth)acrylates can be obtained by reacting an epoxide with (meth)acrylic acid. Specific examples of epoxides that can be considered include epoxides of epoxide-modified olefins, aromatic glycidyl ethers, or aliphatic glycidyl ethers, preferably aromatic or aliphatic glycidyl ethers. Specific examples of possible epoxide-modified olefins include ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, vinyl oxirane, styrene oxide, or epichlorohydrin. Ethylene oxide, propylene oxide, isobutylene oxide, vinyl oxirane, styrene oxide, or epichlorohydrin are preferred, with ethylene oxide, propylene oxide, or epichlorohydrin being particularly preferred, and ethylene oxide and epichlorohydrin being especially preferred. Examples of aromatic glycidyl ethers include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol B diglycidyl ether, bisphenol S diglycidyl ether, hydroquinone diglycidyl ether, alkylation products of phenol / dicyclopentadiene, such as 2,5-bis[(2,3-epoxypropoxy)phenyl]octahydro-4,7-methano-5H-indene, tris[4-(2,3-epoxypropoxy)phenyl]methane isomers, phenolic epoxy novolacs, and cresol-based epoxy novolacs. Aliphatic glycidyl ethers include, for example, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,1,2,2-tetrakis[4-(2,3-epoxypropoxy)phenyl]ethane, and diglycidyl ethers of polypropylene glycol (α,ω-bis(2,3-epoxypropoxy)poly(oxypropylene) (and hydrogenated bisphenol A (2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane)).The epoxide (meth)acrylate preferably has a number-average molar mass Mn of 200 to 20,000, more preferably 200 to 10,000 g / mol, and very preferably 250 to 3,000 g / mol, and the amount of (meth)acrylic groups is preferably 1 to 5, more preferably 2 to 4 per 1,000 g of epoxide (meth)acrylate (determined by gel permeation chromatography using polystyrene standards and tetrahydrofuran as the solvent).

[0125] (Meth)acrylated poly(meth)acrylates are corresponding esters of α,β-ethylenically unsaturated carboxylic acids, preferably (meth)acrylic acid, and more preferably acrylic acid, with polyacrylate polyols, and can be obtained by esterification of poly(meth)acrylate polyols with (meth)acrylic acid.

[0126] Carbonate (meth)acrylates can have various functional groups. The number-average molecular weight Mn of carbonate (meth)acrylates is preferably less than 3000 g / mol, more preferably less than 1500 g / mol, and very preferably less than 800 g / mol (determined by gel permeation chromatography using polystyrene as the standard and tetrahydrofuran as the eluent). Carbonate (meth)acrylates can be obtained by a simple method, such as described in EP0092269A1, which involves transesterifying a carbonate ester with a polyhydric alcohol, preferably a dihydric alcohol (diol, e.g., hexanediol), followed by esterifying the free OH group with (meth)acrylic acid or transesterifying it with a (meth)acrylic ester. They can also be obtained by reacting phosgene, urea derivatives with polyhydric alcohols, dihydric alcohols, etc. Furthermore, meth(acrylates) of polycarbonate polyols, such as reaction products of one of the aforementioned diols or polyols with a carbonate ester, and hydroxyl-containing (meth)acrylates are also possible. Specific examples of suitable carbonate esters include ethylene carbonate, 1,2- or 1,3-propylene carbonate, dimethyl carbonate, diethyl carbonate, or dibutyl carbonate. Specific examples of suitable hydroxyl-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, glyceryl mono- and di(meth)acrylate, trimethylolpropane mono- and di(meth)acrylate, and pentaerythritol mono-, di- and tri(meth)acrylate. Regarding carbonate (meth)acrylates, aliphatic carbonate (meth)acrylates should be used preferentially.

[0127] The coating composition (C1a) is particularly preferably composed of at least one crosslinkable polymer and / or oligomer in a total amount of 5 to 45% by mass, preferably 8 to 40% by mass, and more preferably 9 to 35% by mass, based on the total mass of the coating composition (C1a). The at least one crosslinkable polymer and / or oligomer is selected from the group consisting of i) at least one silicone (meth)acrylate oligomer, preferably strictly one silicone (meth)acrylate oligomer, very preferably strictly one silicone (meth)acrylate oligomer having an average of 2 to 3 unsaturated groups, and ii) other crosslinkable polymers and / or oligomers selected from (meth)acrylic oligomers or polymer compounds, urethane (meth)acrylate, vinyl (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, poly(meth)acrylate, polyether (meth)acrylate, olefin (meth)acrylate, (meth)acrylic oil, and mixtures thereof, preferably urethane (meth)acrylate oligomers.

[0128] Therefore, the coating composition (C1a) contains, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a), at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass of at least one type of silicone (meth)acrylate oligomer, in particular strictly one type of silicone (meth)acrylate oligomer having an average of 2 to 3 unsaturated groups, and based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a), It is particularly preferable to include less than 75% by mass, preferably less than 50% by mass, and more preferably less than 10% by mass, other crosslinkable polymers and / or oligomers selected from (meth)acrylate oligomers or polymer compounds, urethane (meth)acrylate, vinyl (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, poly (meth)acrylate, polyether (meth)acrylate, olefin (meth)acrylate, (meth)acrylate oil, and mixtures thereof, preferably urethane (meth)acrylate oligomers.

[0129] The coating composition (C1a) contains at least one reactive diluent in an amount of 40-85% or 95% by mass, preferably 50-95% or 85% or 83% by mass, and more preferably 55-83% by mass, based on the total mass of the coating composition (C1a). A suitable reactive diluent is polymerizable with the above polymer and / or oligomer compound and can form a master substrate having a copolymerized elastomer network structure of the cured master coating (C1). The term "reactive diluent" refers to a low-mass monomer that can participate in the polymerization reaction to form a polymer. The weight-average molecular weight Mw of such monomer compounds is preferably less than 1000 g / mol, more preferably less than 750 g / mol, as measured by GPC.

[0130] Preferably, the reactive diluent is a free radical polymerizable monomer, and includes ethylenically unsaturated monomers such as (meth)acrylates, styrene, vinyl acetate, and mixtures thereof. Suitable monomers include (meth)acryloyl functional monomers, such as alkyl (meth)acrylates, aryloxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, N-vinyl compounds, and combinations thereof. Suitable monomers are known to those skilled in the art and are listed, for example, in WO2012 / 006207A1.

[0131] Particularly preferred coating compositions (C1a) include, as a reactive diluent, at least one polyfunctional ethylenically unsaturated monomer, i.e., a compound having at least two polymerizable double bonds in one molecule, in order to increase the crosslinking density. Representative examples of such polyfunctional monomers are described, for example, in WO2012 / 006207A1. Particularly preferred reactive diluents are selected from compounds having at least two, preferably at least three, more precisely three, structural units of hexanediol diacrylate and / or general formula (I), wherein the structural units may be different from each other or at least partially identical.

[0132] [ka]

[0133] During the ceremony, Radical R 1 These are, independently of each other, a C2-C8 alkylene group, very preferably a C2 alkylene group. Radical R 2 These are independently H or methyl, The symbol m is an integer in the range of 1 to 15, very preferably 1 to 4 or 2 to 4, independently of each other, except that in at least one of the structural units of formula (I), the symbol m is at least 2, preferably strictly 2. Particularly preferred is that the compound has three identical structural units of general formula (I) and m is 2.

[0134] All structural units of general formula (I) are bonded to the skeleton of the reactive diluent via the symbol [Chemical formula] It is preferably carried out through the bonding of the oxygen atom of the radical -[O-R 1 m - to the carbon atom of the skeleton of the component. Therefore, at least two structural units of general formula (I) are present in a single component, namely the reactive diluent b). Suitable skeletons are selected, for example, from neopentyl glycol, glycerin, trimethylolpropane, trimethylolethane or pentaerythritol.

[0135] The total number of ether groups of the general formula "-O-R 1 -" of the compound is preferably in the range of 4 to 18, more preferably in the range of 5 to 15, and very preferably in the range of 6 to 12. The compound preferably has a number average molecular weight (Mn) in the range of 300 to 2000 g / mol, more preferably 400 to 1000 g / mol.

[0136] The compound preferably has exactly three structural units of formula (I). In that case, the compound has exactly three functional (meth)acrylic groups. Alternatively, each structural unit of formula (I) can also be present more than three times as part of the compound. In that case, for example, the compound may have more than three functional (meth)acrylic groups, such as 4, 5 or 6 (meth)acrylic groups.

[0137] The radical R 1 are each independently of the others a C2-C8 alkylene group, preferably a C2-C6 alkylene group, more preferably a C2-C4 alkylene group, very preferably, each independently of the others, an ethylene group and / or a propylene group, particularly preferably an ethylene group. In particular, the radical R 1 ​All of these are ethylene. In each case, the appropriate propylene group is the radical R having the structure CH2-CH2-CH2-, -CH(CH3)-CH2-, or CH2-CH(CH3)-. 1 However, in all cases, the propylene structure CH2-CH2-CH2- is particularly preferred.

[0138] The symbol m is an integer in the range of 1 to 15, independently of each other. The compound has at least two, preferably at least three, structural units of formula (I), and in at least one of the structural units of formula (I), the symbol m is at least 2. Therefore, the compound has a total of at least three, preferably at least four, general formula "OR 1 It contains the ether group "-".

[0139] Preferably, the compound contains at least 5, more preferably at least 6, of the general formula "OR 1 The compound has an ether group of the general formula "OR 1 The number of ether groups is preferably in the range of 4 to 18, more preferably in the range of 5 to 15, and very preferably in the range of 6 to 12.

[0140] The ether segment present in the structural unit of formula (I) of the aforementioned compound -[OR 1 ] m The proportion is, in total, at least 35% by mass, more preferably at least 38% by mass, very preferably at least 40% by mass, more preferably even more at least 42% by mass, and more particularly at least 45% by mass (in each case, based on the total mass of the compound).

[0141] The number-average molecular mass (Mn) of the compound, as determined by GPC, is preferably in the range of 300 to 2000 g / mol, more preferably 350 to 1500 g / mol, and more particularly 400 to 1000 g / mol.

[0142] Particularly preferred polyfunctional ethylenically unsaturated monomers are at least one compound of general formula (IIa) and / or (IIb).

[0143] [ka]

[0144] In the formula, in each case, independently, R 1 and R 2 , and m has the definitions described above in relation to the structural unit (I), including the preferred embodiments described above. R 3 These are H, C1-C8 alkyl, OH, or OC. 1~8 Alkyl, more preferably C1-C4 alkyl, OH or OC 1~4 It is alkyl, very preferably C1-C4 alkyl or OH, or R 3 is radical-[OR 1 ] m -OC(=O)-C(R 2 )=CH2(wherein, R 1 , R 2 And m has the definitions described above in relation to a structural unit (I), including its preferred embodiment described above.

[0145] Particularly preferred is the use of a polyfunctional ethylenically unsaturated monomer as a reactive diluent for at least one compound of general formula (IIa), in which, Radical R 1 These are, independently of each other, C2-C8 alkylene groups, Radical R 2 These are independently H or methyl, The symbol m is, in each case, an integer variable in the range of 1 to 15, preferably 1 to 10, more preferably 1 to 8 or 2 to 8, very preferably 1 to 6 or 2 to 6, and more particularly 1 to 4 or 2 to 4, wherein in at least one, preferably all, of the structural units of formula (I), m is at least 2. R 3 These are C1-C8 alkyl, OH, or OC. 1~8 Alkyl, more preferably C1-C4 alkyl, OH, or OC 1~4 Alkyl, very preferably C1-C4 alkyl or OH.

[0146] Particularly preferred compounds having at least two structural units of general formula (I) are (meth)acrylates obtained by alkoxyling neopentyl glycol, trimethylolpropane, trimethylolethane, or pentaerythritol a total of 4 to 20 times or 4 to 12 times (e.g., ethoxylation, propoxylation, or ethoxylation and propoxylation), more specifically, (meth)acrylates of neopentyl glycol, trimethylolpropane, trimethylolethane, or pentaerythritol that are exclusively ethoxylated. Most preferred are the corresponding (meth)acrylates derived from alkoxylated trimethylolpropane. These products are commercially available and sold under names such as Sartomer® SR499 and Sartomer® SR502, and Sartomer® SR415 and Sartomer® SR9035, and Sartomer® SR501.

[0147] The coating composition (C1a) comprises, based on the total mass of the coating composition (C1a), at least one reactive diluent in a total amount of 40 to 95% by mass, preferably 50 to 85% by mass, more preferably 55 to 83% by mass, preferably hexanediol diacrylate and / or a (meth)acrylate derived from 6-fold ethoxylated trimethylolpropane.

[0148] The coating composition (C1a) contains at least one photopolymerization initiator in a total amount of 0.01 to 15% by mass, preferably 0.5 to 10% by mass, and more preferably 1 to 8% by mass, based on the total mass of the coating composition (C1a), in order to cure with visible light to (N)IR- and / or UV light. This photopolymerization initiator is decomposed into radicals by light of the irradiated wavelength, thereby initiating radical polymerization. In the case of curing by electron radiation, the presence of such a photopolymerization initiator is not required. It is preferable that the coating composition (C1a) contains at least one photopolymerization initiator that can be decomposed into radicals by light of the irradiated wavelength and initiate radical polymerization.

[0149] Photopolymerization initiators, such as UV photopolymerization initiators, are known to those skilled in the art. Specific examples of those intended include phosphine oxides such as (alkyl)-benzoylphenylphosphine oxide, benzophenone, α-hydroxyalkylaryl ketone, thioxanthone, anthraquinone, acetophenone, benzoin and benzoin ether, ketal, imidazole or phenylglyoxylic acid, and mixtures thereof.

[0150] Examples of phosphine oxides include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphine, phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide, or bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide. Examples of benzophenones include 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. Examples of α-hydroxyalkylaryl ketones include polymers containing copolymers of 1-benzoylcyclohexane-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 2-hydroxy-2-methyl-1-(4-isopropen-2-ylphenyl)propan-1-one. Examples of xanthones and thioxanthones include 10-thioxanthenone, thioxanthen-9-one, xanthen-9-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dichlorothioxanthone, or chloroxanthenone.Examples of anthraquinones include β-methylanthraquinone, tert-butylanthraquinone, anthraquinone carboxylic acid esters, benz[de]anthracene-7-one, benz[a]anthracene-7,12-dione, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, or 2-amylanthraquinone. Examples of acetophenones include acetophenone, acetonaphthoquinone, valerophenone, hexanophenone, α-phenylbutyrophenone, p-morpholinopropiphenone, dibenzosverone, 4-morpholinobenzophenone, p-diacetylbenzene, 4'-methoxyacetophenone, α-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indanone, 1,3,4-triacetylbenzene, 1- Examples of benzoin and benzoin ethers include acetonaphthone, 2-acetonaphthone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophen, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-2-one, or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one. Examples of benzoin and benzoin ethers include 4-morpholinodeoxybenzoin, benzoin, benzoin isobutyl ether, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin isopropyl ether, or 7H-benzoin methyl ether. Examples of ketals include benzyl ketals such as acetophenone dimethyl ketal, 2,2-diethoxyacetophenone, or benzyl dimethyl ketal.Typical mixtures include, for example, 2-hydroxy-2-methyl-1-phenylpropan-2-one and 1-hydroxycyclohexyl phenyl ketone, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone and 1-hydroxycyclohexyl phenyl ketone, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide and 1-hydroxycyclohexyl phenyl ketone, diphenyl(2,4,6-trimethylbenzoyl)phosphine 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 diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.

[0151] Particularly preferred photopolymerization initiators include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphine, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, 1-hydroxycyclohexylphenyl ketone, benzophenone, 1-benzoylcyclohexane-1-ol, 2-hydroxy-2,2-dimethylacetophenone, and 2,2-dimethoxy-2-phenylacetophenone, as well as mixtures thereof. Commercially available photopolymerization initiators include, for example, Irgacure® 184, Irgacure® 500, Irgacure® TPO, Irgacure® TPO-L, and Lucirin® TPO, as well as Darocure® 1173, all available from IGM Resins BV.

[0152] The coating composition (C1a) may optionally further contain at least one additive. The concept of additives is known to those skilled in the art, for example, from Roempp Lexikon, "Lacke und Druckfarben," Thieme Verlag, 1998, p. 13. A preferred additive to be used is at least one rheological additive. This term is also known to those skilled in the art, for example, from Roempp Lexikon, "Lacke und Druckfarben," Thieme Verlag, 1998, p. 497. Here, the terms "rheological additive," "rheological additive," and "rheological auxiliary" are synonymous and interchangeable. Preferred additives are selected from the group consisting of flow control agents, surfactants (such as surfactants, wetting agents, and dispersants), as well as thickeners, thixotropic agents, plasticizers, lubricating additives, and anti-blocking additives, and mixtures thereof. These terms are also known to those skilled in the art, for example, from Roempp Lexikon, "Lacke und Druckfarben," Thieme Verlag, 1998. Flow control agents are components that reduce the viscosity and / or surface tension of the coating material, forming a uniformly flowing film. Wetting agents and dispersants are components that reduce surface tension, generally interfacial tension. Lubricating additives and anti-blocking additives are components that reduce mutual sticking (blocking).

[0153] Specific examples of commercially available additives include products such as Efka® SL3259, Byk® 377, Tego® Rad2500, Tego® Rad2800, Byk® 394, Byk-SILCLEAN3710, Silixan® A250, Novec FC4430, and Novec FC4432. The preferred total amount of at least one additive is, for example, 0.01 to 5% by mass, 0.2, or 0.5 to 3% by mass, based on the total mass of the coating composition (C1a).

[0154] In relation to the present invention, additives such as surface agents may include silicone (meth)acrylate. Such silicone (meth)acrylate-containing additives should not be compared to crosslinkable silicone (meth)acrylate oligomers used as crosslinkable polymers and / or oligomers. This is because, at a minimum, the total amount contained in the coating composition is small in the case of additives, and the chemical functionality or reactivity of silicone (meth)acrylate additives differs, resulting in entirely different technical effects on the coating composition. Silicone (meth)acrylate-containing additives, for example, only affect the surface energy of the coating composition and contribute only slightly to the backbone of the (co)polymer network formed by the crosslinkable polymer and / or oligomer or reactive diluent. Unlike silicone (meth)acrylate-containing additives, silicone (meth)acrylate oligomers used as crosslinkable polymers and / or oligomers retain unsaturated groups that can form free radicals for the crosslinking reaction and, together with the reactive diluent, form the copolymer elastomer network of the cured master coating (C1).

[0155] It is particularly preferable that components (a), (b), (c), and (d) contained in the coating composition (C1a) are all different from each other and not identical.

[0156] A particularly suitable master coating (C1a) is one with the following components (each mass % is based on the total mass of the coating composition (C1a)), namely: — 9-35% by mass of strictly one type of silicone (meth)acrylate oligomer having an average of 2 unsaturated groups, — 55-83% by mass of (meth)acrylates derived from hexanediol diacrylate and / or 6x ethoxylated trimethylolpropane (i.e., compounds having three structural units of general formula (I)), — 1 to 10% by mass of ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate and / or 1-benzoylcyclohexane-1-ol, and — Lubrication and anti-blocking additives in 0 or 0.5-3% by mass Includes.

[0157] The double bond conversion rate of the at least partially cured coating (C1) obtained from (C1a) is preferably at least 70%, more preferably at least 75%, still more preferably at least 80%, very preferably at least 85%, and most especially preferably at least 90%.

[0158] The coating composition (C1a) may include at least one additional component (e) different from components (a) to (d), such as fillers, pigments, thermally activated initiators such as potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, azobisisobutyronitrile, cyclohexylsulfonylacetyl peroxide, diisopropyl parkorate, tert-butyl peroctoate or benzopinacol, cumenehydroperoxide, dicumyl peroxide, tert-butyl perbenzoate, silylated pinacol, alkoxyamines, and organic solvents, and even stabilizers. However, it is preferable that the coating composition (C1a) does not contain organic solvents. The coating composition (C1a) may contain at least one component (e) in a total amount of 0 to 10% by mass, preferably 0 to 5% by mass, and more preferably 0 to 1% by mass, based on the total mass of the coating composition (C1a).

[0159] The coating composition (C1a) may be a solvent-based coating composition or a solid-based coating composition. To promote rapid curing and prevent the generation of large amounts of evaporated solvent during curing, the coating composition (C1a) is preferably a solid coating composition. Therefore, it is advantageous for the coating composition (C1a) to contain a total amount of solvent less than 10% by mass, preferably less than 5% by mass, more preferably less than 1% by mass, and very preferably 0% by mass, based on the total mass of the coating composition (C1a), i.e., very preferably, it is solvent-free. Therefore, it is advantageous for the coating composition (C1a) to have a solid content of 75 to 100% by mass, based on the total mass of the coating composition (C1a), when measured at 125°C and 60 minutes according to DIN EN ISO3251:2008-06. Furthermore, it is advantageous to include compounds (a), (b), (c) and optionally (d) in a total amount of 90-100% by mass, preferably 95-100% by mass, and more preferably 99-100% by mass, based on the total mass of the coating composition (C1a). Most preferably, the coating composition (C1a) consists of compounds (a), (b), (c), and optionally (d).

[0160] The coating composition (C1a) is preferably thiol-free, and more preferably trimethylolpropanetris (3-mercaptopropionate).

[0161] Coating composition (C2a) Any type of coating composition can be used as the coating composition (C2a) in step (2-i) or (2-ii) of the method of the present invention. The coating composition (C2a) can be a physically drying type, a thermosetting type, a chemical curing type, and / or a radiation curing type coating composition (C2a). Preferably, the coating composition (C2a) is a chemically curable, thermosetting, and / or radiation curing coating composition, and more preferably a radiation curing coating composition. Therefore, it is preferable that at least partial curing by step (4) is carried out by radiation curing means. The coating composition (C2a) may be the same as the coating composition (C1a). However, it is preferable that (C2a) is different from (C1a). It is preferable that (C2a) is constructed from components (a) to (e) that are not the same as but similar to components (a) to (e) used in the preparation of (C1a), but it is not necessary to apply the quantitative conditions for (C1a) to (C2a).

[0162] Here, physical drying preferably means the simple evaporation of the solvent(s) for forming the coating (C2). Here, thermal curing preferably involves a curing mechanism that inevitably occurs at temperatures above room temperature (above 23°C). This may be, for example, the formation of radicals or ions, preferably the formation of radicals from an initiator that decomposes at high temperatures, and thus may initiate radical polymerization or ionic polymerization. Specific examples of such thermally activatable initiators include those with a half-life of less than 100 hours at 80°C. Chemical curing preferably refers to the reaction of at least two different, mutually complementary reactive functional groups, such as polycondensation, like the reaction of an OH group with a -COOH group, or polyaddition (which is the reaction of an NCO group with an -OH or amino group).

[0163] If the coating composition (C2a) is a physically drying, thermosetting, and / or chemically curable coating composition, it is prepared using at least one conventional polymer known to those skilled in the art as a binder. In the case of a thermally or chemically curable coating composition, the binder preferably has a crosslinkable functional group. Any conventional crosslinkable functional group known to those skilled in the art is suitable in this context. More specifically, the crosslinkable functional group is selected from the group consisting of hydroxyl groups, amino groups, carboxylic acid groups, thiol groups, isocyanates, polyisocyanates, and epoxides. The polymer is preferably exothermic or endothermic curing or crosslinking, and is preferably curable or crosslinkable in a temperature range of -20°C to 250°C, or 18°C ​​to 200°C. Particularly suitable polymers are at least one polymer selected from the group consisting of polyurethane, polyether, polyester, polyamide, polyurea, polyvinyl chloride, polystyrene, polycarbonate, poly(meth)acrylate, epoxy resin, phenol-formaldehyde resin, and melamine-formaldehyde resin. These polymers may be particularly OH functional. In that case, they may be included in the general term "polyol". Such polyols may be, for example, poly(meth)acrylate polyols, polyester polyols, polyether polyols, polyurethane polyols, polyurea polyols, polyester-polyacrylate polyols, polyurethane-polyacrylate polyions, polyurethane-modified alkyd resins, fatty acid-modified polyester-polyurethane polyols, and further, mixtures of the aforementioned polyols. Preferred polyols are poly(meth)acrylate polyols, polyester polyols, and polyether polyols.

[0164] Here, it is also possible to use at least one polymer that cures with the involvement of isocyanate groups and / or oligomerized isocyanate groups, very preferably at least one corresponding polyurethane and / or at least one corresponding polyurea (for example, what is called a "polyaspartic acid binder"). The polyaspartic acid binder is a component converted by the reaction of an amino-functional compound, particularly a secondary amine, with an isocyanate. When at least one polyurethane is used, a particularly preferred polyurethane resin is one that can be prepared by a polyaddition reaction between a hydroxyl-containing component such as a polyol and at least one polyisocyanate (aromatic and aliphatic isocyanates, di-, tri-, and / or polyisocyanates). Usually, it is necessary to stoichiometrically convert the OH group in the polyol and the NCO group in the polyisocyanate. However, since the polyisocyanate can be added to the polyol component in an amount that results in "excessive crosslinking" or "insufficient crosslinking," it is also possible to change the stoichiometric ratio used. When using epoxy resins, i.e., epoxide resins, it is preferable that the epoxide resin is prepared from a glycidyl ether having terminal epoxide groups and a hydroxyl group as a functional group within the molecule. These are preferably reaction products of bisphenol A and epichlorohydrin, and / or bisphenol F and epichlorohydrin, and mixtures thereof, and can be used in the presence of a reactive diluent. Curing or crosslinking of such epoxide resins can usually be carried out by polymerization of the epoxide groups of the epoxide ring, or by polyaddition reactions in which other reactive compounds as curing agents are stoichiometrically added to the epoxide groups. In the latter case, the presence of 1 active hydrogen equivalent per epoxide group is required accordingly (i.e., 1 active hydrogen equivalent is required for curing per epoxide equivalent). Alternatively, curing or crosslinking of epoxide resins can be carried out by polycondensation of epoxide groups via hydroxyl groups. Specific examples of suitable curing agents include polyamines, particularly (hetero)aliphatic, (hetero)aromatic and (hetero)alicyclic polyamines, polyamidoamines, polyaminoamides, and polycarboxylic acids and their anhydrides.

[0165] The concept of "radiation hardening" has already been discussed above in relation to the coating composition (C1a), so please refer to the relevant section.

[0166] The coating composition (C2a) can be cured by the use of a radiation source, preferably by ultraviolet (UV) irradiation. Therefore, (C2a) is preferably an ultraviolet (UV) irradiation curable coating composition.

[0167] Therefore, suitable product coating compositions (C2a) are as follows: a) At least one compound having at least two unsaturated groups on average, b) Optionally, at least one photopolymerization initiator, and c) Optionally, at least one additive Includes.

[0168] The coating composition (C2a) preferably has at least two unsaturated carbon double bonds on average, more preferably (meth)acrylic groups. For this purpose, the coating composition (C2) may include any of the crosslinkable polymers and / or oligomers or reactive diluents specified above in relation to (C1a), for example, particularly polyesters, polyethers, carbonates, epoxides, poly(meth)acrylates, urethane (meth)acrylates, and / or silicone (meth)acrylate oligomers and / or at least one unsaturated polyester resin and / or 1-, 2-, and / or 3-functional (meth)acrylic esters.

[0169] When curing with visible light, (N)IR, and / or UV light, the coating composition (C2a) preferably contains at least one photopolymerization initiator that can be decomposed into radicals by the irradiated wavelength of light, and these radicals can then initiate radical polymerization. In contrast, when curing with an electron beam, the presence of such a photopolymerization initiator is not required. As the photopolymerization initiator, the same components and amounts described above in relation to the photopolymerization initiator of the coating composition (C1a) can be used.

[0170] The coating composition (C2a) may contain at least one further additive. In that case, the same components specified above may be used in the same amounts as the additive or further component (e) of the coating composition (C1a).

[0171] Furthermore, it is more preferable that the coating composition used as coating composition (C2a) has (meth)acrylic groups. Preferably, this coating composition (C2a) contains at least one urethane (meth)acrylate. It is also preferable that it contains at least one photopolymerization initiator.

[0172] The coating composition (C2a) can be a solvent-based or solid-based coating composition. To promote rapid curing and prevent the generation of large amounts of evaporated solvent during curing, it is preferable that the coating composition (C2a) is a solid-based coating composition, i.e., a coating composition containing only a small amount of solvent. Therefore, it is advantageous that the solid content of the coating composition is 75 to 100% by mass, based on the total mass of the coating composition (C2a), when measured at 125°C for 60 minutes according to DIN EN ISO3251:2008-06. It is also advantageous that the coating composition contains compound (a) and optional compounds (b) and (c) in a total amount of 90 to 100% by mass, preferably 95 to 100% by mass, and more preferably 99 to 100% by mass, based on the total mass of the coating composition (C2a).

[0173] The present invention's composite (S1C1) A further subject of the present invention is a composite (S1C1) comprising a substrate (S1) and a coating (C1) that is at least partially embossed and at least partially cured, wherein the coating (C1) can be obtained by at least partially curing, at least partially embossing, and radiation curing a coating composition (C1a) applied to at least a portion of the surface of the substrate (S1), and the coating composition (C1a) is a radiation-curable coating composition. (a) 5 to 45% by mass of at least one crosslinkable polymer and / or oligomer, (b) at least one reactive diluent in an amount of 40-95% by mass or ~85% by mass, preferably 50-95% by mass or ~85% by mass or ~83% by mass, (c) At least one photopolymerization initiator in 0.01 to 15% by mass, (d) At least one additive in 0-5% by mass Includes, Here, (i) the total amounts of components (a), (b), (c), and (d) are based on the total mass of the coating composition (C1a), and (ii) the total amount of all components present in the coating composition (C1a) is 100% by mass. Here, at least one crosslinkable polymer and / or oligomer (a) comprises at least one silicone (meth)acrylate oligomer in a total amount of at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass, and very preferably 100% by mass, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a). This is a complex (S1C1) characterized by the following:

[0174] It is preferable that all of components (a), (b), (c), and (d) are different from each other.

[0175] In relation to the method of the present invention, and in particular the coating composition (C1a) and substrate (S1) used therein, and furthermore in relation to the coating (C1), all preferred embodiments described herein are also preferred embodiments related to the composite (S1C1) of the present invention.

[0176] The composite (S1C1) of the present invention is preferably obtained by carrying out steps (6) to (9) of the method of the present invention. The substrate (S1) is advantageously a film web, preferably a moving film web, more preferably a continuous moving film web.

[0177] Use according to the present invention A further subject of the present invention is the use of the composite (S1C1) of the present invention as an embossing mold (e2) for an embossing tool (E2) for transferring an embossed structure to at least a portion of the surface of a coating composition (C2a), or to at least a portion of the surface of a coating composition (C2a) applied at least partially on a substrate (S2).

[0178] All preferred embodiments described herein in relation to the methods of the present invention and the composite (S1C1) of the present invention are also preferred embodiments related to the use of the composite (S1C1) of the present invention.

[0179] In this context, the coating composition (C2a) is preferably a radiation-curable coating composition.

[0180] The present invention will be described in particular by the following embodiments.

[0181] Embodiment 1: A method for transferring an embossed structure to at least a portion of the surface of a coating composition (C2a) using a composite (S1C1), the method comprising at least steps (1), (2-i) and (3-i) or (2-ii) and (3-ii), further at least step (4) and optionally step (5-i) or (5-ii), specifically, (1) A step of preparing a composite (S1C1) consisting of a substrate (S1) and a coating (C1) that is at least partially embossed and at least partially cured, and (2-i) A step of preparing a composite (S2C2a) by applying at least one coating composition (C2a) to at least a portion of the surface of a substrate (S2), (3-i) A step of preparing a composite (S1C1C2aS2) by at least partially embossing the coating composition (C2a) of the composite (S2C2a) using the composite (S1C1), or (2-ii) A step to prepare a composite (S1C1C2a) by at least partially embossing a composite (S1C1) and applying at least one coating composition (C2a) to at least a portion of the surface that has been at least partially cured, and then at least partially embossing the coating composition (C2a) using the composite (S1C1), (3-ii) Optionally, a step of applying a substrate (S2) to at least a portion of the surface of the composite (S1C1C2a) formed by the coating composition (C2a) to obtain a composite (S1C1C2aS2), and (4) A step of preparing a composite (S1C1C2) or (S1C1C2S2) by at least partially curing a coating composition (C2a) that has been optionally applied to a substrate (S2), wherein the coating composition (C2a) is in contact with the composite (S1C1) throughout the period of at least partial curing. and (5-i) A step to optionally remove the complex (C2S2) within the complex (S1C1) from the complex (S1C1) and restore the complex (S1C1) prepared in step (1), or (5-ii) Optionally, remove the coating (C2) within the composite (S1C1) from the composite (S1C1) to restore the composite (S1C1) prepared in step (1). Includes, Here, the coating composition (C1a) used to produce a coating (C1) that is at least partially embossed and at least partially cured of the composite (S1C1) used in step (1) and restored in step (5-i) or step (5-ii) is a radiation-curable coating composition. (a) 5 to 45% by mass of at least one crosslinkable polymer and / or oligomer, (b) at least one reactive diluent in an amount of 40 to 95% by mass, (c) At least one photopolymerization initiator in 0.01 to 15% by mass, (d) At least one additive in 0-5% by mass It contains, Here, (i) the total amounts of components (a), (b), (c), and (d) are based on the total mass of the coating composition (C1a), and (ii) the total amount of all components present in the coating composition (C1a) is 100% by mass. Here, at least one crosslinkable polymer and / or oligomer (a) comprises at least one silicone (meth)acrylate oligomer in a total amount of at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass, and very preferably 100% by mass, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a). method.

[0182] Embodiment 2: A method for transferring an embossed structure to at least a portion of the surface of a coating composition (C2a) using a composite (S1C1), the method comprising at least steps (1), (2-i), and (3-i), further at least step (4), and optionally step (5-i), specifically, (1) A step of preparing a composite (S1C1) consisting of a substrate (S1) and a coating (C1) that is at least partially embossed and at least partially cured, (2-i) A step of preparing a composite (S2C2a) by applying at least one coating composition (C2a) to at least a portion of the surface of a substrate (S2), (3-i) A step of preparing a composite (S1C1C2aS2) by at least partially embossing the coating composition (C2a) of the composite (S2C2a) using the composite (S1C1), (4) A step of preparing a composite (S1C1C2S2) by at least partially curing a coating composition (C2a) that has been optionally applied to a substrate (S2), wherein the coating composition (C2a) is in contact with the composite (S1C1) throughout the period of at least partial curing. (5-i) A step to optionally remove the complex (C2S2) within the complex (S1C1) from the complex (S1C1) and restore the complex (S1C1) prepared in step (1), Includes, Here, the coating composition (C1a) used to produce a coating (C1) that is at least partially embossed and at least partially cured of the composite (S1C1) used in step (1) and restored in step (5-i) is a radiation-curable coating composition. (a) 5 to 45% by mass of at least one crosslinkable polymer and / or oligomer, (b) at least one reactive diluent in an amount of 40 to 95% by mass, (c) At least one photopolymerization initiator in 0.01 to 15% by mass, (d) At least one additive in 0-5% by mass It contains, Here, (i) the total amounts of components (a), (b), (c), and (d) are based on the total mass of the coating composition (C1a), and (ii) the total amount of all components present in the coating composition (C1a) is 100% by mass. Here, at least one crosslinkable polymer and / or oligomer (a) comprises at least one silicone (meth)acrylate oligomer in a total amount of at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass, and very preferably 100% by mass, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a). method.

[0183] Embodiment 3: A method for transferring an embossed structure to at least a portion of the surface of a coating composition (C2a) using a composite (S1C1), the method comprising at least steps (1), (2-ii), further at least step (4), and optionally step (5-ii), specifically, (1) A step of preparing a composite (S1C1) consisting of a substrate (S1) and a coating (C1) that is at least partially embossed and at least partially cured, (2-ii) A step to prepare a composite (S1C1C2a) by at least partially embossing a composite (S1C1) and applying at least one coating composition (C2a) to at least a portion of the surface that has been at least partially cured, and then at least partially embossing the coating composition (C2a) using the composite (S1C1), (4) A step of preparing a composite (S1C1C2S2) by at least partially curing a coating composition (C2a) that is at least partially embossed, wherein the coating composition (C2a) is in contact with the composite (S1C1) throughout the period of at least partial curing. and (5-ii) Optionally, remove the coating (C2) within the composite (S1C1) from the composite (S1C1) to restore the composite (S1C1) prepared in step (1). Includes, Here, the coating composition (C1a) used to produce a coating (C1) that is at least partially embossed and at least partially cured of the composite (S1C1) used in step (1) and restored in step (5-ii) is a radiation-curable coating composition. (a) 5 to 45% by mass of at least one crosslinkable polymer and / or oligomer, (b) at least one reactive diluent in an amount of 40 to 95% by mass, (c) At least one photopolymerization initiator in 0.01 to 15% by mass, (d) At least one additive in 0-5% by mass It contains, Here, (i) the total amounts of components (a), (b), (c), and (d) are based on the total mass of the coating composition (C1a), and (ii) the total amount of all components present in the coating composition (C1a) is 100% by mass. Here, at least one crosslinkable polymer and / or oligomer (a) comprises at least one silicone (meth)acrylate oligomer in a total amount of at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass, and very preferably 100% by mass, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a). method.

[0184] Embodiment 4: A method for transferring an embossed structure to at least a portion of the surface of a coating composition (C2a) using a composite (S1C1), the method comprising at least steps (1), (2-ii), and (3-ii), and further at least step (4) and optionally step (5-ii), specifically, (1) A step of preparing a composite (S1C1) consisting of a substrate (S1) and a coating (C1) that is at least partially embossed and at least partially cured, (2-ii) A step to prepare a composite (S1C1C2a) by at least partially embossing a composite (S1C1) and applying at least one coating composition (C2a) to at least a portion of the surface that has been at least partially cured, and then at least partially embossing the coating composition (C2a) using the composite (S1C1), (3-ii) A step of obtaining a composite (S1C1C2aS2) by applying a substrate (S2) to at least a portion of the surface formed by the coating composition (C2a) of the composite (S1C1C2a), (4) A step of preparing a composite (S1C1C2S2) by at least partially curing a coating composition (C2a) that has been applied to a substrate (S2), wherein the coating composition (C2a) is in contact with the composite (S1C1) throughout the period of at least partial curing. (5-i) A step to optionally remove the complex (C2S2) within the complex (S1C1) from the complex (S1C1) and restore the complex (S1C1) prepared in step (1), Includes, Here, the coating composition (C1a) used to produce a coating (C1) that is at least partially embossed and at least partially cured of the composite (S1C1) used in step (1) and restored in step (5-i) is a radiation-curable coating composition. (a) 5 to 45% by mass of at least one crosslinkable polymer and / or oligomer, (b) at least one reactive diluent in an amount of 40 to 95% by mass, (c) At least one photopolymerization initiator in 0.01 to 15% by mass, (d) At least one additive in 0-5% by mass Contains, Here, (i) the total amounts of components (a), (b), (c), and (d) are based on the total mass of the coating composition (C1a), and (ii) the total amount of all components present in the coating composition (C1a) is 100% by mass. Here, at least one crosslinkable polymer and / or oligomer (a) comprises at least one silicone (meth)acrylate oligomer in a total amount of at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass, and very preferably 100% by mass, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a). method.

[0185] Embodiment 5: The method according to any one of Embodiments 1 to 4, wherein in steps (2-i) and (2-ii), the at least one coating composition (C2a) is applied to a dry layer thickness of at least 0.5 μm, at least 1 μm, and more preferably at least 5 μm.

[0186] Embodiment 6: The method according to any one of Embodiments 1 to 5, wherein the embossed structure to be transferred is a microstructure and / or nanostructure, preferably having a structural width in the range of 10 nm to 500 μm, more preferably in the range of 25 nm to 400 μm, very preferably in the range of 50 nm to 250 μm, and more preferably in the range of 100 nm to 100 μm, and also having a structural height in the range of 10 nm to 500 μm, more preferably in the range of 25 nm to 400 μm, very preferably in the range of 50 nm to 300 μm, and more preferably in the range of 100 nm to 200 μm.

[0187] Embodiment 7: The method according to any one of Embodiments 1 to 6, wherein at least one adhesive is applied to the surface of a substrate (S2) that does not come into contact with the coating composition (C2a).

[0188] Embodiment 8: The method according to any one of Embodiments 1 to 7, wherein in step (5-i), a composite (C2S2) is obtained by peeling it off from the composite (S1C1C2S2), and the composite (S1C1) prepared in step (1) is added and restored, or the reverse is performed.

[0189] Embodiment 9: The method according to any one of Embodiments 1 to 7, wherein the coating (C2) of step (5-ii), which is at least partially embossed and at least partially cured, is obtained as an independent film by peeling it from the composite (S1C1C2), and the composite (S1C1) prepared in step (1) is added and restored, or the reverse is done.

[0190] Embodiment 10: The step of removing from the composite (S1C1) is the following step, 5-ia) A step of preparing a composite (S1C1C2S2AL) by applying at least one adhesive layer (AL) to the surface of a substrate (S2) that is not in contact with at least partially embossed coating (C2), 5-ib) Optionally, a step of attaching the composite (S1C1C2S2AL) at least partially to an object (O1), 5-ic) A step of removing, preferably peeling off, a composite (S1C1) from a composite (C2S2AL) that is optionally attached at least partially to an object (O1). The method according to any one of Embodiments 1 to 7, including the method described in each of Embodiments 1 to 7.

[0191] Embodiment 11: The step of removing from the composite (S1C1) is the following step, 5-ii-a) A step of preparing a composite (S1C1C2AL) by applying at least one adhesive layer (AL) to at least a portion of the unstructured surface of a coating (C2) that is at least partially embossed, 5-ii-b) Optionally, a step of attaching the composite (S1C1C2AL) at least partially to an object (O1), 5-ii-c) Optionally, a step of removing, preferably peeling off, a composite (S1C1) from a composite (C2S2AL) that is at least partially attached to an object (O1), or vice versa. The method according to any one of Embodiments 1 to 7, including the method described in each of Embodiments 1 to 7.

[0192] Embodiment 12: The composite (S1C1) prepared in step (1) is used as the embossing mold (e2) of the embossing tool (E2) in steps (2-i), (2-ii), and (3-ii) to transfer the embossed structure of the coating (C1) to the coating composition (C2a) as an embossed structure. The method according to any one of Embodiments 1 to 11, wherein a mirror image of the structured surface of the coating (C1) of the composite (S1C1) used as an embossing mold (e2) is optionally embossed onto the surface of a coating (C2) that is at least partially embossed and at least partially cured, applied to a substrate (S2).

[0193] Embodiment 13: The method according to any one of Embodiments 1 to 12, wherein the substrate (S1) is a film web, preferably a moving film web or a continuous film web, more preferably a continuous moving film web.

[0194] Embodiment 14: The method according to any one of Embodiments 1 to 13, wherein the substrate (S2) is a film web, preferably a moving film web, and more preferably a continuous moving film web.

[0195] Embodiment 15: The method according to any one of Embodiments 1 to 14, wherein the composite (S1C1) used in steps (2-i), (2-ii), and (3-ii) is reusable and can be repeatedly used to transfer at least one embossed structure when carrying out step (5-i) or (5-ii) of the method.

[0196] Embodiment 16: During the execution of process (3-i), the composite (S1C1) in process (3-i) is guided through a first roll that functions as an embossing tool (E2), and the composite (S2C2a) is guided through a second roll positioned opposite to the first roll and rotating in the opposite direction to the first roll or in the same direction as the first roll (co-rotatory), and The method according to any one of embodiments 1 to 15, wherein during the execution of step (3-ii), the composite (S1C1C2a) in step (3-i) is guided via a first roll that functions as an embossing tool (E2), and the substrate (S2) used in step (3-ii) is guided via a second roll positioned opposite to the first roll and rotating in the opposite direction to or in the same direction as the first roll.

[0197] Embodiment 17: At least the partial embossing in step (3-i) is performed at the level of a roll nip formed by two opposing rolls, where both rolls rotate in opposite or co-directions, and the at least partially embossed coating (C1) of composite (S1C1) faces the coating composition (C2a) of composite (S2C2a). and The method according to Embodiment 16, wherein at least partial embossing in step (3-ii) is performed at the level of a roll nip formed by two opposing rolls, where both rolls rotate in opposite or co-directions, and the coating composition (C2a) of the composite (S1C1C2a) faces the substrate (S2).

[0198] Embodiment 18: The composite (S1C1) prepared in step (1) is at least, (6) Apply the radiation-curable coating composition (C1a) to at least a portion of the surface of the substrate (S1) to prepare a composite (S1C1a); (7) At least partially emboss the coating composition (C1a) applied to the surface of the substrate (S1) with at least one embossing tool (E1) which includes at least one embossing mold (e1), (8) At least partially curing a partially embossed coating composition (C1a) applied at least partially to a substrate (S1) that is in contact with at least one embossing mold (e1) of an embossing tool (E1) for at least a period of partial curing, (9) Remove the composite (S1C1) from the embossing mold (e1) of the embossing tool (E1) to prepare a composite (S1C1) that is at least partially embossed and at least partially hardened, or the reverse. The method according to any one of Embodiments 1 to 17, which is obtained by means of the method described herein.

[0199] Embodiment 19: The method according to Embodiment 18, wherein at least one coating composition (C1a) of step (6) is applied to a dry layer thickness of at least 0.5 μm, preferably at least 1 μm, and more preferably at least 5 μm.

[0200] Embodiment 20: The method according to any one of Embodiments 1 to 19, wherein the coating composition (C1a) comprises at least one crosslinkable polymer and / or oligomer in a total amount of 5 to 45% by mass, preferably 8 to 40% by mass, and more preferably 9 to 35% by mass, based on the total mass of the coating composition (C1a).

[0201] Embodiment 21: The method according to any one of Embodiments 1 to 20, wherein the coating composition (C1a) comprises, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a), at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass, and very preferably 100% by mass, at least one silicone (meth)acrylate oligomer, preferably strictly one silicone (meth)acrylate oligomer, more preferably strictly one silicone (meth)acrylate oligomer having an average of 2 to 3 unsaturated groups.

[0202] Embodiment 22: The coating composition (C1a) contains at least one crosslinkable polymer and / or oligomer in a total amount of 5 to 45% by mass, preferably 8 to 40% by mass, more preferably 9 to 35% by mass, based on the total mass of the coating composition (C1a), and the at least one crosslinkable polymer and / or oligomer is i) at least one silicone (meth)acrylate oligomer, preferably exactly one silicone (meth)acrylate oligomer, very preferably exactly one silicone (meth)acrylate oligomer having an average of 2 to 3 unsaturated groups, and ii) other crosslinkable polymers and / or oligomers selected from the group consisting of (meth)acrylated oligomers or polymer compounds, urethane (meth)acrylates, vinyl (meth)acrylates, epoxy (meth)acrylates, polyester (meth)acrylates, poly(meth)acrylates, polyether (meth)acrylates, olefin (meth)acrylates, (meth)acrylated oils, and mixtures thereof, preferably urethane (meth)acrylate oligomers, according to any one of Embodiments 1 to 21.

[0203] Embodiment 23: The coating composition (C1a) contains a free-radical polymerizable monomer, preferably an ethylenically unsaturated monomer, more preferably a polyfunctional ethylenically unsaturated monomer, as a reactive diluent, according to any one of Embodiments 1 to 22.

[0204] Embodiment 24: The coating composition (C1a) is composed of hexanediol diacrylate and the general formula (I)

[0205]

Chemical formula

[0206] Embodiment 25: The method according to Embodiment 24, wherein the compound has three identical structural units of formula (I) and the symbol m is at least 2, preferably strictly 2.

[0207] Embodiment 26: The method according to Embodiment 24 or 25, wherein a particularly preferred compound having at least two structural units of general formula (I) is a (meth)acrylate obtained by alkoxyling neopentyl glycol, trimethylolpropane, trimethylolethane, or pentaerythritol by a total of 4 to 20 times or 4 to 12 times (e.g., ethoxylation, propoxylation, or ethoxylation and propoxylation), and more specifically, a (meth)acrylate obtained by exclusively ethoxyling neopentyl glycol, trimethylolpropane, trimethylolethane, or pentaerythritol.

[0208] Embodiment 27: The method according to any one of Embodiments 1 to 6, wherein the coating composition (C1a) comprises at least one reactive diluent, preferably hexanediol diacrylate and / or a (meth)acrylate derived from 6-fold ethoxylated trimethylolpropane, in a total amount of 40 to 95% by mass, preferably 50 to 85% by mass, more preferably 55 to 83% by mass, based on the total mass of the coating composition (C1a).

[0209] Embodiment 28: The method according to any one of Embodiments 1 to 27, wherein the coating composition (C1a) contains at least one photopolymerization initiator in a total amount of 0.01 to 15% by mass, preferably 0.5 to 10% by mass, and more preferably 1 to 8% by mass, based on the total mass of the coating composition (C1a).

[0210] Embodiment 29: The method according to any one of Embodiments 1 to 28, wherein the photopolymerization initiator contained in the coating composition (C1a) is selected from phosphine oxides including (alkyl-)benzoylphenylphosphine oxide, benzophenone, α-hydroxyalkylaryl ketone, thioxanthone, anthraquinone, acetophenone, benzoin and benzoin ether, ketal, imidazole or phenylglyoxylic acid and mixtures thereof, preferably diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphineate, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, benzophenone, 1-benzoylcyclohexane-1-ol, 2-hydroxy-2,2-dimethylacetophenone and 2,2-dimethoxy-2-phenylacetophenone and mixtures thereof.

[0211] Embodiment 30: The method according to any one of Embodiments 1 to 29, wherein the coating composition (C1a) contains at least one additive in a total amount of 0.01 to 5% by mass, preferably 0.2 or 0.5 to 5% by mass, and more preferably 0.5 to 3% by mass, based on the total mass of the coating composition (C1a).

[0212] Embodiment 31: The method according to any one of Embodiments 1 to 30, wherein the coating composition (C1a) contains, based on the total mass of the coating composition (C1a), an amount of less than 10% by mass, preferably less than 5% by mass, and more preferably less than 1% by mass of an organic solvent, and is very preferably free of organic solvents.

[0213] Embodiment 32: The method according to any one of Embodiments 1 to 30, wherein the coating composition (C1a) is composed of components (a), (b), (c), and optionally (d) in a total amount of 90 to 100% by mass, preferably 95 to 100% by mass, and more preferably 99 to 100% by mass, based on the total mass of the coating composition (C1a).

[0214] Embodiment 33: A composite (S1C1) comprising a substrate (S1) and a coating (C1) that is at least partially embossed and at least partially cured, wherein the coating (C1) is obtained by at least partially curing and at least partially embossing a coating composition (C1a) applied to at least a portion of the surface of the substrate (S1) by radiation curing, and the coating composition (C1a) is a radiation-curable coating composition. (a) 5 to 45% by mass of at least one crosslinkable polymer and / or oligomer, (b) at least one reactive diluent in an amount of 40 to 95% by mass, (c) At least one photopolymerization initiator in 0.01 to 15% by mass, (d) At least one additive in 0-5% by mass Includes, Here, (i) the total amounts of components (a), (b), (c), and (d) are based on the total mass of the coating composition (C1a), and (ii) the total amount of all components present in the coating composition (C1a) is 100% by mass. Here, the composite (S1C1) comprises at least one crosslinkable polymer and / or oligomer (a), with a total amount of at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass, and very preferably 100% by mass, of at least one silicone (meth)acrylate oligomer, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a).

[0215] Embodiment 34: The composite (S1C1) according to Embodiment 33, wherein the composite (S1C1) is obtained by carrying out steps (6) to (9) of the method described in Embodiment 18 or 19.

[0216] Embodiment 35: The composite (S1C1) according to Embodiment 33 or 34, wherein the substrate (S1) is a film web, preferably a moving film web, more preferably a continuous moving film web.

[0217] Embodiment 36: Use of the composite (S1C1) according to any one of Embodiments 33 to 35 as an embossing mold (e2) for an embossing tool (E2) for transferring an embossed structure to at least a portion of the surface of a coating composition (C2a), or to at least a portion of the surface of a coating composition (C2a) applied at least partially onto a substrate (S2).

[0218] Embodiment 37: The method according to any one of Embodiments 1 to 5, wherein the radiation-curable coating composition (C1a) contains at least one reactive diluent in an amount of 50 to 95% by mass, or 50 to 85% by mass, or 50 to 83% by mass, based on the total mass of the coating composition (C1a).

[0219] Embodiment 38: The composition according to any one of Embodiments 33 to 36, wherein the radiation-curable coating composition (C1a) contains at least one reactive diluent in an amount of 50 to 95% by mass, or 50 to 85% by mass, or 50 to 83% by mass, based on the total mass of the coating composition (C1a).

[0220] Measurement or determination method 1. Determining mold filling The determination of mold filling is carried out using a commercially available scanning electron microscope (SEM). With the SEM, it is possible to compare, for example, the surface morphology of a certain lattice structure having features with a structure width of, for example, 10 nm to 1000 μm and a structure depth in the range of 1 nm to 1000 μm of different master films (S1C1) after embossing. If a sharp shape such as the tip of a structure formed into a triangle can be completely replicated, the filling of the mold is considered to be complete. Following the comparison of the surface morphology of each master film (S1C1), the mold filling can also be compared. 2. Determination of flow time The flow time is determined in accordance with DIN EN ISO2431 (date: March 2012). The method is to measure the flow time using a 4 mm viscosity cup (No. 4), a 5 mm viscosity cup (No. 5), and a 6 mm viscosity cup (No. 6) at room temperature (20 °C).

[0221] A flow time in the range of 40 or 50 to 100 seconds measured with a 4 mm viscosity cup, a flow time in the range of 30 to 100 seconds measured with a 5 mm viscosity cup, and a flow time in the range of 30 to 200 seconds, preferably 30 to 150 seconds, more preferably 30 to 115 seconds measured with a 6 mm viscosity cup are considered to be within the allowable range. Therefore, a coating composition with a flow time exceeding 200 seconds using a 6 mm viscosity cup is considered not to be advantageous. This is because the coating composition does not spread fast enough with a uniform layer thickness over the entire width of the substrate or composite, the quality of mold filling and replication deteriorates, and as the flow time becomes longer, the risk of air entering the applied coating composition increases. On the other hand, when using a 4 mm viscosity cup and the flow time is less than 40 or 50 seconds, it is considered to be disadvantageous. This is because, for example, when applied with a roll-to-roll (R2R) embossing device, the coating composition easily flows off the substrate, thereby not providing sufficient cohesive force within the layer, and thus it is not possible to achieve a layer thickness sufficient for embossing microstructures and nanostructures with sufficient mold filling and transfer quality.

[0222] 3. Adhesion determination 3.1 Cross-hatch test Adhesion will be determined by a cross-hatch test in accordance with DIN EN ISO2409 (dated June 2013). This test uses a double-check method to examine the adhesion strength of the coating layer under investigation to the substrate. A Byk Gardner cross-hatch tester with a 2mm cut interval will be used manually. Afterwards, Tesa tape No. 4651 will be pressed onto the damaged area and peeled off to remove the delamination area. The evaluation will be based on a characteristic value from 0 (minimal delamination) to 5 (very much delamination). An average value of 3.5 or less will be considered sufficient.

[0223] 3.2 St. Andrew's Cross Adhesion strength is determined by a proprietary cross-cut test. In this test, a St. Andrew's Cross (length: 10 cm, angle: 45°) is manually cut into the coating layer with a scalpel. Then, Tesa Tape No. 4651 is pressed onto the damaged area and peeled off to remove the delaminate area. If no delamination of the coating layer is observed after cutting and peeling off the tape, the adhesion strength of the coating layer is evaluated as "OK". If delamination of the coating layer is observed after cutting and peeling off the tape, the adhesion strength of the coating layer is evaluated as "not OK".

[0224] 4. Determining the success rate of replication The success or failure of replication is determined visually, and the percentage of the successfully replicated area is determined. Here, a successfully replicated area is defined as being in the range of 0% to 100%. If less than 100% of the area is replicated, this means that the corresponding percentage of the area could not be removed from the embossing mold, in other words, that a portion of the coating C1 in the form of S1C1 remained attached to the embossing mold (e1) of the embossing tool (E1), or that a portion of the coating C2 remained attached to the composite (S1C1) after separation.

[0225] 5. Determination of layer thickness distribution The layer thickness distribution is determined by measuring the layer thickness of the composite S1C1 containing the imprinted structure. In other words, the total thickness measured for the layer stack S1C1 is the sum of the heights of the substrate S1, the residual layer of coating C1, and the structures formed in or on the coating C1. Thickness measurements were performed using an ElektroPhysik MiniTest® 2100 microprocessor thickness gauge and an F1.6 probe in accordance with DIN EN ISO 2808 (dated May 2007), procedure 12A (measurement uncertainty: ±(1% + 1 μm)). The composite S1C1 was placed on a flat ferromagnetic plate and measured in the absence of a ferromagnetic substrate. Layer thickness was measured at nine predetermined measurement points in a 3 × 3 matrix arrangement on a 15 cm × 15 cm patch of S1C1. All measurement points were spaced 5 cm apart. The first measurement point, or starting point, was located 2.5 cm from the top and 2.5 cm from the left side of the 15 cm x 15 cm patch of S1C1. Therefore, the second measurement point was located 2.5 cm from the top and 7.5 cm from the left side of the 15 cm x 15 cm patch of S1C1.

[0226] 6. Determination of flexibility Each composite (S1C1) was folded 180° to assess its flexibility. If no cracks and / or damage were visually observed within the coating (C1) during and / or after folding, the evaluation was "OK". Conversely, if cracks and / or damage were visually observed in the coating (C1) during and / or after folding, the evaluation was "Not OK". [Examples]

[0227] Examples and Comparative Examples of the Invention The examples and comparative examples of the present invention described below are for illustrative purposes only and should not be construed as imposing any limitations.

[0228] Unless otherwise specified, quantities expressed as parts are parts by mass, and quantities expressed as percentages are mass percentages in each case.

[0229] 1. Raw materials and ingredients used Hostaphan (registered trademark) GN CT01B - A commercially available PET film that has been chemically treated on both sides to enhance coating adhesion, with a layer thickness of 175 μm. Also available is a commercially available PET film with a layer thickness of 125 μm, supplied by SKC Corporation of Korea, which is double-sided urethane coated to enhance adhesion to inks and coatings, particularly UV-curable inks.

[0230] Laromer (registered trademark) UA9033 (L UA9033) - Aliphatic urethane acrylate manufactured by BASF SE Laromer (registered trademark) UA9089 (L UA9089) - Aliphatic urethane acrylate manufactured by BASF SE Hexanediol diacrylate (HDDA) Hydroxypropyl acrylate (HPA) Sartomer® CN9800 (CN9800) - Aliphatic silicone acrylate manufactured by Sartomer. Sartomer® 499 (SR499) - 6x ethoxylated TMPTA (trimethylolpropane triacrylate) manufactured by Sartomer. Sartomer® SR344 (manufactured by Arkema) - Polyethylene Glycol (400) Diacrylate Irgacure(registered trademark) 184 (I-184) - Commercial photopolymerization initiator manufactured by BASF SE Commercial photopolymerization initiator manufactured by Irgacure® TPO-L (I-TPO-L)-BASF SE Tego® Rad2500 (TR 2500) - Lubricant and anti-blocking additive (silicone acrylate) manufactured by Evonik.

[0231] 2. Examples 2.1 Production of the coating composition (C1a) according to the present invention (C1a-1) and production of the corresponding comparative coating composition (C1a-2) Coating compositions suitable as coating compositions (C1a) for the production of composite (S1C1) were prepared according to Table 1 below. The flow time measured at room temperature (20°C) ranged from 26 to 172 seconds for the production of C1a-5 and C1a-9.

[0232] [Table 1]

[0233] The flow times for Examples C1a-2 to C1a-8 of the present invention, where the total amount of reactive diluent measured by the method described in 2 (Determination of Flow Time) above is 40 to 80% by mass based on the total mass of the coating composition (C1a), are within the acceptable range from 50 seconds measured with a 4 mm viscosity cup to 200 seconds measured with a 6 mm viscosity cup. On the other hand, the flow times for Comparative Example C1a-1 (total amount of reactive diluent 35% by mass), Comparative Example C1a-10 (total amount of reactive diluent 25% by mass), and Comparative Example C1a-11 (total amount of reactive diluent 25% by mass, KR2009 / 0068490A, composition in accordance with Example 1) are unfavorably high and therefore outside the acceptable range.

[0234] 2.2 Production of a composite (S1C1) using the coating composition (C1a-5) according to the present invention and production of a composite (S1C1) using the comparative coating composition (C1a-9) The production of numerous different compositions (S1C1) according to Table 2 below is carried out using a roll-to-plate (R2P) embossing apparatus having a nickel embossing die (e1) with a desired image of the structure to be embossed. The image of the structure on the embossing die (e1) corresponds to the image of the structure to be embossed onto the coating composition (C2a) in a subsequent step.

[0235] In these embodiments, nickel embossing dies (e1) having various positive-type structures were used. Specifically, the following structures were used: • Microstructure M1 (a three-dimensional triangular structure with a height of 61 μm and a periodic repeat of 130 μm, or • Microstructure M2 (two-dimensional triangular structure with a height of 42 μm and a space between structures of 55 μm) An embossing mold with a specific feature was used.

[0236] For this purpose, one of each of the above-described coating compositions C1a-5 and C1a-9 is applied to the embossing mold (e1) of the embossing tool (E1), and a PET film as the substrate (S1) is attached thereon. Next, the stacks consisting of the obtained film and each coating composition are passed under a pressing roll, and the coating compositions are at least partially cured using a UV-LED lamp while the embossing device is in contact with the coating compositions of each stack. The coatings, which have a negative structure compared to the embossing mold (e1) and are at least partially cured together with the film, are then separated from the embossing device to obtain a structured film (master film) as a composite (S1C1). Subsequently, the master film is subjected to post-exposure with a UVA lamp. The symbol "-" in the table indicates that such post-curing was not performed.

[0237] [Table 2]

[0238] Master films A and B, having microstructure M1, are used to determine mold filling, adhesion, and the success or failure of replication (see section 2.3.1). They are also used in the manufacture and evaluation of transfer films, as described in sections 2.4 to 2.5.2 below. Master films C, D, E, and F, having microstructure M2, are used to determine the uniformity of layer thickness as described in section 2.3.2 below. To manufacture these master films, coating compositions (C1a-5) and (C1a-9) are used, and correspondingly, coating (C1) is obtained from coating composition (C1a-5) or (C1a-9), respectively, to obtain a composite (S1C1) having microstructure M1 or M2 as an embossed structure.

[0239] In another series of experiments, composites (S1C1) were produced according to the manufacturing parameters of "master film C" shown in Table 2. Here, coating composition (C1a-5) was replaced with one of the coating compositions (C1a-1) to (C1a-8), (C1a-10), or (C1a-11) shown in Table 1, respectively, to obtain master films G to P.

[0240] Master films G to P prepared from coating compositions (C1a1) to (C1a-8), (C1a-10), or (C1a-11) all showed acceptable layer thicknesses within the range of 203 to 225 μm. For master films G to O, the flexibility was measured on the 7th day after production using the method described in item 6 above and was found to be "OK". Only the flexibility of master film P, prepared from comparative coating composition (C1a-11), was "not OK". Furthermore, when master films G to P were observed with an Olympus stereomicroscope SZX12, an unacceptable amount of air entrapment was confirmed in the case of master film P prepared from the comparative coating composition (C1a-11).

[0241] 2.3 Examination of the Master Film (S1C1) 2.3.1 Determination of Adhesion and Mold Filling Properties The findings of the studies conducted on master films A and B are summarized in Table 3 below. These studies were carried out according to the methods described above.

[0242] [Table 3]

[0243] From the data in Table 3, it can be seen that the master film A of the present invention (cross-hatch test, St. Andrew's Cross test) shows good adhesion, but the adhesion achievable with comparative master film B is insufficient in comparison (cross-hatch test evaluation 5, St. Andrew's Cross test minus). If the adhesion of the master coating (C1) on the substrate (S1), or in these examples the adhesion of the coating compositions (C1-5) and (C1-9) on the PET film is insufficient, problems may occur during embossing on both the coating composition (C1a) and, subsequently, on the coating composition (C2a) when the master film is used as an embossing mold (e2).

[0244] The success rate of copying master film A remained at a good level, similar to that of master film B (Table 3, Success Rate of Copying). Therefore, no residue remained on the embossed mold (e1) even with the coating composition used in this invention.

[0245] The mold-filling properties of master films A and B were determined as described above by visually inspecting and comparing SEM images of triangular features embossed on a coating composition (C1a) applied to a substrate (S1) using the embossing mold (e1) of the embossing tool (E1) (Figure 3). Comparing the SEM images of master films A and B, it can be seen that the structure, including sharp details such as edges and triangular features, is completely and equally transferred from the embossing mold to the coating composition (C1a). Therefore, even when a large amount of silicone (meth)acrylate oligomer was introduced into the coating composition (C1a) according to the present invention, no decrease in mold-filling properties was observed. This was expected from the difference in surface tension between coating compositions (C1a-5) and (C1a-9). Thus, it was observed that in both cases of coating compositions C1a-1 and C1a-2, the negative mold feature portion in the mold was completely and equally filled.

[0246] Based on the above, it can be concluded that only master film A yields favorable results in all the characteristics examined (adhesion, mold filling ability, and replication success rate).

[0247] 2.3.2 Determination of Uniformity of Layer Thickness The investigations and studies conducted for master films C, D, E, and F are summarized in Table 4 below. Each investigation was carried out according to the method described above. In this series of experiments, the applied pressure (3.3 bar) and the slot size of the coater used to apply the coating composition (3.28 mm) were kept the same.

[0248] [Table 4]

[0249] The data in Table 4 shows that, in the case of master films C and E used in the present invention, the maximum difference in layer thickness (delta Δ(S1C1) from the minimum to the maximum layer thickness) was significantly reduced for the two processing speeds compared to comparative master films D and F. This is also indicated by the much smaller standard deviation. Furthermore, not only was the layer thickness of the applied coating composition much more uniform, but the average layer thickness itself could also be increased.

[0250] If the thickness of the master coating (C1a) is too uneven across the width of the substrate (S1), problems may arise when embossing both the coating composition (C1a) and subsequent coating compositions (C2a). The reproduction quality of the image of the structure from the embossing die (e1) of the embossing tool (E1) is generally improved, especially at large dimensions, with greater uniformity of the thickness of the coating composition (C1a). This is because the pressure applied to impress the positive features of the embossing die (e1) of the embossing tool (E1) into the coating composition (C1a) is evenly distributed, allowing for equivalent impressions across the entire width of the embossing tool. Therefore, a uniform thickness of the coating composition (C1a) results in higher reproduction quality of the features of the embossing die (e1) in a coating (C1) with a uniform residual layer across the entire width, or nearly the entire width, of the film. As a result, when the composite (S1C1) is used as an embossing mold itself, such as an embossing mold (e2), if the thickness of the coating (C1) is uniform, it is possible to improve the transfer of the embossed structure to the coating composition (C2a). Here again, the pressure applied to the composite (S1C1) is distributed more evenly throughout the composite (S1C1), enabling higher quality replication and more reproducible transfer of the embossed structure in the coating composition (C2a).

[0251] In summary, master films C and E show a significant improvement in the uniformity of layer thickness compared to master films D and F.

[0252] 2.4 Manufacturing of Transfer Film (S1C1C2) Next, master films (S1C1), each possessing structure M1, are used in a roll-to-plate (R2P) embossing machine, and the coating composition (C2a) is applied to the structured surface of each master film to a dry layer thickness of 40 μm. The resulting laminated stack of master film and coating composition (C2a) is temporarily backed with a TAC film to protect the coating composition (C2a) from oxygen and mechanical influences. The resulting laminate consists of the master film (S1C1), the coating composition (C2a) applied on it, and the TAC film attached to the coating composition (C2a). This laminate is then passed under a pressing roll (applied pressure of 6 bar) while the coating composition (C2a) is at least partially cured using a UV-LED lamp. The lamp used in this experiment was an Easytec 365nm, 6W UV-LED lamp (lamp power 100%, 2 m / min, 2 passes). In this way, after removing the protective TAC film, a composite (S1C1C2-1) is obtained from master film A, and a composite (S1C1C2-2) is obtained from master film B.

[0253] The coating composition used (C2a) is a commercially available radiation-curable coating composition comprising at least one urethane acrylate, at least one photopolymerization initiator, and a commercially available additive.

[0254] 2.5 Examination of the complex (S1C1C2) 2.5.1 (i) Separation behavior as a function of time from the formation of the composite (S1C1) to the application of the coating composition (C2a), and ii) Separation behavior as a function of time from the application of the coating composition (C2a) to the composite (S1C1). Considering the master film (S1C1) used for embossing, the separation behavior of the structured master film and the generated coating (C2) due to changes in the master film (S1C1), which is represented by the reproduction quality, over time is investigated and summarized in Table 5 below. The coating (C2) is removed from the composite (S1C1) by peeling it off. Note that "-" in the table indicates that a specific investigation item was not performed.

[0255] [Table 5]

[0256] When using master film B, the success rate of replication during separation of master film (S1C1) and coating (C2) was significantly below 100%. When master film (S1C1) was prepared from coating composition (C1a-9), and coating composition (C2a) was applied 5 days after direct separation following curing, the success rate was as low as 0%. Therefore, most of the coating (C2) could not be separated or removed from the coating (C1) of master film B without damaging the coating (C2) or master film B. Master film "P" prepared from the comparative coating composition (C1a-11) described in Table 2 and below remained tacky even after curing, causing these master films to stick together during storage, resulting in poor separation behavior from the coating (C2) immediately after curing and 1 day after curing, with a success rate of 0%. In contrast, when using the investigated master film A, the replication success rate during separation was 100% or nearly 100% (97%), regardless of the elapsed time from master film production to coating composition (C2a) application or the elapsed time after embossing and curing of the coating composition (C2a) applied to the master film (S1C1). In other words, by using master film A, the replication success rate (as an indicator of separation behavior) is very high, regardless of the aging of the master film itself, and the storage and transport of the laminated stack (S1C1C2) composed of the master film (S1C1) and coating (C2) becomes possible. Therefore, compared to master film B, master film A allows for the coating composition (C2a) to be applied directly to the master film, applied after several days, or applied and stored together with the master film (S1C1) before separating the coating (C2) from the master film (S1C1). Furthermore, it enables protection of the imprinted structure of the composite (S1C1), clean release without residue from the composite (S1C1), thereby improving the reusability of the composite (S1C1) as an embossing mold, and obtaining an embossed coating (C2) as a self-supporting film.Furthermore, the same explanation can be given for master films G to O prepared from coating compositions (C1a-1) to (C1a-8) and (C1a-10) after 9 days, demonstrating that the separation behavior of coating (C2) immediately after curing and one day after curing was 100%.

[0257] 2.5.2 Mold filling The mold-filling properties of the coating composition (C2a) on master films A and B, which can be used as embossing molds, were determined by visually inspecting and comparing SEM images of the triangular features transferred to the coating composition (C2a) by embossing, as described above. In this embossing, the same coating composition (C2a) was applied to master foil A or B 11 days after its preparation, and peeled off immediately after curing (Figure 4). Comparing the SEM images of the embossed and cured coatings (C2) after separation from master films A and B, it can be seen that structures including sharp details such as edges and triangular features were completely and equally transferred from master films A and B to the coating composition (C2a). In Figure 4, the coating (C2) obtained after separation from master film A according to the present invention is denoted as coating C2-1. Correspondingly, the coating (C2) obtained after separation from master film B is denoted as coating C2-2. Therefore, even when a large amount of silicone (meth)acrylate oligomer was introduced into the coating composition (C1a) according to the present invention, mold-filling properties were not lost or reduced. This was expected because the surface energies of coating compositions (C1-5) and (C1-9) differed from the surface tension of coating composition (C2a). Consequently, complete and equivalent transfer of positive mold features was observed in master films A and B containing coating compositions (C1a-5) and (C1a-9). [Explanation of Symbols]

[0258] 1 Embossed area 2 Press Roll 3 Lighting Unit 4 Press Roll 5 Formwork 6, 7 Film web roller 8 Master Film Web 9 Filmweb 10 Transfer device 11 Film Web Roller 17 Master press cylinder 19 Film Web Roller 27 Coating Application Units 30 Master Transfer Device

Claims

1. A method for transferring an embossed structure to at least a portion of the surface of a coating composition (C2a) using a composite (S1C1), the method comprising at least steps (1), (2-i) and (3-i) or (2-ii) and (3-ii), further at least step (4) and optionally step (5-i) or (5-ii), specifically, (1) A step of preparing a composite (S1C1) consisting of a base material (S1) and a coating (C1) that is at least partially embossed and at least partially cured, and (2-i) A step of preparing a composite (S2C2a) by applying at least one coating composition (C2a) to at least a portion of the surface of a substrate (S2), (3-i) A step of preparing a composite (S1C1C2aS2) by at least partially embossing the coating composition (C2a) of the composite (S2C2a) using the composite (S1C1), or (2-ii) A step of preparing a composite (S1C1C2a) by applying at least one coating composition (C2a) to at least a portion of the surface of a composite (S1C1) that is at least partially embossed and at least partially cured, and then using the composite (S1C1) to emboss the coating composition (C2a) at least partially. (3-ii) Optionally, a step of applying a substrate (S2) to at least a portion of the surface of the composite (S1C1C2a) formed by the coating composition (C2a) to obtain a composite (S1C1C2aS2), and (4) A step of preparing a composite (S1C1C2) or (S1C1C2S2) by at least partially curing a coating composition (C2a) that has been optionally applied to a substrate (S2), wherein the coating composition (C2a) is in contact with the composite (S1C1) throughout the period of at least partial curing. and (5-i) A step to optionally remove the complex (C2S2) within the complex (S1C1) from the complex (S1C1) to restore the complex (S1C1) prepared in step (1), or (5-ii) Optionally, a step to remove the coating (C2) within the composite (S1C1) from the composite (S1C1) to restore the composite (S1C1) prepared in step (1). Includes, Here, the coating composition (C1a) used to produce the at least partially embossed and at least partially cured coating (C1) of the composite (S1C1) used in step (1) and restored in step (5-i) or step (5-ii) is a radiation-curable coating composition. (a) 5 to 45% by mass of at least one crosslinkable polymer and / or oligomer, (b) at least one reactive diluent in an amount of 40 to 95% by mass, (c) 0.01 to 15% by mass of at least one photopolymerization initiator, and (d) At least one additive in 0 to 5% by mass It contains, Here, (i) the total amounts of components (a), (b), (c), and (d) are based on the total mass of the coating composition (C1a), and (ii) the total amount of all components present in the coating composition (C1a) is 100% by mass. Here, at least one crosslinkable polymer and / or oligomer (a) comprises at least one silicone (meth)acrylate oligomer in a total amount of at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass, and very preferably 100% by mass, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a). A method characterized by the following:

2. The method according to claim 1, wherein the radiation-curable coating composition (C1a) comprises at least one reactive diluent in an amount of 50 to 95% by mass, or 50 to 85% by mass, or 50 to 83% by mass, based on the total mass of the coating composition (C1a).

3. The method according to claim 1 or 2, wherein the embossed structure to be transferred is a microstructure and / or nanostructure, preferably having a structural width in the range of 10 nm to 500 μm, more preferably in the range of 25 nm to 400 μm, very preferably in the range of 50 nm to 250 μm, and more preferably in the range of 100 nm to 100 μm, and also having a structural height in the range of 10 nm to 500 μm, more preferably in the range of 25 nm to 400 μm, very preferably in the range of 50 nm to 300 μm, and more preferably in the range of 100 nm to 200 μm.

4. The method according to any one of claims 1 to 3, wherein at least one adhesive is applied to the other surface of the substrate (S2) that is not coated with the coating composition (C2a).

5. The process of removing the complex (S1C1) is as follows: 5-i-a) A step of preparing a composite (S1C1C2S2AL) by applying at least one adhesive layer (AL) to the surface of a substrate (S2) that is not in contact with at least partially embossed coating (C2), 5-i-b) Optionally, a step of attaching the composite (S1C1C2S2AL) to an object (O1) at least partially. 5-i-c) A step of removing, preferably peeling off, a composite (S1C1) from a composite (C2S2AL) that has been optionally attached to an object (O1) at least partially, or 5-ii-a) A step of preparing a composite (S1C1C2AL) by applying at least one adhesive layer (AL) to at least a portion of the unstructured surface of a coating (C2) that has been at least partially embossed, 5-ii-b) Optionally, a step of attaching the composite (S1C1C2AL) at least partially to an object (O1), 5-ii-c) A step of optionally removing, preferably peeling off, a composite (S1C1) from a composite (C2S2AL) that is at least partially attached to an object (O1). The method according to any one of claims 1 to 4, including the method described in any one of claims 1 to 4.

6. The composite (S1C1) prepared in step (1) is used as the embossing mold (e2) of the embossing tool (E2) to transfer the embossed structure of the coating (C1) to the coating composition (C2a) in steps (3-i), (2-ii), and (3-ii). The method according to any one of claims 1 to 5, wherein a mirror image of the structured surface of the coating (C1) of the composite (S1C1) used as an embossing mold (e2) is applied to the surface of a coating (C2) which is at least partially embossed and at least partially cured, and the mirror image of the structured surface of the coating (C2) of the composite (S1C1) used as an embossing mold (e2) is applied to a substrate (S2), and the surface is embossed.

7. The method according to any one of claims 1 to 6, wherein the base material (S1) is a film web, preferably a moving film web or a continuous film web, more preferably a continuous moving film web, and / or the base material (S2) is a film web, preferably a moving film web, more preferably a continuous moving film web.

8. The method according to any one of claims 1 to 7, wherein the composite (S1C1) used in steps (3-i), (2-ii), and (3-ii) is reusable and can be repeatedly used to transfer at least one embossed structure when carrying out step (5i) or (5-ii) of the method.

9. The composite (S1C1) prepared in step (1) is at least, (6) Apply the radiation-curable coating composition (C1a) to at least a portion of the surface of the substrate (S1) to prepare a composite (S1C1a). (7) At least partially embossing a coating composition (C1a) applied to the surface of a substrate (S1) with at least one embossing tool (E1) comprising at least one embossing mold (e1), (8) A coating composition (C1a) that is at least partially applied to a substrate (S1) and at least partially embossed is at least partially cured, wherein the substrate (S1) is in contact with at least one embossing mold (e1) of an embossing tool (E1) throughout the period of at least partial curing. (9) Remove the composite (S1C1) from the embossing mold (e1) of the embossing tool (E1) to prepare a composite (S1C1) that is at least partially embossed and at least partially hardened, or the reverse. The method according to any one of claims 1 to 8, obtained by...

10. The method according to any one of claims 1 to 9, wherein the coating composition (C1a) comprises, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a), at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass, and very preferably 100% by mass, at least one silicone (meth)acrylate oligomer, preferably strictly one silicone (meth)acrylate oligomer, more preferably strictly one silicone (meth)acrylate oligomer having an average of 2 to 3 unsaturated groups.

11. The method according to any one of claims 1 to 10, wherein the coating composition (C1a) comprises a free radical polymerizable monomer, preferably an ethylenically unsaturated monomer, more preferably a polyfunctional ethylenically unsaturated monomer, as a reactive diluent.

12. The coating composition (C1a) comprises at least one reactive diluent, wherein the reactive diluent may be hexanediol diacrylate and a general formula (I) which may be different from each other or at least partially the same. 【Chemistry 1】 (In the formula, Radical R １ They are independent of each other, C ２ -C ８ Alkylene group, very preferably C ２ It is an alkylene group, Radical R ２ These are independently H or methyl, The symbol m is an integer in the range of 1 to 15, very preferably 1 to 4 or 2 to 4, independently of each other, provided that in at least one of the structural units of formula (I), the symbol m is at least 2, preferably strictly 2. The method according to any one of claims 1 to 11, wherein the compound is selected from compounds containing at least two, preferably at least three, and more preferably three, structural units represented by .

13. The method according to any one of claims 1 to 11, wherein the coating composition (C1a) comprises, based on the total mass of the coating composition (C1a), at least one reactive diluent, preferably hexanediol diacrylate and / or a (meth)acrylate derived from hexa-ethoxylated trimethylolpropane, in a total amount of 40 to 95% by mass, preferably 50 to 85% by mass, more preferably 55 to 83% by mass.

14. The method according to any one of claims 1 to 13, wherein the photopolymerization initiator contained in the coating composition (C1a) is selected from diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphine, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, benzophenone, 1-benzoylcyclohexane-1-ol, 2-hydroxy-2,2-dimethylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and mixtures thereof.

15. A composite (S1C1) comprising a substrate (S1) and a coating (C1) that is at least partially embossed and at least partially cured, wherein the coating (C1) can be obtained by at least partially curing a coating composition (C1a) applied to at least a part of the surface of the substrate (S1) and then at least partially embossing it by radiation curing, wherein the coating composition (C1a) is a radiation-curable coating composition, (a) 5 to 45% by mass of at least one crosslinkable polymer and / or oligomer, (b) at least one reactive diluent in an amount of 40 to 95% by mass, (c) 0.01 to 15% by mass of at least one photopolymerization initiator, and (d) At least one additive in 0 to 5% by mass Includes, Here, (i) the total amounts of components (a), (b), (c), and (d) are based on the total mass of the coating composition (C1a), and (ii) the total amount of all components present in the coating composition (C1a) is 100% by mass. Herein, the composite (S1C1) is characterized in that at least one crosslinkable polymer and / or oligomer (a) comprises at least one silicone (meth)acrylate oligomer in a total amount of at least 25% by mass, preferably at least 50% by mass, more preferably at least 90% by mass, and very preferably 100% by mass, based on the total mass of all crosslinkable polymers and / or oligomers contained in the coating composition (C1a).

16. The composite (S1C1) according to claim 15, wherein the radiation-curable coating composition (C1a) contains at least one reactive diluent in an amount of 50 to 95% by mass, or 50 to 85% by mass, or 50 to 83% by mass, based on the total mass of the coating composition (C1a).

17. The composite (S1C1) according to claim 15 or 16, wherein the composite (S1C1) is obtained by carrying out steps (6) to (9) of the method described in claim 9.

18. Use of the composite (S1C1) according to any one of claims 15, 16, or 17 as an embossing mold (e2) for an embossing tool (E2) for transferring an embossed structure to at least a portion of the surface of a coating composition (C2a) or to at least a portion of the surface of a coating composition (C2a) applied at least partially onto a substrate (S2).

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