Micro-cut patterning article and method of making the same

Abstract

A patterned article includes a carrier layer having a microstructured first major surface and an opposing second major surface. The first major surface includes a plurality of upper edges and a plurality of lower edges spaced apart along a thickness direction of the carrier layer and defining respective upper and lower portions of the first major surface. The lower portion is disposed between the upper portion and the second major surface. The article includes a first functional layer disposed on the lower portion but not the upper portion of the first major surface. The first functional layer includes at least one first microcut inorganic layer including a plurality of cut edges substantially coextensive with the plurality of lower edges. A method of making the patterned article is provided. An article that can be made by transferring the functional layer from the patterned article is provided.

Description

Background Technology

[0001] Sputtering is a high-precision vacuum deposition process that can deposit inorganic thin films with single-digit nanometer thickness control over large areas and is suitable for roll-to-roll manufacturing. Sputtering can be used to deposit stacks of inorganic thin film layers, such as metal layers and metal oxide layers, onto a substrate. The materials, thicknesses, and arrangement sequences of the inorganic thin film layers with different refractive indices can be selected to fine-tune the aesthetic appearance and transmission properties of the finished product. Summary of the Invention

[0002] This specification generally relates to patterned articles comprising at least one micro-cut layer and methods for manufacturing such patterned articles.

[0003] In some aspects of this specification, a patterned article is provided. The patterned article includes a carrier layer having a microstructured first main surface and an opposite second main surface. The first main surface includes a plurality of upper edges and a plurality of lower edges spaced apart along the thickness direction of the carrier layer and defining respective upper and lower portions of the first main surface. The lower portion is disposed between the upper portion and the second main surface. The article includes a first functional layer disposed on the lower portion of the first main surface, not the upper portion. The first functional layer includes at least one first micro-cut inorganic layer including a plurality of cut edges substantially co-extending with the plurality of lower edges.

[0004] In some aspects of this specification, a method for manufacturing a patterned article is provided. The method includes providing a transfer article comprising a carrier layer having opposing first and second main surfaces, and a functional layer disposed on the first main surface; providing a tool comprising a plurality of microstructures, each microstructure comprising at least one cutting edge; arranging the transfer article and the tool adjacent to each other such that the functional layer faces the plurality of microstructures; contacting the transfer article with the tool such that the tool embosses and cuts into the transfer article to form a cut pattern in the functional layer and to form a plurality of structures defining an upper and lower portion of the first main surface in the carrier layer. The lower portion is disposed between the upper portion and the second main surface. A first portion of the functional layer is disposed on the upper portion of the first main surface, and a second portion of the functional layer is disposed on the lower portion of the first main surface. The first and second portions of the functional layer are separated from each other along the cut pattern.

[0005] In some aspects of this specification, a patterned article comprising a multilayer film is provided. The multilayer film includes a first polymer layer; a functional layer including opposing first and second main surfaces, wherein the first main surface is disposed on the first polymer layer; and a second polymer layer disposed on the second main surface of the functional layer. The functional layer includes a multilayer stack comprising at least one micro-cut metal layer and at least one metal oxide or metal nitride layer. Each micro-cut metal layer has an average thickness in the range of 5 nanometers to 500 nanometers and includes a notch pattern forming any of the following: (i) a pattern of discretely spaced plates corresponding to and defined by the notch pattern, wherein there is substantially no portion of metal layer disposed between the closest adjacent plates; or (ii) a continuous pattern corresponding to a pattern of discretely spaced plates corresponding to the notch pattern removed from the metal layer.

[0006] These and other aspects will become apparent from the detailed description that follows. However, in no way should this brief overview be construed as limiting the subject matter for which protection may be claimed. Attached Figure Description

[0007] Figure 1 It is a schematic cross-sectional view of the carrier layer according to some implementation schemes.

[0008] Figure 2 It is a schematic cross-sectional view of a patterned article including functional layers according to some implementation schemes.

[0009] Figures 3 to 4 It is a schematic cross-sectional view of a patterned article including a first functional layer and a second functional layer according to some implementation schemes.

[0010] Figure 5A It is a schematic cross-sectional view of another patterned article including a first functional layer and a second functional layer according to some implementation schemes.

[0011] Figure 5B It is based on some implementation schemes corresponding to Figure 5A A schematic cross-sectional view of a patterned article in which the second functional layer has been removed.

[0012] Figures 6 to 8 It is a schematic cross-sectional view of the functional layers according to some implementation schemes.

[0013] Figure 9 This is a schematic top-view plan view of a patterned functional layer according to some implementation schemes, showing the line edge roughness.

[0014] Figures 10A to 10B It is a schematic cross-sectional view of a patterned article including an outer coating according to some implementation schemes.

[0015] Figures 11 to 13 It is a schematic top view of a patterned article including a first functional layer and a second functional layer according to some implementation schemes.

[0016] Figures 14 to 16 It is a schematic top view of a patterned article including functional layers according to some implementation schemes.

[0017] Figure 17 It is a schematic cross-sectional view of the transferred article according to some implementation schemes.

[0018] Figure 18 This is a schematic diagram of a method for manufacturing patterned articles according to some implementation schemes.

[0019] Figure 19 It is a schematic cross-sectional view of the microstructure of a tool for manufacturing patterned articles according to some implementation schemes.

[0020] Figure 20 It is a schematic cross-sectional view of a patterned article including a multilayer film according to some implementation schemes.

[0021] Figure 21 It is a schematic perspective view of an exemplary base with curved surfaces.

[0022] Figure 22 It is a schematic perspective view of a patterned article comprising a multilayer film disposed on a substrate having a curved surface, according to some embodiments. Detailed Implementation

[0023] Reference is made in the following description to the accompanying drawings, which form part of the invention and illustrate various embodiments by way of example. The drawings are not necessarily drawn to scale. It should be understood that other embodiments may be conceived and practiced without departing from the scope or spirit of this specification. Therefore, the following detailed description should not be considered limiting.

[0024] In some aspects, this specification generally relates to transfer articles comprising a dimensionally stable but flexible transfer substrate having a functional layer comprising at least one (e.g., very thin) inorganic layer. In some embodiments, the inorganic layer in the functional layer of the transfer article is formed by a sputtering process and has a thickness of, for example, from about 3 nanometers (nm) to about 2000 nm. According to some embodiments, the transfer article comprising the stable transfer substrate and at least one thin inorganic layer is subsequently contacted with a microstructured tool to emboss the substrate and form a pattern of cut edges in the inorganic layer that accurately corresponds to the pattern of the cutting edge of the tool. The precise pattern of the cut edges can form an array of plate and mesh patterns, wherein the plate and mesh patterns can be disposed in different planes.

[0025] In some embodiments, the patterned article of this specification provides a transferable conductive layer with a thickness of, for example, less than about 3 micrometers, which can be used as a touch sensor or antenna for a wide variety of applications, such as 5G, or for other antenna applications utilizing frequencies in the range of, for example, 0.1 GHz to 300 GHz. In some embodiments, the micro-cut inorganic layer provides a fine-wire conductive mesh material that can be manufactured without multiple post-plating steps. In some embodiments, the patterned article comprising a diffusely reflective micro-cut inorganic layer is stretched and applied to a non-planar or structured surface in at least one dimension. For example, the plate network in the micro-cut inorganic layer can expand by different amounts to accommodate stretching and strain during the application process and conform to the surface. Once applied to the surface, the patterned article forms a micro-cut article with a precisely arranged plate, which is small enough to provide tunable reflective properties with a consistent color and mirror-like aesthetic appearance at a selected viewing angle relative to the main surface of the micro-cut article.

[0026] Because the pattern of the cut edges in a micro-machined inorganic layer can be a faithful reproduction of the pattern on a microstructured tool, the precise arrangement of the plates allows for more precise control over the aesthetic appearance and / or conductivity of articles comprising stacks of inorganic materials when the article is stretched and applied or adhesively bonded to a composite surface in one or more directions to form a laminated article. For example, micromachining of the inorganic layer can also enable the inorganic layer to transmit electromagnetic signals within a desired frequency range, which could allow the article to be used in communication devices.

[0027] Figure 1 This is a schematic cross-sectional view of the carrier layer 110 according to some implementation schemes. Figures 2 to 3This is a schematic cross-sectional view of patterned articles 100 and 100' according to some embodiments. In some embodiments, the patterned articles 100, 100' include a carrier layer 110, which includes a microstructured first main surface 112 and an opposing second main surface 114. The first main surface 112 includes a plurality of upper edges 121 and lower edges 123, which are spaced apart along the thickness direction of the carrier layer 110 (refer to the z-direction of the xyz coordinate system illustrated) and define respective upper portions 125 and lower portions 127 of the first main surface 112, wherein the lower portions 127 are disposed between the upper portions 125 and the second main surface 114. In some embodiments, the upper portions 125 and lower portions 127 are arranged with corresponding first and second regular patterns (e.g., a grid pattern and a regular pattern of spaced-apart plates, as further described elsewhere herein). Patterned articles 100, 100' include a first functional layer 130 disposed on the lower portion (127) of a first main surface 112, rather than the upper portion (125). The first functional layer 130 includes at least one first micro-cut inorganic layer 131, which includes a plurality of cut edges 133 substantially co-extending with the plurality of lower edges 123. The first functional layer 130 may be a single first micro-cut inorganic layer 131 or may include a plurality of layers as further described elsewhere herein.

[0028] In some embodiments, the patterned article 100' further includes a second functional layer 230 disposed on the upper portion (125) rather than the lower portion (127) of the first main surface 112, wherein the second functional layer 230 includes at least one second micro-cutting inorganic layer 231, the at least one second micro-cutting inorganic layer including a plurality of cut edges 233 substantially co-extending with a plurality of upper edges 121. The second functional layer 230 may be a single second micro-cutting inorganic layer 231 or may include a plurality of layers as further described elsewhere herein.

[0029] In some embodiments, the cut edges 133 and / or 233 are arranged in a regular pattern (e.g., a regular pattern of straight line segments). In some embodiments, the cut edges 133 and / or 233 may have a linear shape and may be arranged as a plurality of substantially parallel (e.g., parallel at 20 degrees, or within 10 degrees, or parallel at 5 degrees) line segments (see example...). Figures 11 to 16 ), or arranged into multiple substantially parallel first line segments (e.g., parallel to Figures 11 to 15 The x-direction) and a second line segment that is substantially parallel to the first line segment (e.g., at 20 degrees, or within 10 degrees, or at 5 degrees). Figures 11 to 15 (in the y-direction). In various embodiments, the cut edges 133, 233 (e.g., the total number of cutting line segments of the first functional layer 130 and (when present) the second functional layer 230) are spaced at a rate of 1 mm. 2Approximately 0.3 to approximately 2000, or per mm 2 Approximately 1 to approximately 1000, or per mm 2 Approximately 10 to approximately 500, or per mm 2 Approximately 20 to approximately 200, or per mm 2 Approximately 50 to approximately 100 exist on the first main surface 112.

[0030] Microstructures are typically structures having a width ranging from about 0.1 micrometers to about 2000 micrometers in each of at least two orthogonal dimensions (e.g., height and width). Microcutting layers generally refer to layers with notches that define elements of the layer having at least one dimension ranging from about 0.1 micrometers to about 2000 micrometers in the plane of the layer. Layers can be microcut using tools with microstructures, where each microstructure has at least one cutting edge. Such tools can be made using conventional micromachining processes (e.g., cutting microstructured diamond into cylindrical rolls using diamond cutting tools made by focused ion milling). For example, cutting tools for micromachining and methods of manufacturing such cutting tools are described in, for example, U.S. Patent Nos. 7,140,812 (Bryan et al.) and 8,443,704 (Burke et al.). Microcutting typically produces a width (e.g., corresponding to...) Figure 19 The tip width Wt, schematically shown, is greater than the minimum lateral dimension of the element formed by micro-machining (e.g., Figure 19 The diagram schematically illustrates a sharp cut edge with a width (W1) much smaller (e.g., at least twice, four times, or eight times smaller). Such a cut may be referred to as a micro-cut. For example, cut edge 133 and / or cut edge 233 may be micro-cut edges.

[0031] A functional layer including at least one micro-cutting layer can be referred to as a micro-cutting functional layer. In some embodiments, each of the functional layers 130 and 230 is a micro-cutting layer having a cut pattern substantially the same as that of the corresponding micro-cutting inorganic layer.

[0032] The cut edges (e.g., cut edges 133 and 233) of layers (e.g., inorganic layers 131 and 231) disposed on the upper (125) or lower (127) portion of the first main surface 112 may refer to the edges between the sidewalls of the layer and the main surfaces of the layer facing the upper (125) or lower (127) portion of the first main surface 112. Alternatively, the cut edges of the layer may refer to the side edges of the layer extending between the upper and lower main surfaces of the layer. When, in a top plan view, at least 60% of the total length of each of the plurality of edges extends along at least 60% of the total length of the other plurality of edges, the plurality of edges (e.g., 133, 233) may be described as substantially co-extending with the other plurality of edges (e.g., 123, 121). In some embodiments, at least 70%, or at least 80%, or at least 90%, or at least 95% of the total length of each of the plurality of edges extends along at least 70%, or at least 80%, or at least 90%, or at least 95% of the total length of the other plurality of edges.

[0033] In various embodiments, a functional layer (e.g., functional layer 130 or 230) may comprise a stack of one or more layers selected to provide a functional property to an article of manufacture including the functional layer, such functional properties including, for example, electromagnetic properties, which may include, for example, conductive properties or reflective or transmissive properties, aesthetic properties, environmental properties or antimicrobial properties.

[0034] In some embodiments, the patterned article 100' is configured such that the second functional layer 230 can be transferred from the carrier layer 110 to the first adhesive layer 267 (see, for example...). Figure 18 This leaves the first functional layer 130 disposed on the carrier layer 110. For example, after the second functional layer 230 has been transferred, the patterned article 100' can then correspond to the patterned article 100. In some embodiments, the patterned article 100 is configured such that the first functional layer 230 can be transferred from the carrier layer 110 to the adhesive layer 268 (see, for example...). Figure 18 In some embodiments, the patterned article 100' is a transfer article configured such that the second functional layer 230 can be transferred from the carrier layer 110 to the first adhesive layer 267, thereby leaving the first functional layer 130 disposed on the carrier layer 110, such that the first functional layer 130 can be transferred from the carrier layer 110 to the second adhesive layer 268. As further described elsewhere herein, the carrier layer 110 may include a release coating to facilitate the transfer of the first functional layer 130 and the second functional layer 230.

[0035] In some embodiments, the first main surface 112 of the carrier layer 110 includes a plurality of structures 129 having an average width W0 along at least one direction and defining gaps therebetween having an average width W1 along at least one direction. The plurality of structures 129 have an average height h0, and the first functional layer has an average thickness t0. The second functional layer 230 may have an average thickness substantially the same as the average thickness t0 of the first functional layer 130 (e.g., within 10%, within 5%, or within 3%). The average height h0 may be greater than the average thickness t0, such as... Figures 2 to 3 This is shown schematically, or it may be approximately the same as the average thickness t0, such as... Figure 4 This is schematically shown, or may be less than the average thickness t0, such as... Figures 5A to 5B Schematic illustration. In some embodiments, the average spacing (h0) between the upper portion (125) and the lower portion (127) along the thickness direction (z-direction) of the carrier layer 110 is greater than the average thickness t0 of the first functional layer 130. In some embodiments, the average spacing (h0) between the upper portion (125) and the lower portion (127) along the thickness direction (z-direction) of the carrier layer 110 is less than the average thickness t0 of the first functional layer 130'. In some embodiments, the average spacing (h0) between the upper portion (125) and the lower portion (127) along the thickness direction (z-direction) of the carrier layer 110 is within 10% of the average thickness t0 of the first functional layer 130'. Figure 4 and Figure 5A These are schematic cross-sectional views of patterned articles 102 and 104, respectively. Except for the thickness of the functional layer, these patterned articles may correspond to patterned article 100'. Figure 5B This is a schematic cross-sectional view of patterned article 104', which corresponds to patterned article 104 except that functional layer 230” has been removed. In patterned article 102, functional layers 130’ and 230’ each have an average thickness that is approximately the same as the average spacing (h0) of the upper (125) and lower (127) along the thickness direction (z-direction) of the carrier layer 110. In patterned article 104, functional layers 130” and 230” each have an average thickness greater than the average spacing (h0) of the upper (125) and lower (127) along the thickness direction (z-direction) of the carrier layer 110.

[0036] In some embodiments, when the patterned article 100 is disposed on the flat surface 174, the upper portion (125) and the lower portion (127) of the first main surface 112 are disposed in corresponding first planes 176 and 178 that are separated from each other (e.g., separated by an average interval h0) along the thickness direction (z direction) of the carrier layer 110.

[0037] In some embodiments, the average spacing (h0) between the upper portion (125) and the lower portion (127) along the thickness direction (z-direction) of the carrier layer 110 is at least 0.3 micrometers, or at least 0.5 micrometers, or at least 0.7 micrometers. In some such embodiments or in others, the average spacing (h0) between the upper portion (125) and the lower portion (127) along the thickness direction (z-direction) of the carrier layer is no greater than 10 micrometers, or no greater than 5 micrometers, or no greater than 3 micrometers, or no greater than 2 micrometers, or no greater than 1.5 micrometers. For example, the average spacing can be in the range of 0.3 micrometers to 10 micrometers, or 0.5 micrometers to 5 micrometers, or 0.5 micrometers to 3 micrometers, or 0.7 micrometers to 2 micrometers. In some embodiments, the first functional layer and / or the second functional layer has a thickness in the range of 100 nm to 2000 nm. In some embodiments, the patterned article (e.g., 100, 100', 102, 104, or 104') has a thickness T1 of, for example, less than 10 micrometers, less than 5 micrometers, or less than 3 micrometers. For example, the thickness T1 of the patterned article may be greater than 0.5 micrometers.

[0038] Figures 6 to 8 This is a schematic cross-sectional view of functional layers 330, 330', and 330" which may correspond to functional layer 130 or 230 (e.g., in some embodiments, functional layers 130 and 230 may be obtained by micro-machining functional layers 330, 330', or 330" as further described elsewhere herein). Functional layer 330 includes layers 331a, 331b, and 331c and has opposing first outermost main surfaces 303 and 305. In some embodiments, layers 331a, 331b, and 331c include at least one metal layer and at least one metal oxide or metal nitride layer. Functional layer 330' has opposing first outermost main surfaces 303' and 305' and includes functional layer 330 disposed between first layer 431a and second layer 431b. First layer 431a and second layer 431b may be a first organic layer and a second organic layer and / or a first polymer layer and a second polymer layer. The polymer layer can be understood as an organic polymer layer unless otherwise specified. Functional layer 330” includes a first layer 431a and a second layer 431b, and at least layers 331a to 331f disposed between the first layer 431a and the second layer 431b. In some embodiments, the functional layer includes a plurality of inorganic layers (e.g., at least one metal layer and at least one metal oxide layer). In some embodiments, each inorganic layer of the functional layer has a thickness of, for example, from about 1 nm to about 500 nm, or from about 1 nm to about 250 nm, or from about 3 nm to about 200 nm, or from about 5 nm to about 100 nm, or from about 10 nm to about 50 nm.

[0039] In some embodiments, the functional layer (or, for example, the first functional layer 130 and / or the second functional layer 230) may include at least one organic layer and at least one inorganic layer. For example, a patterned article may include a first functional layer comprising at least one first micro-cut inorganic layer and at least one micro-cut organic layer substantially co-elongating with the first micro-cut inorganic layer. The patterned article may also include a second functional layer comprising at least one second micro-cut inorganic layer and at least one micro-cut organic layer substantially co-elongating with the second micro-cut inorganic layer. The patterning techniques described herein can be applied in a single step (e.g., using tool 333) to a functional layer comprising at least one organic layer and at least one inorganic layer, as opposed to conventional patterning techniques where the organic and inorganic layers are patterned in separate steps (e.g., etching). For example, the functional layer may include a metal layer disposed between polymer layers. For example, it has been found that including a polymer layer with a metal layer in a functional layer can improve the mechanical robustness of the functional layer during processing.

[0040] In some embodiments, the functional layer comprises at least two metal layers. In some embodiments, the functional layer comprises at least two metal oxide layers, or at least two metal nitride layers, or at least one metal oxide layer and at least one metal nitride layer. For example, for any of the functional layers 330, 330', or 330'", layer 331a may be a metal layer, layer 331b may be a metal oxide layer or a metal nitride layer, and layer 331c may be a metal layer; or layer 331a may be a metal oxide layer or a metal nitride layer, layer 331b may be a metal, and layer 331c may be a metal oxide layer or a metal nitride layer. In some embodiments of functional layer 330', layer 331a is a metal layer, layer 331b is a metal oxide layer, layer 331c is a polymer layer, layer 331d is a metal oxide layer, layer 331e is a metal layer, and layer 331f is a metal oxide layer. In some embodiments, one or more of these metal oxide layers are replaced by metal nitride layers. Other suitable functional layers are described, for example, in International Application Publication No. WO2020 / 240419 (Gotrik et al.).

[0041] In some embodiments, at least one of the first polymer layer 431a and the second polymer layer 431b comprises or is formed of acrylate or acrylamide. In some embodiments, the first polymer layer 431a and the second polymer layer 431b are or comprise respective first acrylate layer and second acrylate layer.

[0042] Metals suitable for the metal layer include, for example, copper, aluminum, silver, gold, titanium, indium, tin, zinc, zirconium, and their alloys. Oxides suitable for the metal oxide layer include aluminum oxide, silicon oxide, aluminum silicate, aluminum-silicon oxynitride, CuO, silver oxide, TiO2, ITO, ZnO, zinc aluminum oxide, ZrO2, and yttrium-stabilized zirconium oxide. Suitable nitrides include, for example, aluminum-silicon nitride, Si3N4, and TiN. Any metal oxide or nitride described herein for the metal layer may be used in oxide or nitride layers. Because silicon is a quasi-metal, silicon oxide will be considered a metal oxide and silicon nitride will be considered a metal nitride as used herein.

[0043] In some embodiments, the functional layer (e.g., functional layers 130, 230, 330, 330', or 330" or another functional layer described elsewhere herein) includes at least one micro-machined metal layer. In some embodiments, the at least one micro-machined metal layer includes or is formed of silver. For example, layer 331b may be a silver layer, and each of layers 331a and 331b may be a metal oxide layer. For example, an oxide-protected silver layer can be used in plasma applications. In some embodiments, the micro-machined functional layer includes an oxide-protected silver layer between polymer layers (e.g., layers 431a and 431b). According to some embodiments, the method of this specification allows for the patterning of a functional layer including an oxide-protected silver layer and a polymer layer by micromachining. It has been found difficult to fabricate patterned functional layers including an oxide-protected silver layer and a polymer layer using conventional techniques (e.g., dry or wet lithography).

[0044] The line edge roughness of the cut edge can be substantially less than that produced by conventional patterning processes such as stripping lithography. Figure 9This is a schematic top plan view of a patterned functional layer according to some embodiments, illustrating line edge roughness. The roughness parameter Ra can be used for line edge roughness. For example, edge 747 has a line edge roughness Ra, which can be described as the average of the absolute values ​​of the displacement of edge 747 from its average position 888. In some embodiments, the average line edge roughness Ra of multiple notched edges and / or notched patterns can be less than 1 micrometer, or less than 500 nm, or less than 100 nm, and can be as low as, for example, 10 nm. In some embodiments, the patterned article includes at least one first micro-machining inorganic layer (e.g., disposed on the lower portion of the microstructured master surface), which includes multiple notched edges with an average line edge roughness Ra of less than 1 micrometer or within the range described elsewhere herein. In some embodiments, the patterned article also includes at least one second micro-machining inorganic layer (e.g., disposed on the upper portion of the microstructured master surface), which includes multiple notched edges with an average line edge roughness Ra of less than 1 micrometer or within the range described elsewhere herein. In some embodiments, the patterned article comprises at least one micro-cut metal layer, wherein each micro-cut metal layer has a notch pattern. In some embodiments, for each micro-cut metal layer, the average line edge roughness Ra of the notch pattern is less than about 1 micrometer or within the range described elsewhere herein.

[0045] The functional layers 330, 330', and 330" can be applied by, for example, reactive evaporation, (e.g., reactive) sputtering, chemical vapor deposition, plasma-enhanced chemical vapor deposition, and / or atomic layer deposition. Suitable methods for forming functional layers are described, for example, in U.S. Patent Application Publication No. 2012 / 0208033 (Weigel et al.) and U.S. Patent Nos. 4,696,719 (Bischoff); 4,722,515 (Ham); 4,842,893 (Yializis et al.); 4,954,371 (Yializis); and 5,018,048 (Shaw et al.). ); 5,032,461 (Shaw et al.); 5,097,800 (Shaw et al.); 5,125,138 (Shaw et al.); 5,440,446 (Shaw et al.); 5,547,908 (Furuzawa et al.); 6,045,864 (Lyons et al.); 6,231,939 (Shaw et al.); 6,214,422 (Yializis); 8,658,248 (Anderson et al.); 9,034,459 (Condo et al.); and 10,693,024 (Weigel et al.).

[0046] Any of the patterned articles 100, 100', 102, 104, 104' may further include an outer coating disposed on the first main surface 112. Figures 10A to 10B Patterned articles 101 and 101' are schematically shown, including corresponding outer coatings 111 and 111' disposed on respective patterned articles 100 and 100'. Outer coatings 111, 111' may be provided to modify dielectric properties and / or protect functional layers. For example, in some embodiments, outer coatings 111, 111' may be adapted to be transferred together with functional layers 130 and / or 230 (e.g., in some embodiments, the outer coating is a conformal coating that can be transferred together with the functional layer). In other embodiments, outer coatings 111, 111' may be provided when, for example, the corresponding patterned articles 100, 100' are not intended to be used as transfer articles.

[0047] Figures 11 to 13 This is a schematic top plan view of a patterned article including a plurality of spaced-apart plates 444 separated from each other along a pattern 433 and a continuous pattern 448 (e.g., a grid pattern). The plates 444 may correspond to one of the first functional layers 130 and the second functional layer 230 (or one of the first inorganic layers 131 and the second inorganic layer 231), and the pattern 448 may correspond to the other functional layer of the first functional layer 130 and the second functional layer 230 (or the other inorganic layer of the first inorganic layer 131 and the second inorganic layer 231). In some embodiments, at least one second micro-cut inorganic layer 231 includes a plurality of spaced-apart plates 444. In some such embodiments or other embodiments, at least one first micro-cut inorganic layer 131 includes a grid pattern. In some embodiments, at least one second micro-cut inorganic layer 231 includes a grid pattern 448. In some such embodiments or other embodiments, at least one first micro-cut inorganic layer 131 includes a plurality of spaced-apart plates 444. In various implementations, the exposed surface of plate 444 may be substantially flat or may have a wavy shape.

[0048] Figure 14 It is a schematic top plan view of a plurality of spaced-apart plates 444 that may correspond to a patterned article (e.g., patterned article 100) after the second functional layer 230, which is arranged in a grid pattern, has been removed, or may correspond to the second functional layer after the second functional layer 230, which is arranged in a pattern of plates, has been transferred from the patterned article (e.g., patterned article 100') (e.g., to an adhesive layer).

[0049] Figure 15is a schematic top plan view of a grid pattern 448 that can correspond to a patterned article (e.g., patterned article 100) after a second functional layer 230 provided in a pattern of spaced-apart plates has been removed, or can correspond to the second functional layer after the second functional layer 230 provided in a grid has been transferred (e.g., transferred to an adhesive layer) from a patterned article (e.g., patterned article 100').

[0050] The plates 444 have in-plane dimensions Wa and Wb that are orthogonal, and the grid pattern 448 has a line width Wc. In some embodiments, at least one of Wa and Wb is less than 2000 microns, or less than 1000 microns, or less than 500 microns, or less than 250 microns, or less than 150 microns, or less than 100 microns. In some such embodiments or in other embodiments, each of Wa and Wb is at least 10 microns or at least 20 microns. In some embodiments, 0.2 < Wa / Wb < 5 or 0.25 < Wa / Wb < 4 or 1 / 3 < Wa / Wb < 3. In some embodiments, the line width Wc is at least 0.25 microns, or at least 0.5 microns, or at least 1 micron, or at least 2 microns or at least 3 microns. In some such embodiments or in other embodiments, the line width Wc is no greater than 100 microns, or no greater than 50 microns, or no greater than 30 microns, or no greater than 20 microns, or no greater than 10 microns. For example, in some embodiments, the line width Wc is in the range of 0.5 microns to 50 microns, or 1 micron to 50 microns, or 2 microns to 30 microns, or 2 microns to 20 microns. In some embodiments, the center-to-center spacing between the plates 444 (along the x direction and / or along the y direction) is less than 2000 microns, or less than 1000 microns, or less than 500 microns, or less than 250 microns, or less than 150 microns, or less than 100 microns. In embodiments where the plates 444 are rectangular, Wa and Wb are the width and length of the rectangular shape, which can be a square shape since a square is a special rectangle. The plates 444 can have any other suitable shape, such as circular or oval. For a general shape, Wa can be taken as the length of the shortest in-plane line that extends completely across the shape and passes through the centroid of the shape, and Wb can be understood as the maximum dimension of the shape in a direction in a plane orthogonal to the shortest in-plane line.

[0051] Figure 16This is a schematic top plan view of a plurality of spaced-apart strips 544 extending along the same first direction (y-direction). The strips 544 may correspond to a first functional layer 130 or a second functional layer 230, or may correspond to at least one first micro-machining inorganic layer or at least one second micro-machining inorganic layer. In some embodiments, at least one first micro-machining inorganic layer 131 comprises a plurality of spaced-apart strips 544 extending along the same first direction (y-direction). In some embodiments, at least one second micro-machining inorganic layer 231 comprises a plurality of spaced-apart strips 544 extending along the same first direction (y-direction). The strips 544 may be considered as plates having a large aspect ratio (e.g., Wb / Wa > 5 or Wb / Wa > 10).

[0052] In some implementations, in a top view (along the negative z-direction), the total area of ​​the lower portion 127 does not exceed 50% of the total area of ​​the first main surface 112. For example, Figure 12 The grid pattern 448 can be set on the lower part 127. As another example, Figure 13 The plate 444 may be disposed on the lower portion 127. In a top plan view, the total area of ​​the first main surface 112 includes the areas of the upper portion 125 and the lower portion 127, but excludes the area of ​​the vertical sidewalls. In some embodiments, in a top plan view, the total area of ​​the lower portion is less than 50% or less than 40%, or less than 30%, or less than 20%, or less than 10% of the total area of ​​the first main surface. In some such embodiments or in other embodiments, in a top plan view, the total area of ​​the lower portion 127 is at least 0.01%, or at least 0.1%, or at least 0.5%, or at least 1%, or at least 2% of the total area of ​​the first main surface. In some embodiments, the second functional layer 230 is transferred from the carrier layer 110, thereby leaving the first functional layer 130 disposed on the lower portion 127, which can then be transferred to another layer. In some embodiments, it may be desirable for the article including the first functional layer (e.g., disposed on the lower portion 127 or transferred to another layer) to have light-transmitting properties. In some or other implementations, it is preferable that, in a top plan view, the total area of ​​the lower portion 127 is less than 10% of the total area of ​​the first main surface 112. For example, in a top plan view, the total area of ​​the lower portion 127 may be about 8% or less of the total area of ​​the first main surface 112.

[0053] In some embodiments, the first functional layer 130 and / or the second functional layer 230 are free of cracks or substantially free of cracks. In some embodiments, the first micro-cutting inorganic layer 131 and / or the second micro-cutting inorganic layer 231 are free of cracks or substantially free of cracks. A layer can be described as substantially free of cracks when cracks are not visible to the human eye at 10 cm intervals (visible to a person with 20 / 20 visual acuity under normal indoor lighting conditions as described in UNE-EN 12464-1:2012). Cracks are different from notches because cutting leaves features different from cracks (e.g., tool marks). In some embodiments, the first inorganic layer 131 and / or the second inorganic layer 231 include multiple notch (e.g., micro-notches) edges and there are no cracks extending between the different notch edges.

[0054] In some embodiments, the patterned article is configured such that the first functional layer 130 and / or the second functional layer 230 can be transferred from the carrier layer 110 to the adhesive layer (see, for example...). Figure 18 The transfer product (267 or 268 in the text). Figure 17 This is a schematic cross-sectional view of a transfer article 200, which can be used to manufacture patterned articles as further described elsewhere herein and includes a carrier layer 210 that may correspond to carrier layer 110 prior to patterning. The transfer article 200 includes a functional layer 430 (e.g., corresponding to functional layer 130 or 230 or another functional layer described elsewhere herein) and a carrier layer 210, which includes a substrate 226 and a release coating 228 disposed on the substrate 226 and facing the functional layer 430 (or, for example, the first functional layer 130 and / or the second functional layer 230). The substrate 226 may be a monolithic substrate or may include two or more layers 226a and 226b, such as... Figure 17The diagram is schematically shown. In some embodiments, substrate 226 comprises polyethylene terephthalate (PET) or biaxially oriented polypropylene (BOPP), or is formed from PET or BOPP. For example, PET may be uniaxially or biaxially oriented. In some embodiments, release coating 228 is or comprises a metal layer or a doped semiconductor layer. The metal layer may conveniently be formed from Al, Zr, Cu, NiCr, NiFe, Ti, or Nb, and may have a thickness of, for example, from about 3 nm to about 3000 nm. For example, the doped semiconductor layer may be formed from Si, B-doped Si, Al-doped Si, or P-doped Si with a thickness of about 3 nm to about 3000 nm. A particularly suitable doped semiconductor layer for the release layer is Al-doped Si, wherein the Al component percentage is about 10%. In some such embodiments or in other embodiments, the peel value between release coating 228 and functional layer 430 is 2 g / in to 50 g / in. In some embodiments, carrier layer 110 or 210 is or comprises aluminum-coated PET or aluminum-coated BOPP. The release layer can be prepared by, for example, evaporation, reactive evaporation, sputtering, reactive sputtering, chemical vapor deposition, plasma-enhanced chemical vapor deposition, or atomic layer deposition. Other suitable substrates for release coating are described in International Application Publication No. WO2020 / 240419 (Gotrik et al.).

[0055] The substrate 226 of the carrier layer 210 may be or include a low-modulus layer (e.g., a layer with a Young's modulus in the range of 50 MPa to 1000 MPa, or 100 MPa to 500 MPa). For example, the substrate may include a first polymer layer 226a (e.g., a PET or BOPP layer) facing the functional layer 430 and disposed on the second polymer layer 226b, which may be a low-modulus layer. The low-modulus layer may be an acrylic adhesive, such as an acrylic pressure-sensitive adhesive. For example, a low-modulus layer can reduce the pressure required to complete the patterning process and can improve the accuracy of replicating cutting edge patterns from micro-cutting tools. In other embodiments, the substrate 226 may be, for example, a monolithic PET or BOPP film.

[0056] Figure 18This is a schematic cross-sectional view of a method for manufacturing patterned articles 300 (e.g., corresponding to patterned article 100 or another patterned article described elsewhere herein) or 300' (e.g., corresponding to patterned article 100' or another patterned article described elsewhere herein) and transferring the functional layers of the resulting patterned articles 300, 300' to other layers to form patterned articles 301 and 302. Break symbols 776 and 777 are included to indicate that processes to the left and right of break symbols 776, 777 can be performed on the same or different (e.g., consecutive roll-to-roll) process lines. In some embodiments, the portion to the right of break symbol 776 is omitted (or performed as a separate process), and the method is a method for manufacturing patterned article 300. In some embodiments, the portion to the right of break symbol 777 is omitted (or performed as a separate process), and the method is a method for manufacturing patterned articles 300' and / or patterned article 301. In some embodiments, the method is a method for manufacturing patterned articles 301 and / or 302.

[0057] In some embodiments, a method for manufacturing patterned articles 300, 300', 301, and / or 302 (or 100, 100', or another patterned article described elsewhere herein) is provided. The method may include providing a transfer article 200, wherein the transfer article includes a carrier layer 210 having opposing first main surfaces 212 and second main surfaces 214, and includes a functional layer 430 disposed on the first main surface 212. The method may also include providing a tool 333 including a plurality of microstructures 335, wherein each microstructure includes at least one cutting edge 337; arranging the transfer article 200 and the tool 333 adjacent to each other such that the functional layer 430 faces the plurality of microstructures 335; and contacting the transfer article 200 with the tool 333 such that the tool 333 embosses and cuts into the transfer article to form a pattern of cuts 433 in the functional layer 430 and to form a plurality of structures 255 in the carrier layer defining an upper portion 225 and a lower portion 227 of the first main surface 212. The lower portion 227 is disposed between the upper portion 225 and the second main surface 214. A first portion 630 of the functional layer 430 is disposed on the upper portion 225 of the first main surface 212, and a second portion 730 of the functional layer 430 is disposed on the lower portion 227 of the first main surface 212. The first portion 630 and the second portion 730 of the functional layer 430 are separated from each other along the pattern of the cut 433. For example, the first portion 630 and the second portion 730 of the functional layer 430 may correspond to the second functional layer 230 and the first functional layer 130, respectively. For example, when the second portion 730 comprises a circular or elliptical plate, at least one cutting edge 337 may be a single continuous cutting edge, or when the second portion is a rectangular plate, at least one cutting edge 337 may include at least two opposing cutting edges (e.g., opposing first and second cutting edges, and opposing third and fourth cutting edges).

[0058] The steps of bringing the transfer article 200 into contact with the tool 333 such that the tool 333 embosses and cuts into the transfer article to form a pattern of cuts 433 in the functional layer 430 and to form a plurality of structures 255 defining the upper portion 225 and the lower portion 227 of the first main surface 212 in the carrier layer can be performed at elevated temperatures (e.g., 80 to 120°C) and / or using increased tool force (e.g., 500 to 20,000 pounds per foot of tool width), as this has been found to provide improved cutting and separation between the upper and lower portions.

[0059] In some embodiments, the patterned article 300 is a transfer article configured such that a first portion 630 of the functional layer 430 can be transferred from the carrier layer 210 to the first adhesive layer 267, thereby leaving a second portion 730 of the functional layer 430 disposed on the carrier layer 210, such that the second portion 730 of the functional layer 430 can be transferred from the carrier layer 210 to the second adhesive layer 268.

[0060] Figure 18 The arrows indicate the directions of movement of tool 333 and various rollers and films or other articles during the implementation of the method. Roller 341 may be disposed on the side of the transfer article 200 opposite to tool 333, which may be a generally cylindrical tool. In some embodiments, the method includes transferring a first portion 630 to a first adhesive layer 267 to form a patterned article 301, the patterned article including a layer 277 disposed on the first adhesive layer 267 opposite to the transferred first portion 630. Layer 277 may be, for example, a release layer. Roller 342 may be used in this step. In some embodiments, the method includes transferring a second portion 730 to a second adhesive layer 268 to form a patterned article 302, the patterned article including a layer 278 disposed on the second adhesive layer 268 opposite to the transferred second portion 730. Layer 278 may be, for example, a release layer. Roller 343 may be used in this step.

[0061] In some embodiments, functional layer 430 is an inorganic layer. In other embodiments, functional layer 430 is an organic layer. In some embodiments, functional layer 430 includes at least one inorganic layer (e.g., at least one of layers 331a to 331f) and / or functional layer includes at least one organic layer (e.g., at least one of layers 431a and 431b).

[0062] As further described elsewhere herein, in some embodiments, one of the upper portion 225 or the lower portion 227 includes a grid pattern 448 having an average linewidth Wc ranging from 0.5 micrometers to 50 micrometers, or Wc may be within another range described elsewhere herein. In some embodiments, in a top plan view, the lower portion 227 has a total area less than 50% of the total area of ​​the first main surface 212, or the total area of ​​the lower portion 227 may be within any range described elsewhere herein. In some embodiments, the functional layer 430 has a thickness ranging from 100 nm to 2000 nm, and the patterned articles 300, 300', 301, or 302 may have a thickness, for example, less than 10 micrometers, less than 5 micrometers, or less than 3 micrometers. In some embodiments, the plurality of microstructures 335 have an average width W1, for example, ranging from 0.5 micrometers to 10 micrometers. In some embodiments, the plurality of microstructures 335 have an average height h1, for example, ranging from 0.5 micrometers to 50 micrometers, or from 0.5 micrometers to 20 micrometers, or from 0.5 micrometers to 10 micrometers.

[0063] Figure 19 This is a schematic cross-sectional view of the microstructure 535 of the tool. For example, this microstructure may correspond to the microstructure 335 of tool 333. Microstructure 535 has opposing cutting edges 437 adapted to cut elements having a width W1 in a layer. The cutting edge 437 has a tip width Wt, which may be twice the radius of curvature of the tip. In some embodiments, the tip width Wt may be, for example, less than about 1 micrometer, or less than about 0.5 micrometers, or less than about 0.3 micrometers. In some such embodiments or in other embodiments, the tip width Wt may be, for example, greater than about 0.01 micrometers or greater than about 0.05 micrometers.

[0064] Patterned articles 301 and / or 302 can be used to manufacture additional patterned articles by removing layers 277 or 278 and adhering the exposed surface of adhesive layers 267 or 268 to another surface. Alternatively or otherwise, additional patterned articles can be manufactured by adhering additional layers to patterned articles 301 and / or 302.

[0065] Figure 20It is a schematic cross-sectional view of a patterned article 501 according to some implementation schemes. The patterned article 501 includes a multilayer film 500 comprising a first polymer layer 431a; a functional layer 530 comprising opposing first and second main surfaces 503 and 505 (e.g., corresponding to 303 and 305), wherein the first main surface 503 is disposed on the first polymer layer 431a, and wherein the functional layer 530 comprises a multilayer stack (e.g., corresponding to 330 or 330” in the portion between layers 431a and 431b), the multilayer stack comprising at least one micro-cut metal layer (e.g., one of 331a, 331b, or 331c) and at least one metal oxide or metal nitride layer (e.g., different one of 331a, 331b, and 331c); and a second polymer layer 431b disposed on the second main surface of the functional layer. Each micro-cut metal layer may have an average thickness in the range of 5 nm to 500 nm or 10 nm to 250 nm, and The pattern includes a notch 433, which is formed as: (i) a pattern of discretely spaced plates 444 (or 544) corresponding to and defined by the notch 433, wherein there is substantially no metal layer between the nearest adjacent plates 444a and 444b (e.g., any metal initially present in the space 548 between plates 444a and 444b after the cutting of the functional layer can be removed, with possible exceptions being small amounts of metal, such as metal flakes or trace amounts, left when the metal initially present in the space 548 is removed), or (ii) a continuous pattern 448 corresponding to the pattern of the discretely spaced plates 444 corresponding to the pattern of the notch 433 removed from the metal layer. At least one metal oxide or metal nitride layer may be at least one micro-cut metal oxide or metal nitride layer and may have a notch pattern substantially the same as that of at least one micro-cut metal layer.

[0066] In some embodiments, the multilayer film 500 further includes a first adhesive layer 511 disposed on the first polymer layer 431a; a first polymer film layer 521 disposed on the first adhesive layer 511; a second adhesive layer 512 disposed on the second polymer layer 431b; and a second polymer film layer 522 disposed on the second adhesive layer 512. For example, the first adhesive layer 511 may correspond to Figure 18 One of the adhesive layers 267 and 268 is schematically shown, and the first polymer film layer 521 may correspond to Figure 18One of layers 277 and 278, schematically shown, or layers 277 or 278, may be a release liner that is removed and replaced with a film layer permanently bonded to the adhesive layer. A second adhesive layer 512 and a second polymer film layer 522 may then be attached to the second polymer layer 431b. For example, a second adhesive layer 512 and a second polymer film layer 522 may be added to protect the functional layer 530. In some embodiments, the second adhesive layer 512 and / or the second polymer film layer 522 are optically transparent (e.g., at least 80% transmittance and no more than 10% haze as measured, for example, ASTM D1003-13 "Standard Test Method for Haze and Luminous Transmittance of Transparent Plastics"). In some such embodiments or in others, the first adhesive layer 511 and / or the first polymer film layer 521 are optically transparent. In some embodiments, the first polymer film layer 521 is a release liner that is removed, for example, before the multilayer film is applied to the substrate. Layers 522, 512 and / or 521 may be omitted optionally.

[0067] Figure 21 This is a schematic perspective view of base 550, and Figure 22 This is a schematic perspective view of a patterned article 1000 including a multilayer film 500 disposed on a portion 555 of the main surface 551 of a substrate 550. In some embodiments, the patterned article 1000 includes a substrate 550, with the multilayer film 500 disposed on and substantially conforming to at least a portion 555 of the main surface 551 of the substrate. The portion 555 of the main surface 551 may be nonplanar and / or may be bent about two mutually orthogonal axes (e.g., x' and y' axes). The shape bent about the two mutually orthogonal axes may alternatively or otherwise be referred to as a shape having a composite curvature. In some embodiments, the multilayer film 500 is stretched and shaped such that the multilayer film 500 substantially conforms to at least a portion 555 of the main surface 551 of the substrate 550. For example, the multilayer film 500 may initially be a generally planar film, such as... Figure 20 The diagram is schematically illustrated. To adapt this membrane to a nonplanar surface (e.g., the nonplanar surface of a sphere) curved about two mutually orthogonal axes, such as portion 555, the membrane is stretched and shaped such that it can be adapted to portion 555, as shown below. Figures 21 to 22 It is shown schematically in the middle.

[0068] In some embodiments, if the functional layer (e.g., 130, 230, 330, 330', 330", 430) comprises a metal or metal oxide layer, the patterned article of this specification may have at least one of the effects of antimicrobial, antibacterial, or antibiofilm effects. Multiple metal oxides (MOx) can be used in such applications provided that the metal oxide layer exhibits at least a 1-log reduction, at least a 2-log reduction, at least a 3-log reduction, or at least a 4-log reduction in microbial activity against Staphylococcus aureus and Streptococcus mutans after 24 hours of contact. After testing according to ISO test method ISO 22196:2011 "Measurement of antibacterial activity on plastics and other non-porous surfaces," the logarithmic reduction is measured with appropriate modifications to the test method to suit the test material.

[0069] Suitable antimicrobial metals and metal oxides for the functional layer include, for example, silver, silver oxide, copper oxide, gold oxide, zinc oxide, magnesium oxide, titanium oxide, chromium oxide, and mixtures, alloys, and combinations thereof. In some embodiments, the metal oxide in the functional layer is selected from, for example, AgCuZnOx, Ag-doped ZnOx, Ag-doped ZnO, Ag-doped TiO2, Al-doped ZnO, and TiOx.

[0070] In various embodiments, the functional layer may contain any antimicrobially effective amount of metal, metal oxide MOx, or mixtures and combinations thereof. In various embodiments, the metal oxide layer may contain, for example, per 100 cm³. 2 MOx less than 100 mg, less than 40 mg, less than 20 mg, or less than 5 mg.

[0071] In another embodiment, the functional layer may have dielectric properties and be able to transmit electromagnetic signals within a selected frequency range that can be used in 5G communication devices or other communication devices. For example, if the tanδ of the patterned functional layer is about 0.12 or less when measured at 9.5 GHz in the cavity of a split-pillar dielectric resonator as described in IPC standard TM-6502.5.5.13, the layer may be more transparent to communication signals transmitted between mobile devices compared to its non-micro-machined state. In some embodiments, the micro-machined functional layer may have a true dielectric constant of about 33 and a complex dielectric constant of about 4.

[0072] In some embodiments, the shape and size of the plate 444 and / or the grid pattern 448 can be configured to provide transparency for near-infrared signals, which allows for the formation of a highly conformal near-infrared sensor cover on the surface. In some embodiments, the plate and the spaces therebetween can be configured to provide reflectivity for near-infrared signals and transparency for visible light. For example, such a configuration can form a highly conformal visible light sensor cover.

[0073] In some embodiments, the shape and size of the plate 444 and / or the grid pattern 448 can result in color changes, reflections, transmissions, or other aesthetic effects of the functional layer, which can provide a usable decorative film that can be applied to complex or composite surfaces, such as, for example, the exterior or interior of a vehicle. For example, in some embodiments, the transfer article including the micro-machined inorganic layer is reflective at visible wavelengths of 400 nm to 750 nm or 400 nm to 700 nm, and at least partially transparent at wavelengths greater than about 830 nm. For example, some plates 444 may oxidize over time when exposed to environmental conditions, and this detectable color change can be used to assess, for example, the shelf life of the product. If the color change is undesirable, one or both surfaces of the micro-machined metal layer may be covered by one or more protective barrier layers, such as metal oxides. In some embodiments, the metal layer may be configured such that the plate provides a color-changing effect when exposed to light in a selected wavelength range (such as, for example, when the article is stretched along a two- or three-dimensional surface with composite curvature).

[0074] Example

[0075] These embodiments are for illustrative purposes and are not intended to limit the scope of the appended claims. Unless otherwise specified, all parts, percentages, ratios, etc., in the embodiments and the remainder of the specification are by weight.

[0076] Materials and sources

[0077]

[0078] Micro-cutting and embossing tools are manufactured according to the following specifications :

[0079] A tool is produced by diamond cutting 12-micrometer (μm) deep grooves in a cylindrical roller using conventional machining methods. The grooves are cut at 45-degree and -45-degree angles relative to the circumference of the roller. The spacing between the grooves is 300 μm. The resulting tool is a cross-groove forming a diamond-shaped raised area, with the grooves intersecting at 45-degree angles. Half of the pattern is cut using a tool with a 0.15 μm tip on a diamond cutting edge. The diamond cutting edge with the tip has an included angle of 60 degrees.

[0080] Next, the pattern is removed from the roller by peeling a thin copper layer from the surface of the cylinder with the aforementioned groove pattern. This thin copper sheet is then plated with Ni using a conventional Ni electroplating method to form a negative sheet with the cutting groove pattern. Electroplating of the nickel sheet from the pattern with the cutting edge characteristics results in raised edges in the nickel sheet.

[0081] The back of the nickel pads are then polished smooth and welded together to form a roller sleeve. This sleeve is then mounted onto a temperature-controlled mandrel, which is then installed in a laminator.

[0082] Pattern Description

[0083]

[0084] Test methods

[0085] Micro-cutting verification test

[0086] Light leakage from fractures in a film fabrication was observed using a VHX-6000 series Keyence digital microscope (Keyence Corporation of America, Itasca, IL) with a 100x objective lens in visible light transmission mode. The crack was visible as a region of higher visible light transmittance surrounded by a non-fractured surface with lower visible light transmittance.

[0087] Preparation Example 1. Ag-coated transfer stack

[0088] The transfer film in this embodiment was manufactured on a roll-to-roll vacuum coater with a second evaporator and curing system added between the plasma pretreatment station and the first sputtering system, similar to the coater described in U.S. Patent Application Publication No. 2010 / 0316852A1 (Condo et al.), and using an evaporator as described in U.S. Patent No. 8,658,248 (Anderson et al.). The coater was screwed onto an irregularly sized roll (980 microinches (0.0250 mm) thick, 14 inches (35.6 cm) wide) of an aluminized biaxially oriented polypropylene film release layer (trade name TORAYFAN PMX2, from Toray Plastics (America), North Kingstown, RI). The release layer was then advanced at a constant linear speed of 32 fpm (9.8 m / min).

[0089] A first acrylate layer, tricyclodecanediethanol diacrylate (trade name SARTOMER SR833S from Sartomer USA, Exton, PA), was applied to the release layer via ultrasonic atomization and flash evaporation to create a coating width of 12.5 inches (31.8 cm). The liquid monomer flow rate into the evaporator was 0.67 mL / min. The nitrogen flow rate was 100 standard cubic centimeters / min (sccm), and the evaporator temperature was set to 500℉ (260°C). The processing barrel temperature was 14℉ (-10°C). This monomer coating was then immediately cured downstream using an electron beam curing gun operating at 7.0 kV and 10.0 mA to produce an acrylate thickness of 180 nm.

[0090] On top of the first acrylate layer, a silver reflector layer was deposited by direct current (DC) sputtering with a >99% silver cathode target. The system was operated at 3kW with a line velocity of 30 fpm (9.1 m / min). Two subsequent depositions with the same power and line velocity were performed to form a 90 nm silver layer.

[0091] On top of the silver layer, an oxide layer of silicon-aluminum oxide is deposited by alternating current (AC) reactive sputtering. The cathode has a Si (90%) / Al (10%) target and is derived from Soleras Advanced Coatings US, Biddeford, ME. During sputtering, the cathode voltage is controlled by a feedback control loop that monitors the voltage and controls the oxygen flow rate. A 32 kW power system is used to deposit a 12 nm thick silicon-aluminum oxide layer onto the cured silver reflector. Similar to those described in U.S. Patent Application Publication No. 2020 / 0016879A1 (Gotrik et al.) and U.S. Patent Application Publication No. 2020 / 0136086A1 (Gotrik et al.), the TorayFAN PMX2 film and the aluminum surface of the first organic layer are separated with a 180° peel force of 7.2 g / in (0.283 g / mm).

[0092] Preparation Example 2. Weather-resistant Al-based MIM transfer stack

[0093] The coating machine was threaded tightly using an irregularly sized roller (980 microinches (0.0250 mm) thick, 14 inches (35.6 cm) wide) of an aluminized polyethylene (PET) film release layer (trade name TORAYFAN MT60, obtained from Toray Plastics (America), North Kingstown, RI). The release layer with a coated first acrylate layer was prepared according to the procedure described in Part 1 of Preparation Example 1. An aluminum reflector layer was deposited on top of the first acrylate layer. A conventional DC sputtering process using argon gas and operating at 2 kW was used to deposit a 60 nm thick Al layer. The cathode Al target was obtained from ACI Alloys, San Jose, California.

[0094] A second acrylate layer is applied on top of the reflective Al layer. The second acrylate layer is produced from a monomer solution via atomization and evaporation of SARTOMER SR833S+3% CN 147 (from Sartoma America, Exton, PA). The acrylate layer is applied using a flow rate of 0.67 mL / min to the atomizer; the gas flow rate is 60 sccm, and the evaporator temperature is 260 °C. Once condensed onto the Al layer, the coated acrylate is cured with an electron beam operating at 7 kV and 10 mA to provide a 290 nm thick layer. This second acrylate layer provides the insulating layer for a functional metal-insulator-metal (MIM) transfer stack.

[0095] A first inorganic barrier layer is applied on top of the second acrylate layer. The barrier layer is an oxide material applied via an AC reactive sputtering deposition process using a 40 kHz AC power supply. The cathode has a Si (90%) / Al (10%) spinning target and is sourced from Solera Advanced Coatings, USA. During sputtering, the cathode voltage is controlled by a feedback control loop that monitors the voltage and controls the oxygen flow rate. A 12 nm thick layer of silicon-aluminum oxide is deposited onto the second acrylate layer using a 16 kW power system.

[0096] A second reflective layer is deposited on top of the first inorganic barrier layer in a manner similar to that of the first reflective layer. A conventional DC sputtering process using argon gas and operating at 2kW power is used to deposit the second reflective layer as an 8nm thick Al layer.

[0097] On top of the second reflective layer, a second inorganic barrier layer is applied in the same manner as the first inorganic barrier layer.

[0098] A third acrylate layer was deposited on top of the second inorganic barrier layer. This layer was produced from a monomer solution by atomization and evaporation of SARTOMERSR833S + 6% DYNASYLAN 1189 (obtained from Evonik Industries, Essen, DE). The flow rate of this mixture into the atomizer was 0.67 mL / min. The gas flow rate was 60 sccm, and the evaporator temperature was 260°C. Once condensed onto the second inorganic barrier layer, the coated acrylate was cured with an electron beam operating at 7 kV and 10 mA to provide a 290 nm thick layer. Similar to those described in U.S. Patent Application Publication No. 2020 / 0016879A1 (Gotrik et al.) and U.S. Patent Application Publication No. 2020 / 0136086A1 (Gotrik et al.), the aluminum surface of the Toray MT60 film and the first organic layer will be separated with a peel force of 180° at 7.2 g / in (0.283 g / mm).

[0099] Example 1. Transfer-based micro-cutting and embossing products .

[0100] Preparation Example 1 was subjected to roll-to-roll lamination against a micro-cutting and embossing tool 1 at 240℉, and backing was applied at 240℉ using a steel roll laminator with a lamination force of 500 psi and a backing force of 3 psi and an input tension of 1 psi (after micro-cutting and embossing) to micro-cut the surface. Atomic force microscopy (AFM) showed that the embossed area of ​​the third acrylate layer was 600 nm lower than the surface of the surrounding non-embossed area of ​​the third acrylate layer. AFM also showed that the line edge roughness of the cut edge in the non-embossed area was approximately 200 nm.

[0101] Example 2. Transfer of non-embossed areas

[0102] The first OCA film was rapidly (<1 second) laminated onto the non-embossed third acrylate layer of Example 1. The OCA was then rapidly (<1 second) removed, bringing the contacting third acrylate and the attached multilayer to the OCA surface. The remaining TORAYFAN MT60 release liner with residual micro-cutting and embossing features was set aside.

[0103] The “micro-cutting verification test” confirmed the presence of micro-cuts with a 10 μm gap between the transferred multilayers on the top of the OCA surface. Accidental, unintentional fractures were observed within the transferred multilayer regions.

[0104] Example 3. Transfer of embossed area

[0105] The adhesive surface of 8518 was then laminated onto the remaining TORAYFAN MT60 release liner, which had the remaining micro-cutting and embossing features from Example 2. 8518 was then slowly removed from the TORAYFAN MT60, revealing the micro-cutting and embossing features. A “micro-cutting confirmation test” confirmed the presence of a 10 μm multilayer feature on the 8518 surface. Occasional fractures were observed along the 10 μm wide multilayer feature present on the 8518 surface.

[0106] Example 4 .

[0107] Example 1 was repeated using micro-machining and embossing tool 2. Example 4 was observed under an atomic force microscope (AFM), and the functional layers at different heights were observed (see example...). Figure 3 ).

[0108] Example 5 .

[0109] Example 2 was completed by replacing Example 1 with Example 4. A 4 μm gap exists between the transferred multilayers on top of the OCA surface.

[0110] Example 6 .

[0111] Example 3 was completed by replacing Example 2 with Example 5. A 4 μm wide multilayer feature was present on the 8518 surface. Atomic force microscopy measured the line edge roughness of the cut edge in the non-embossed region to be approximately 600 nm.

[0112] Example 7 .

[0113] Example 1 was repeated using Preparation Example 2. Example 7 was observed under an atomic force microscope (AFM), and the functional layers at different heights were observed (see example...). Figure 3 ).

[0114] Example 8 .

[0115] Example 2 was completed by replacing Example 1 with Example 7. When compared with Example 2, far fewer unintentional fractures were observed in the transferred multilayer region.

[0116] Terms such as “about” will be understood in the context in which they are used and described by those skilled in the art. If it is unclear to those skilled in the art in the context of their use and description of “about” to express quantities of characteristic size, quantity, and physical properties, then “about” will be understood to mean within 10% of a specified value. A quantity given a specified value as “about” can be precisely the specified value. For example, if it is unclear to those skilled in the art in the context of their use and description of this specification, a quantity having a value of about 1 means that the quantity has a value between 0.9 and 1.1, and that the value can be 1.

[0117] All cited references, patents, and patent applications are incorporated herein by reference in their entirety in a consistent manner. In the event of any inconsistency or contradiction between the incorporated references and this application, the information in the foregoing description shall prevail.

[0118] Unless otherwise stated, the description of elements in the accompanying drawings should be understood to apply equally to corresponding elements in the other drawings. While specific embodiments have been illustrated and described herein, those skilled in the art will recognize that various alternative and / or equivalent embodiments may be used instead of the illustrated and described embodiments without departing from the scope of this disclosure. This application is intended to cover any modifications, variations, or combinations of the specific embodiments discussed herein. Therefore, this disclosure is intended to be limited only by the claims and their equivalents.

Claims

1. A patterned article, the patterned article comprising: A carrier layer comprising a microstructured first main surface and an opposite second main surface, the first main surface comprising a plurality of upper edges and a plurality of lower edges, the upper edges and the lower edges being spaced apart along the thickness direction of the carrier layer and defining corresponding upper and lower portions of the first main surface, the lower portions being disposed between the upper portions and the second main surface; A first functional layer is disposed on the lower portion of the first main surface rather than the upper portion, the first functional layer comprising at least one first micro-cutting inorganic layer, the at least one first micro-cutting inorganic layer comprising a plurality of cut edges substantially co-extending with the plurality of lower edges; as well as A second functional layer disposed on the upper portion rather than the lower portion of the first main surface, the second functional layer comprising at least one second micro-cutting inorganic layer, the at least one second micro-cutting inorganic layer comprising a plurality of cut edges substantially co-extending with the plurality of upper edges, wherein the at least one second micro-cutting inorganic layer comprises a plurality of spaced plates.

2. The patterned article according to claim 1, wherein the patterned article is a transfer article configured such that the second functional layer can be transferred from the carrier layer to the first adhesive layer, thereby leaving the first functional layer disposed on the carrier layer, so that the first functional layer can be transferred from the carrier layer to the second adhesive layer.

3. The patterned article according to claim 1, wherein the at least one first micro-cut inorganic layer comprises a grid pattern.

4. The patterned article according to claim 1, wherein when the patterned article is disposed on a flat surface, the upper and lower portions of the first main surface are disposed in corresponding first planes and planes that are separated from each other along the thickness direction of the carrier layer.

5. The patterned article according to any one of claims 1 to 4, wherein the average spacing between the upper portion and the lower portion along the thickness direction of the carrier layer is in the range of 0.3 micrometers to 10 micrometers.

6. A method for manufacturing patterned articles, the method comprising: Provide a transfer article, the transfer article comprising: A carrier layer having opposite first and second main surfaces; and A functional layer is disposed on the first main surface; A tool comprising multiple microstructures, each microstructure including at least one cutting edge; The transfer article and the tool are arranged adjacent to each other such that the functional plane is oriented towards the plurality of microstructures; and The tool is used to contact the transfer article, causing the tool to emboss and cut into the transfer article to form a cut pattern in the functional layer and to form a plurality of structures defining an upper and lower portion of the first main surface in the carrier layer, the lower portion being disposed between the upper portion and the second main surface, a first portion of the functional layer being disposed on the upper portion of the first main surface, and a second portion of the functional layer being disposed on the lower portion of the first main surface, the first portion and the second portion of the functional layer being separated from each other along the cut pattern.

7. The method according to claim 6, wherein the functional layer comprises at least one inorganic layer.

8. The method of claim 6, wherein the functional layer comprises at least one organic layer.

9. The method according to any one of claims 6 to 8, wherein the patterned article is a transfer article configured such that the first portion of the functional layer can be transferred from the carrier layer to the first adhesive layer, thereby leaving the second portion of the functional layer disposed on the carrier layer, such that the second portion of the functional layer can be transferred from the carrier layer to the second adhesive layer.

10. The method according to any one of claims 6 to 8, wherein one of the upper portion or the lower portion comprises a grid pattern with an average linewidth in the range of 0.5 micrometers to 50 micrometers.

11. The method according to any one of claims 6 to 8, wherein in a top plan view, the total area of ​​the lower portion is less than 40% of the total area of ​​the first main surface.

12. A patterned article comprising a multilayer film, said multilayer film comprising: First polymer layer; A functional layer comprising opposing first and second main surfaces, the first main surface disposed on the first polymer layer, the functional layer comprising a multilayer stack comprising at least one micro-cut metal layer and at least one metal oxide or metal nitride layer, each micro-cut metal layer having an average thickness in the range of 5 nanometers to 500 nanometers and comprising a notch pattern forming any of the following: (i) A pattern of discretely spaced plates, the pattern of which corresponds to and is defined by the cutout pattern, wherein there are substantially no portions of the metal layer between the closest adjacent plates, or (ii) A continuous pattern, the continuous pattern corresponding to a pattern of discretely spaced plates corresponding to the cut pattern being removed from the metal layer; and A second polymer layer is disposed on the second main surface of the functional layer.

13. The patterned article of claim 12, further comprising a substrate, wherein the multilayer film is disposed on at least a portion of a main surface of the substrate and substantially conforms to at least a portion of the main surface of the substrate, the portion of the main surface being bent about two mutually orthogonal axes.

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