Microcut patterned articles and methods for manufacturing the same

Abstract

The patterned article includes a carrier layer having a microstructured first major surface and an opposite second major surface. The first major surface includes a plurality of upper and lower edges spaced apart along a thickness of the carrier layer, defining respective upper and lower portions of the first major surface. The lower edges are disposed between the upper and second major surfaces. The article includes a first functional layer disposed on the lower but not upper portion of the first major surface. The first functional layer includes at least one first micro-cut inorganic layer including a plurality of cut edges substantially coextensive with the plurality of lower edges. Methods for manufacturing patterned articles are provided. Articles are provided that can be manufactured by transferring a functional layer from a patterned article.

Description

Background Art

[0001] Sputtering is a high-precision vacuum deposition process capable of depositing inorganic thin films with single-digit nanometer thickness control over large areas, and can be suitable for roll-to-roll manufacturing. Using sputtering, laminates of inorganic thin film layers such as, for example, metal layers and metal oxide layers can be deposited on a substrate. The materials, thicknesses, and arrangement order of thin inorganic layers having different refractive indices can be selected to finely adjust the aesthetic appearance and transmission properties of an article. Summary of Invention

[0002] The present specification generally relates to patterned articles comprising at least one micro-cut layer, and to methods of making such patterned articles.

[0003] In some aspects of the present specification, a patterned article is provided. The patterned article comprises a carrier layer having a microstructured first major surface and an oppositely facing second major surface. The first major surface comprises a plurality of top ends and bottom ends spaced apart along the thickness direction of the carrier layer, defining respective upper portions and lower portions of the first major surface. The lower portions are disposed between the upper portions and the second major surface. The article comprises a first functional layer disposed on the lower portions rather than the upper portions of the first major surface. The first functional layer comprises at least one first micro-cut inorganic layer comprising a plurality of cut ends that are substantially coextensive with the plurality of bottom ends.

[0004] In some aspects of this specification, a method for manufacturing a patterned article is provided. The method includes the steps of: preparing a transfer article, which includes a carrier layer having a first main surface and a second main surface facing opposite directions, and a functional layer disposed on the first main surface; preparing 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; and contacting the transfer article with the tool such that the tool embosses and cuts the transfer article to form a cut pattern in the functional layer and to form a plurality of structures in the carrier layer defining the upper and lower parts of the first main surface. The lower part is located between the upper part and the second main surface. The first part of the functional layer is located on the upper part of the first main surface, and the second part of the functional layer is located on the lower part of the first main surface. The first and second parts of the functional layer are separated from each other along the cut pattern.

[0005] In some aspects of this specification, patterned articles comprising multilayer films are provided. The multilayer film comprises a first polymer layer, a functional layer comprising a first principal surface and a second principal surface facing opposite directions, wherein the first principal surface is disposed on the first polymer layer, and a second polymer layer disposed on the second principal surface of the functional layer. The functional layer comprises a multilayer laminate comprising at least one microcut metal layer and at least one metal oxide layer or metal nitride layer. Each microcut metal layer has an average thickness in the range of 5 nanometers to 500 nanometers and includes a pattern of cuts that forms either (i) a pattern of spaced individual plates defined by the cuts, corresponding to the pattern of cuts, where portions of the metal layer are not substantially located between the nearest adjacent plates, or (ii) a continuous pattern corresponding to the pattern of cuts, corresponding to the removal of a pattern of spaced individual plates from the metal layer.

[0006] These and other aspects will become apparent from the detailed description below. However, in no case should this brief summary be construed as limiting the subject matter of the claims. [Brief explanation of the drawing]

[0007] [Figure 1] This is a schematic cross-sectional view of a carrier layer according to several embodiments. [Figure 2] This is a schematic cross-sectional view of a patterned article including a functional layer, according to several embodiments. [Figure 3] This is a schematic cross-sectional view of a patterned article, including a first functional layer and a second functional layer, according to several embodiments. [Figure 4] This is a schematic cross-sectional view of a patterned article, including a first functional layer and a second functional layer, according to several embodiments. [Figure 5A] This is a schematic cross-sectional view of another patterned article including a first functional layer and a second functional layer, according to several embodiments. [Figure 5B] This is a schematic cross-sectional view of a patterned article corresponding to the patterned article of Figure 5A, in which the second functional layer has been removed according to several embodiments. [Figure 6] This is a schematic cross-sectional view of a functional layer according to several embodiments. [Figure 7] This is a schematic cross-sectional view of a functional layer according to several embodiments. [Figure 8] This is a schematic cross-sectional view of a functional layer according to several embodiments. [Figure 9] This is a schematic top view of a patterned functional layer showing line edge roughness according to several embodiments. [Figure 10A] This is a schematic cross-sectional view of a patterned article including an overcoat, according to several embodiments. [Figure 10B] This is a schematic cross-sectional view of a patterned article including an overcoat, according to several embodiments. [Figure 11]This is a schematic top view of a patterned article, including a first functional layer and a second functional layer, according to several embodiments. [Figure 12] This is a schematic top view of a patterned article, including a first functional layer and a second functional layer, according to several embodiments. [Figure 13] This is a schematic top view of a patterned article, including a first functional layer and a second functional layer, according to several embodiments. [Figure 14] This is a schematic top view of a patterned article including a functional layer, according to several embodiments. [Figure 15] This is a schematic top view of a patterned article including a functional layer, according to several embodiments. [Figure 16] This is a schematic top view of a patterned article including a functional layer, according to several embodiments. [Figure 17] This is a schematic cross-sectional view of a transfer article according to several embodiments. [Figure 18] This is a schematic diagram of a method for manufacturing patterned articles according to several embodiments. [Figure 19] This is a schematic cross-sectional view of the microstructure of a tool for manufacturing patterned articles according to several embodiments. [Figure 20] This is a schematic cross-sectional view of a patterned article including a multilayer film according to several embodiments. [Figure 21] This is a schematic perspective view of an exemplary substrate having a curved surface. [Figure 22] This is a schematic perspective view of a patterned article comprising a multilayer film disposed on a curved substrate, according to several embodiments. [Modes for carrying out the invention]

[0008] In the following description, reference is made to the accompanying drawings, which form a part of the present specification, and in which various embodiments are shown by way of illustration. The drawings are not necessarily to scale. It should be understood that other embodiments can be conceived and practiced without departing from the scope or spirit of the present specification. Therefore, the following detailed description for carrying out the invention is not to be interpreted in a restrictive sense.

[0009] In some aspects, the present disclosure generally relates to a transfer article comprising a dimensionally stable yet flexible transfer substrate, the transfer article having a functional layer comprising at least one (e.g., ultra-thin) inorganic layer thereon. In some embodiments, the inorganic layer(s) in the functional layer of the transfer article is formed by a sputtering process and has a thickness, for example, from about 3 nanometers (nm) to about 2000 nm. According to some embodiments, a transfer article comprising a stable transfer substrate and at least one thin inorganic layer is subsequently contacted with a microstructuring tool to emboss the substrate, and a pattern of cut edges that faithfully corresponds to the pattern of cutting edges of the tool is formed in the inorganic layer. The precise pattern of cut edges may form an array of plates and a mesh pattern, and the plates and mesh pattern may be arranged in different planes.

[0010] In some embodiments, the patterned articles herein provide a transferable conductive layer having a thickness of, for example, less than about 3 micrometers, which can be used as a touch sensor or an antenna for a wide range of applications such as 5G, or other antenna applications utilizing frequencies in the range of, for example, 0.1 GHz to 300 GHz. In some embodiments, the microcut inorganic layer provides a fine wire conductive mesh material that can be manufactured without multiple post-plating steps. In some embodiments, a patterned article comprising a microcut inorganic layer, which may be diffusely reflective, is stretched in at least one dimension and applied to a non-planar or structured surface. For example, the network of plates in the microcut inorganic layer can accommodate elongation and strain during the application process and stretch to varying degrees to conform to the surface. When applied to a surface, the patterned article forms a microcut article that has an accurate arrangement of plates sufficiently small to provide adjustable reflective performance with consistent color and mirror-like aesthetic appearance at a selected viewing angle relative to its main surface.

[0011] Since the pattern of cut edges in the microcut inorganic layer can be a faithful reproduction of the pattern on the microstructured tool, the accurate arrangement of the plates enables more accurate control of the aesthetic appearance and / or conductivity of an article comprising a laminate of inorganic materials when the article is stretched in one or more directions, applied or adhesively bonded to a composite surface to form a laminated article. Microcutting the inorganic layer renders the inorganic layer transparent to electromagnetic signals within a desired frequency range, thereby enabling fabrication of articles useful, for example, in communication devices.

[0012] Figure 1 is a schematic cross-sectional view of a carrier layer 110 according to several embodiments. Figures 2 and 3 are schematic cross-sectional views of patterned articles 100 and 100' according to several embodiments. In some embodiments, the patterned articles 100 and 100' include a carrier layer 110 comprising a microstructured first main surface 112 and a second main surface 114 facing the opposite direction. The first main surface 112 defines the upper 125 and lower 127 of the first main surface 112, spaced apart along the thickness direction of the carrier layer 110 (the z direction when referring to the illustrated xyz coordinate system), and the lower 127 includes a plurality of upper ends 121 and lower ends 123 located between the upper 125 and the second main surface 114. In some embodiments, the upper 125 and lower 127 are arranged in first and second regular patterns, respectively (e.g., a mesh pattern and a regular pattern of spaced plates, as further described elsewhere in this specification). The patterned articles 100, 100' include a first functional layer 130 positioned on the lower (127) rather than the upper (125) of the first main surface 112. The first functional layer 130 includes at least one first microcut inorganic layer 131, which includes a plurality of cut edges 133 having substantially the same extent as a plurality of lower edges 123. The first functional layer 130 may be a single first microcut inorganic layer 131, or it may include a plurality of layers as further described elsewhere in this specification.

[0013] In some embodiments, the patterned article 100' further includes a second functional layer 230 located on the upper (125) rather than the lower (127) of the first main surface 112, and comprising at least one second microcut inorganic layer 231 having a plurality of cut edges 233 having substantially the same spread as a plurality of upper edges 121. The second functional layer 230 may be a single second microcut inorganic layer 231 or may comprise a plurality of layers as further described elsewhere herein.

[0014] In some embodiments, the cut ends 133 and / or 233 are arranged in a regular pattern (e.g., a regular pattern of straight line segments). In some embodiments, the cut ends 133 and / or 233 may have a linear shape and may be arranged in a plurality of substantially parallel (e.g., 20 degrees, or within 10 degrees, or 5 degrees parallel) line segments (e.g., see Figures 11-16), or a plurality of substantially parallel first line segments (e.g., parallel in the x-direction in Figures 11-15) and substantially perpendicular (e.g., 20 degrees, or within 10 degrees, or 5 degrees perpendicular) substantially parallel second line segments (e.g., parallel in the y-direction in Figures 11-15). In various embodiments, the cut ends 133, 233 (e.g., the total number of cut line segments in the first functional layer 130 and, if present, the second functional layer 230) are approximately 0.3 to approximately 2000 / mm 2 Approximately 1 to 1000 / mm 2 Approximately 10 to 500 / mm 2 Approximately 20 to 200 / mm 2 , or approximately 50-100 / mm 2 It is located on the first principal surface 112.

[0015] A microstructure is generally a structure having at least two orthogonal dimensions (e.g., height and width) in the range of about 0.1 micrometers to about 2000 micrometers. A microcut layer generally refers to a layer having cuts that define elements of the layer, having at least one dimension in the plane of the layer in the range of about 0.1 micrometers to about 2000 micrometers. A layer can be microcut using a tool having a microstructure, where each microstructure has at least one cutting end. Such tools can be manufactured using conventional microfabrication processes (e.g., diamond cutting of microstructures onto a cylindrical roll using a diamond cutting tool made by focused ion milling). Cutting tools for microfabrication and methods for manufacturing such cutting tools are described, for example, in U.S. Patent No. 7,140,812 (Brian et al.) and No. 8,443,704 (Burke et al.). Microcutting generally produces sharp cut edges with a width (e.g., corresponding to the tip width Wt schematically shown in Figure 19) that is substantially smaller (e.g., at least twice, at least four times, or at least eight times smaller) than the minimum lateral dimension of the element formed by microcutting (e.g., width W1 schematically shown in Figure 19). Such cuts are sometimes called microcuts. For example, cut edges 133 and / or cut edges 233 may be microcut edges.

[0016] A functional layer containing at least one microcut layer is sometimes referred to as a microcut functional layer. In some embodiments, each of the functional layers 130 and 230 is a microcut layer having substantially the same cut pattern as the corresponding microcut inorganic layer.

[0017] The cut ends (e.g., cut ends 133 and 233) of layers (e.g., inorganic layers 131 and 231) located on the upper (125) or lower (127) of the first main surface 112 may refer to the ends between the side walls of the layers and the main surfaces of the layers facing the upper (125) or lower (127) of the first main surface 112. Alternatively, the cut ends of a layer may refer to the side ends of the layers extending between the upper and lower main surfaces of the layers. Multiple ends (e.g., 133, 233) can be described as having substantially the same extent as another set of multiple ends (e.g., 123, 121) if, in a top view, at least 60% of the total length of each set of multiple ends extends along at least 60% of the total length of another set of multiple ends. In some embodiments, at least 70%, at least 80%, at least 90%, or at least 95% of the total length of each of the multiple ends extends along at least 70%, at least 80%, at least 90%, or at least 95% of the total length of the other multiple ends.

[0018] In various embodiments, the functional layer (e.g., functional layer 130 or 230) may include a laminate of one or more layers selected to provide an article containing a functional layer having some functional properties, the functional properties of which may include, for example, electrical conductivity or reflective or transmissive properties, aesthetic properties, environmental properties, or antimicrobial properties, for example, electromagnetic properties.

[0019] 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), while leaving the first functional layer 130 positioned on the carrier layer 110. For example, after the second functional layer 230 has been transferred, the patterned article 100' may 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, while leaving the first functional layer 130 positioned on the carrier layer 110, thereby allowing the first functional layer 130 to be transferred from the carrier layer 110 to the second adhesive layer 268. As further described elsewhere in this specification, 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.

[0020] In some embodiments, the first main surface 112 of the carrier layer 110 includes a plurality of structures 129 that define gaps between them, each having an average width W0 along at least one direction and 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 that is approximately 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 as schematically shown in Figures 2 and 3, approximately the same as the average thickness t0 as schematically shown in Figure 4, or less than the average thickness t0 as schematically shown in Figures 5A and 5B. In some embodiments, the average separation distance (h0) of the upper (125) and lower (127) of the carrier layer 110 along the thickness direction (z direction) is greater than the average thickness t0 of the first functional layer 130. In some embodiments, the average separation distance (h0) between the upper (125) and lower (127) of the carrier layer 110 along the thickness direction (z direction) is less than the average thickness t0 of the first functional layer 130''. In some embodiments, the average separation distance (h0) between the upper (125) and lower (127) of the carrier layer 110 along the thickness direction (z direction) is within 10% of the average thickness t0 of the first functional layer 130'. Figures 4 and 5A are schematic cross-sectional views of patterned articles 102 and 104, respectively, which may correspond to patterned article 100' except for the thickness of the functional layer. Figure 5B is a schematic cross-sectional view of patterned article 104', which may correspond to patterned article 104 except that the functional layer 230'' is removed. In patterned article 102, the functional layers 130' and 230' each have an average thickness approximately equal to the average separation distance (h0) of the upper (125) and lower (127) of the carrier layer 110 along the thickness direction (z direction). In patterned article 104, the functional layers 130' and 230' each have an average thickness greater than the average separation distance (h0) of the upper (125) and lower (127) of the carrier layer 110 along the thickness direction (z direction).

[0021] In some embodiments, when the patterned article 100 is placed on a flat surface 174, the upper (125) and lower (127) portions of the first main surface 112 are positioned on first planes 176 and 178, respectively, that are spaced apart from each other (e.g., by an average separation distance h0) along the thickness direction (z direction) of the carrier layer 110.

[0022] In some embodiments, the average separation distance (h0) between the upper (125) and lower (127) of the carrier layer 110 along the thickness direction (z direction) is at least 0.3 micrometers, at least 0.5 micrometers, or at least 0.7 micrometers. In some such embodiments, or in other embodiments, the average separation distance (h0) between the upper (125) and lower (127) of the carrier layer along the thickness direction (z direction) is 10 micrometers or less, 5 micrometers or less, 3 micrometers or less, 2 micrometers or less, or 1.5 micrometers or less. For example, the average separation distance may be in the range of 0.3 micrometers to 10 micrometers, 0.5 micrometers to 5 micrometers, 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 have 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. The thickness T1 of the patterned article may be greater than, for example, 0.5 micrometers.

[0023] Figures 6 to 8 are schematic cross-sectional views of functional layers 330, 330', and 330'', any of which may correspond to functional layer 130 or 230 (for example, in some embodiments, functional layers 130 and 230 can be obtained by microcutting functional layer 330, 330', or 330'', as further described elsewhere in this specification). Functional layer 330 includes layers 331a, 331b, and 331c, and has a first outermost principal surface 303 and a second outermost principal surface 305 facing opposite directions. In some embodiments, layers 331a, 331b, and 331c include at least one metal layer and at least one metal oxide layer or metal nitride layer. Functional layer 330' includes a functional layer 330 having a first outermost main surface 303' and a second outermost main surface 305' facing opposite directions, and positioned between the first layer 431a and the second layer 431b. The first layer 431a and the second layer 431b may be first and second organic layers and / or first and second polymer layers. The polymer layers can be understood as organic polymer layers unless otherwise indicated. Functional layer 330'' includes the first layer 431a and the second layer 431b, and at least layers 331a to 331f positioned 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, about 1 nm to about 500 nm, about 1 nm to about 250 nm, about 3 nm to about 200 nm, about 5 nm to about 100 nm, or about 10 nm to about 50 nm.

[0024] In some embodiments, a functional layer (or, for example, a first functional layer 130 and / or a 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 microcut inorganic layer and further comprising at least one microcut organic layer having substantially the same extent as the first microcut inorganic layer. The patterned article may further include a second functional layer comprising at least one second microcut inorganic layer and further comprising at least one microcut organic layer having substantially the same extent as the second microcut inorganic layer. The patterning techniques described herein may be applied to a functional layer comprising at least one organic layer and at least one inorganic layer in a single step (e.g., using tool 333), in contrast to conventional patterning techniques in which one or more organic layers and one or more inorganic layers are patterned in separate (e.g., etching) steps. For example, a functional layer may include a metal layer placed between polymer layers. It has been shown that including a polymer layer with a metal layer in the functional layer improves, for example, the mechanical robustness of the functional layer during processing.

[0025] In some embodiments, the functional layer includes at least two metal layers. In some embodiments, the functional layer includes at least two metal oxide layers, at least two metal nitride layers, or at least one metal oxide layer and at least one metal nitride layer. For example, for any functional layer 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 the 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 with metal nitride layers. Other suitable functional layers are described, for example, in International Publication No. 2020 / 240419 (Gotrik et al.).

[0026] In some embodiments, at least one of the first polymer layer 431a and the second polymer layer 431b contains or is formed from an acrylate or acrylamide. In some embodiments, the first polymer layer 431a and the second polymer layer 431b are, respectively, first and second acrylate layers, or contain or are formed from them.

[0027] Suitable metals for the metal layer include, for example, copper, aluminum, silver, gold, titanium, indium, tin, zinc, zirconium, and alloys thereof. Suitable oxides for the metal oxide layer include, for example, aluminum oxide, silicon oxide, aluminum silicon oxide, aluminum silicon oxynitride, CuO, silver oxide, TiO2, ITO, ZnO, aluminum zinc oxide, ZrO2, and yttria-stabilized zirconia. Suitable nitrides include, for example, aluminum silicon nitride, Si3N4, and TiN. Any oxide or nitride of any of the metals described herein may be used in the oxide layer or nitride layer. Since silicon is a metalloid, in the terminology used herein, silicon oxide is considered a metal oxide, and silicon nitride is considered a metal nitride.

[0028] In some embodiments, a functional layer (e.g., functional layers 130, 230, 330, 330', or 330'', or another functional layer described elsewhere herein) comprises at least one microcut metal layer. In some embodiments, at least one microcut metal layer comprises or is formed from silver. For example, layer 331b may be a silver layer, and each of layers 331a and 331b may be a metal oxide layer. The oxide-protected silver layer is useful, for example, in plasmon applications. In some embodiments, the microcut functional layer comprises an oxide-protected silver layer between polymer layers (e.g., layers 431a and 431b). The methods herein, according to some embodiments, can enable a functional layer comprising an oxide-protected silver layer and a polymer layer to be patterned by microcutting. It has been found difficult to fabricate a patterned functional layer comprising an oxide-protected silver layer and a polymer layer using the prior art (e.g., dry or wet lithography).

[0029] The line edge roughness of the cut edges can be substantially smaller than that obtained from conventional patterning processes, such as lift-off lithography. Figure 9 is a schematic top view of a patterned functional layer showing line edge roughness according to several embodiments. A roughness parameter Ra may 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 ​​in the displacement of edge 747 from the average position 888 of edge 747. In some embodiments, the average line edge roughness Ra of a plurality of cut edges and / or patterns of cuts can be less than 1 micrometer, less than 500 nm, or less than 100 nm, and may be as low as, for example, 10 nm. In some embodiments, the patterned article includes at least one first microcut inorganic layer (e.g., located below a microstructured main surface) containing a plurality of cut edges having 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 microcut inorganic layer (e.g., positioned on top of a microstructured main surface) having a plurality of cut edges having an average line edge roughness Ra of less than 1 micrometer or within the range described elsewhere herein. In some embodiments, the patterned article includes at least one microcut metal layer, each microcut metal layer having a pattern of cuts. In some embodiments, for each microcut metal layer, the average line edge roughness Ra of the cut pattern is less than 1 micrometer or within the range described elsewhere herein.

[0030] Various layers of the functional layers 330, 330', and 330'' may be applied by, for example, reactive deposition, (e.g., reactive) sputtering, chemical deposition, plasma-enhanced chemical deposition, and / or atomic layer deposition. Preferred methods for forming the functional layers are, for example, U.S. Patent Application Publication No. 2012 / 0208033 (Weigel et al.), and U.S. Patents No. 4,696,719 (Bischoff); No. 4,722,515 (Ham); No. 4,842,893 (Yializis et al.); No. 4,954,371 (Yializis), No. 5,018,048 (Shaw et al.); No. 5,032,461 (Shaw et al.); No. 5,097,800 (Shaw et al.); This is described in publications No. 5,125,138 (Shaw et al.); No. 5,440,446 (Shaw et al.); No. 5,547,908 (Furuzawa et al.); No. 6,045,864 (Lyons et al.); No. 6,231,939 (Shaw et al.); No. 6,214,422 (Yializis); No. 8,658,248 (Anderson et al.); No. 9,034,459 (Condo et al.); and No. 10,693,024 (Weigel et al.).

[0031] Any of the patterned articles 100, 100', 102, 104, and 104' may further include an overcoat placed on the first main surface 112. Figures 10A and 10B schematically show patterned articles 101 and 101', each including an overcoat 111 and 111' placed on top of the patterned articles 100 and 100', respectively. The overcoats 111 and 111' may be provided to alter dielectric properties and / or to protect the functional layer(s). In some embodiments, the overcoats 111 and 111' may be adapted to be transferred together with, for example, the functional layer(s) 130 and / or 230 (for example, in some embodiments, the overcoat is a conformal coating that can be transferred together with the functional layer(s).). In other embodiments, the overcoats 111 and 111' may be provided when the corresponding patterned articles 100 and 100' are not intended to be used, for example, as transfer articles.

[0032] Figures 11 to 13 are schematic top views of a patterned article comprising a plurality of spaced plates 444 and a continuous pattern 448 (e.g., a mesh pattern) spaced apart from each other along a cut pattern 433. The plates 444 may correspond to one of the first functional layer 130 and the second functional layer 230 (or one of the first inorganic layer 131 and the second inorganic layer 231), and the pattern 448 may correspond to the other of the first functional layer 130 and the second functional layer 230 (or the other of the first inorganic layer 131 and the second inorganic layer 231). In some embodiments, at least one second microcut inorganic layer 231 includes a plurality of spaced plates 444. In some such embodiments, or in other embodiments, at least one first microcut inorganic layer 131 includes a mesh pattern. In some embodiments, at least one second microcut inorganic layer 231 includes a mesh pattern 448. In some such embodiments, or in other embodiments, at least one first microcut inorganic layer 131 includes a plurality of spaced plates 444. In various embodiments, the exposed surfaces of the plates 444 may be substantially flat or undulating.

[0033] Figure 14 is a schematic top view of several spaced plates 444, which may correspond to a patterned article (e.g., patterned article 100) after the second functional layer 230 arranged in a mesh pattern has been removed, or to a second functional layer 230 arranged in a plate pattern after the second functional layer 230 has been transferred (e.g., to an adhesive layer) from a patterned article (e.g., patterned article 100') to a plate.

[0034] Figure 15 is a schematic top view of a mesh pattern 448, which may correspond to a patterned article (e.g., patterned article 100) after the second functional layer 230 arranged in a pattern of spaced plates has been removed, or to a second functional layer 230 arranged in a mesh after the second functional layer 230 has been transferred (e.g., to an adhesive layer) from a patterned article (e.g., patterned article 100').

[0035] The plate 444 has in-plane orthogonal dimensions of Wa and Wb, and the mesh pattern 448 has a line width Wc. In some embodiments, at least one of Wa and Wb is less than 2000 micrometers, less than 1000 micrometers, less than 500 micrometers, less than 250 micrometers, less than 150 micrometers, or less than 100 micrometers. In some of such embodiments, or in other embodiments, each of Wa and Wb is at least 10 micrometers or at least 20 micrometers. In some embodiments, 0.2<Wa / Wb<5, 0.25<Wa / Wb<4, or 1 / 3<Wa / Wb<3. In some embodiments, the line width Wc is at least 0.25 micrometers, at least 0.5 micrometers, at least 1 micrometer, at least 2 micrometers, or at least 3 micrometers. In some of such embodiments, or in other embodiments, the line width Wc is 100 micrometers or less, 50 micrometers or less, 30 micrometers or less, 20 micrometers or less, or 10 micrometers or less. For example, in some embodiments, the line width Wc is within the range of 0.5 micrometers to 50 micrometers, 1 micrometer to 50 micrometers, 2 micrometers to 30 micrometers, or 2 micrometers to 20 micrometers. In some embodiments, the center-to-center spacing (along the x-direction and / or along the y-direction) between the plates 444 is less than 2000 micrometers, less than 1000 micrometers, less than 500 micrometers, less than 250 micrometers, less than 150 micrometers, or less than 100 micrometers. In embodiments where the plate 444 is rectangular, Wa and Wb are the width and length of the rectangle, which may be a square since a square is a special case of a rectangle. The plate 444 may have any other suitable shape such as circular or elliptical. For general shapes, Wa can be interpreted as the length of the shortest in-plane line extending across the entire shape and passing through the center of gravity of the shape, and Wb can be understood as the maximum dimension of the shape in the in-plane direction orthogonal to the shortest in-plane line.

[0036] Figure 16 is a schematic top view of a plurality of spaced 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 to at least one first microcut inorganic layer or at least one second microcut inorganic layer. In some embodiments, at least one first microcut inorganic layer 131 includes a plurality of spaced strips 544 extending along the same first direction (y-direction). In some embodiments, at least one second microcut inorganic layer 231 includes a plurality of spaced strips 544 extending along the same first direction (y-direction). The strips 544 may be considered plates having a large aspect ratio (e.g., Wb / Wa > 5 or Wb / Wa > 10).

[0037] In some embodiments, in the top view (along the minus z direction), the lower part 127 has a total area of ​​50 percent or less of the total area of ​​the first main surface 112. For example, the mesh pattern 448 in Figure 12 may be located on the lower part 127. As another example, the plate 444 in Figure 13 may be located on the lower part 127. The total area of ​​the first main surface 112 in the top view includes the areas of the upper part 125 and the lower part 127, but does not include the area of ​​the vertical side walls. In some embodiments, in the top view, the lower part has a total area of ​​less than 50 percent, less than 40 percent, less than 30 percent, less than 20 percent, or less than 10 percent of the total area of ​​the first main surface. In some such embodiments, or in other embodiments, in the top view, the lower part 127 has a total area of ​​at least 0.01 percent, at least 0.1 percent, at least 0.5 percent, at least 1 percent, or at least 2 percent of the total area of ​​the first main surface. In some embodiments, the second functional layer 230 is transferred from the carrier layer 110, leaving the first functional layer 130 positioned on the lower 127, and the first functional layer 130 can then be transferred to another layer. In some embodiments, it may be desirable that the article containing the first functional layer (for example, positioned on the lower 127 or transferred to another layer) be optically transparent. In some such embodiments, or in other embodiments, in the top view, it may be preferable that the lower 127 has a total area of ​​less than 10% of the total area of ​​the first main surface 112. For example, in the top view, the lower 127 may have a total area of ​​about 8% or less of the total area of ​​the first main surface 112.

[0038] In some embodiments, the first functional layer 130 and / or the second functional layer 230 are crack-free or substantially crack-free. In some embodiments, the first microcut inorganic layer 131 and / or the second microcut inorganic layer 231 are crack-free or substantially crack-free. A layer can be described as substantially crack-free if the cracks are not visible to a person (by an uncorrected person with normal vision (20 / 20 vision) under normal indoor lighting conditions as may be described in the UNE-EN 12464-1:2012 standard) at a distance of 10 cm. A crack is different from a cut because a cut leaves a different mark (e.g., tool marks) than a crack. In some embodiments, the first inorganic layer 131 and / or the second inorganic layer 231 include multiple cut (e.g., microcut) ends and do not include cracks extending between different cut ends.

[0039] In some embodiments, the patterned article is a transfer article configured such that a first functional layer 130 and / or a second functional layer 230 can be transferred from a carrier layer 110 to an adhesive layer (see, for example, 267 or 268 in Figure 18). Figure 17 is a schematic cross-sectional view of a transfer article 200, which includes a carrier layer 210 before patterning, which may be used in producing a patterned article as further described elsewhere in this specification and which may correspond to the carrier layer 110. The transfer article 200 includes a carrier layer 210 which includes a functional layer 430 (for example, corresponding to functional layer 130 or 230, or another functional layer as described elsewhere in this specification), 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, as schematically shown in Figure 17. In some embodiments, the substrate 226 includes or is formed from polyethylene terephthalate (PET) or biaxially oriented polypropylene (BOPP). The PET may be, for example, uniaxially oriented or biaxially oriented. In some embodiments, the release coating 228 is a metal layer or a doped semiconductor layer, or includes them. The metal layer may, conveniently, be formed from Al, Zr, Cu, NiCr, NiFe, Ti, or Nb, and may have a thickness of, for example, about 3 nm to about 3000 nm. The doped semiconductor layer may be formed from Si, B-doped Si, Al-doped Si, or P-doped Si, and may have a thickness of, for example, about 3 nm to about 3000 nm. A particularly suitable doped semiconductor layer for the release layer is Al-doped Si, with an Al composition percentage of about 10%. In some such embodiments, or in other embodiments, the peel value between the release coating 228 and the functional layer 430 is 2 to 50 grams / inch. In some embodiments, the carrier layer 110 or 210 is aluminum-coated PET or aluminum-coated BOPP, or includes them.The release layer may be prepared, for example, by vapor deposition, reaction vapor deposition, sputtering, reaction sputtering, chemical vapor deposition, plasma-enhanced chemical vapor deposition, or atomic layer deposition. Other suitable release-coated substrates are described, for example, in International Publication No. 2020 / 240419 (Gotrik et al.).

[0040] The substrate 226 of the carrier layer 210 may be a low modulus layer (for example, a layer having a Young's modulus in the range of 50 MPa to 1000 MPa, or 100 MPa to 500 MPa), or may include a low modulus layer. For example, the substrate may include a first polymer layer 226a (for example, a PET or BOPP layer) disposed on a second polymer layer 226b that faces the functional layer 430 and may be a low modulus layer. The low modulus layer may be an acrylic adhesive, such as an acrylic pressure-sensitive adhesive. The low modulus layer can reduce the pressure required to complete the patterning process, and can improve, for example, the fidelity of pattern reproduction at the cutting edge of a micro-cutting tool. In other embodiments, the substrate 226 is, for example, a monolithic PET or BOPP film.

[0041] Figure 18 is a schematic cross-sectional view of a method for manufacturing a patterned article 300 or a patterned article 300' (corresponding to, for example, patterned article 100 or another patterned article described elsewhere in this specification), and a method for transferring the functional layers of the resulting patterned articles 300, 300' to other layers to form patterned articles 301 and 302. Interruption symbols 776 and 777 are included to indicate that the processes to the left and right of interruption symbols 776 and 777 may be performed on the same or different (e.g., continuous roll-to-roll) process lines. In some embodiments, the portion to the right of interruption 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 interruption symbol 777 is omitted (or performed as a separate process), and the method is a method for manufacturing patterned article 300' and / or patterned article 301. In some embodiments, the method is a method for manufacturing patterned articles 301 and / or 302.

[0042] In some embodiments, methods are provided for manufacturing patterned articles 300, 300', 301, and / or 302 (or 100, 100', or other patterned articles as described elsewhere in this specification). The method may include the step of preparing a transfer article 200, which includes a carrier layer 210 having a first main surface 212 and a second main surface 214 facing opposite directions, and a functional layer 430 disposed on the first main surface 212. The method may further include the steps of: providing a tool 333 comprising a plurality of microstructures 335, each microstructure comprising at least one cutting edge 337; arranging a transfer article 200 and the tool 333 adjacent to each other such that the functional layer 430 faces the plurality of microstructures 335; and bringing the transfer article 200 into contact with the tool 333 such that the tool 333 embosses and cuts the transfer article 200 to form a cut pattern 433 on the functional layer 430 and forms a plurality of structures 255 on the carrier layer that define the upper 225 and lower 227 of the first main surface 212. The lower 227 is located between the upper 225 and the second main surface 214. The first portion 630 of the functional layer 430 is positioned on the upper part 225 of the first main surface 212, and the second portion 730 of the functional layer 430 is positioned on the lower part 227 of the first main surface 212. The first portion 630 and the second portion 730 of the functional layer 430 are spaced apart from each other along the cut pattern 433. The first portion 630 and the second portion 730 of the functional layer 430 may correspond, for example, to a second functional layer 230 and a first functional layer 130, respectively. At least one cutting edge 337 may be a single continuous cutting edge when the second portion 730 includes a circular or elliptical plate, or 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) when the second portion is a rectangular plate.

[0043] The step of bringing the transfer article 200 into contact with the tool 333 so that the tool 333 embosses and cuts the transfer article 200 to form a cut pattern 433 on the functional layer 430 and forms multiple structures 255 on the carrier layer that define the upper 225 and lower 227 of the first main surface 212 can be performed at high temperatures (e.g., 80-120°C) and / or increased tool force (e.g., 500-20,000 pounds per foot of tool width) and has been found to result in improved cuts and separation between the upper and lower parts.

[0044] In some embodiments, the patterned article 300 is a transfer article configured such that the first portion 630 of the functional layer 430 can be transferred from the carrier layer 210 to the first adhesive layer 267, leaving the second portion 730 of the functional layer 430 positioned on the carrier layer 210, thereby allowing the second portion 730 of the functional layer 430 to be transferred from the carrier layer 210 to the second adhesive layer 268.

[0045] The various arrows in Figure 18 indicate the direction of movement of the tool 333 and various rollers and film or other articles as the method is performed. The roller 341 may be located on the opposite side of the transfer article 200 from the tool 333, which may generally be a cylindrical tool. In some embodiments, the method includes the step of transferring a first portion 630 to a first adhesive layer 267 to form a patterned article 301, which includes a layer 277 positioned on the first adhesive layer 267 opposite to the transferred first portion 630. The layer 277 may be, for example, a release layer. A roller 342 can be used in this step. In some embodiments, the method includes the step of transferring a second portion 730 to a second adhesive layer 268 to form a patterned article 302, which includes a layer 278 positioned on the second adhesive layer 268 opposite to the transferred second portion 730. The layer 278 may be, for example, a release layer. A roller 343 can be used in this step.

[0046] In some embodiments, the functional layer 430 is an inorganic layer. In other embodiments, the functional layer 430 is an organic layer. In some embodiments, the functional layer 430 includes at least one inorganic layer (e.g., at least one of layers 331a to 331f) and / or the functional layer includes at least one organic layer (e.g., at least one of layers 431a and 431b).

[0047] As further described elsewhere in this specification, in some embodiments, one of the upper 225 or lower 227 includes a mesh pattern 448, the mesh pattern 448 having an average line width Wc in the range of 0.5 micrometers to 50 micrometers, or Wc may be in another range described elsewhere in this specification. In some embodiments, in the top view, the lower 227 has a total area of ​​less than 50 percent of the total area of ​​the first main surface 212, or the total area of ​​the lower 227 may be in any range described elsewhere in this specification. In some embodiments, the functional layer 430 has a thickness in the range of 100 nm to 2000 nm, and the patterned articles 300, 300', 301, or 302 may have a thickness of, for example, less than 10 micrometers, less than 5 micrometers, or less than 3 micrometers. In some embodiments, the multiple microstructures 335 have an average width W1 in the range of, for example, 0.5 to 10 micrometers. In some embodiments, the multiple microstructures 335 have an average height h1 in the range of, for example, 0.5 to 50 micrometers, or 0.5 to 20 micrometers, or 0.5 to 10 micrometers.

[0048] Figure 19 is a schematic cross-sectional view of the microstructure 535 of the tool. The microstructure may correspond, for example, to the microstructure 335 of the tool 333. The microstructure 535 has opposing cutting ends 437 adapted to cut elements having a width W1 into a layer. The cutting ends 437 have a tip width Wt which can 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, 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.

[0049] The patterned articles 301 and / or 302 can be used to produce additional patterned articles by removing layer 277 or 278 and bonding the exposed surface of the adhesive layer 267 or 268 to another surface. Alternatively, or in addition, further patterned articles can be produced by bonding an additional layer to the patterned articles 301 and / or 302.

[0050] Figure 20 is a schematic cross-sectional view of a patterned article 501 according to several embodiments. The patterned article 501 includes a multilayer film 500, the multilayer film 500 including a first polymer layer 431a and a functional layer 530 including a first main surface 503 and a second main surface 505 (e.g., corresponding to 303 and 305) facing opposite directions, the first main surface 503 being disposed on the first polymer layer 431a, the functional layer 530 including a multilayer laminate (e.g., corresponding to a 330 or 330'' portion between layers 431a and 431b) including at least one microcut metal layer (e.g., one of 331a, 331b, or 331c) and at least one metal oxide layer or metal nitride layer (e.g., one different of 331a, 331b, or 331c), and a second polymer layer 431b disposed on the second main surface of the functional layer. Each microcut metal layer may have an average thickness in the range of 5 nanometers to 500 nanometers or 10 nanometers to 250 nanometers, and the cut pattern 433 includes a cut pattern 433 that forms either (i) a pattern of spaced-out individual plates 444 (or 544) defined by the cut, where a portion of the metal layer is substantially not located between the nearest adjacent plates 444a and plate 444b (for example, after cutting the functional layer, any metal initially present in the space 548 between plates 444a and plate 444b can be removed except for small amounts of metal, such as metal flakes or trace amounts of metal left behind when the metal initially present in the space 548 is removed), or (ii) a continuous pattern 448 corresponding to removing the pattern of spaced-out individual plates 444 from the metal layer, corresponding to the cut pattern 433. At least one metal oxide layer or metal nitride layer may be at least one metal oxide microcut layer or metal nitride microcut layer, and may have substantially the same cut pattern as at least one microcut metal layer.

[0051] In some embodiments, the multilayer film 500 further includes a first adhesive layer 511 disposed on a first polymer layer 431a, a first polymer film layer 521 disposed on the first adhesive layer 511, a second adhesive layer 512 disposed on a 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 one of the adhesive layers 267 and 268 schematically shown in Figure 18, the first polymer film layer 521 may correspond to one of the layers 277 and 278 schematically shown in Figure 18, or layer 277 or 278 may be a release liner that is removed and replaced with a film layer, the film layer being permanently bonded to the adhesive layer. The second adhesive layer 512 and the second polymer film layer 522 can then be attached to the second polymer layer 431b. The second adhesive layer 512 and the second polymer film layer 522 may be added, for example, 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., with a luminous transmittance of at least 80% and a haze of 10% or less, as determined according to ASTM D1003-13 “Standard Test Method for Haze and Luminous Transmittance of Transparent Plastics”). In some such embodiments, or in other embodiments, 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, for example, a release liner that is removed before the multilayer film is applied to the substrate. Layers 522, 512, and / or 521 may be omitted at will.

[0052] Figure 21 is a schematic perspective view of a substrate 550, and Figure 22 is a schematic perspective view of a patterned article 1000 including a multilayer film 500 placed on a portion 555 of the main surface 551 of the substrate 550. In some embodiments, the patterned article 1000 includes a substrate 550 and a multilayer film 500 placed on at least a portion 555 of the main surface 551 of the substrate and substantially conforming to the portion 555. The portion 555 of the main surface 551 may be a non-planar surface and / or curved around two mutually orthogonal axes (e.g., the x' axis and the y' axis). A curved shape around two mutually orthogonal axes may alternatively or additionally be called a shape having composite curvature. In some embodiments, the multilayer film 500 is stretched and molded so 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 flat film, as schematically shown in Figure 20. To adapt such a film to a non-flat surface (e.g., a sphere) such as a portion 555 that is curved around two mutually orthogonal axes, the film is stretched and molded to conform to the portion 555, as schematically shown in Figures 21 and 22.

[0053] In some embodiments, if the functional layer (e.g., 130, 230, 330, 330', 330'', 430) includes a metal layer or a metal oxide layer, the patterned articles of this specification may have at least one of the following effects: antimicrobial effect, antimicrobial effect, or antibiofilm effect. A wide variety of metal oxides MOx can be used in such applications, as long as the metal oxide layer exhibits at least 1 log reduction, at least 2 log reduction, at least 3 log reduction, or at least 4 log reduction against Staphylococcus aureus and Streptococcus mutans after 24 hours of contact. The log reduction values ​​are measured according to the ISO test method ISO 22196:2011 "Measurement of antibacterial activity on plastics and other non-porous surfaces," using the test method appropriately modified to suit the test material.

[0054] 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 of the functional layer is selected from AgCuZnOx, Ag-doped ZnOx, Ag-doped ZnO, Ag-doped TiO2, Al-doped ZnO, and TiOx.

[0055] In various embodiments, the functional layer may include any antimicrobially effective amount of metal, metal oxide MOx, or mixtures and combinations thereof. In various embodiments, the metal oxide layer may be, for example, 100 cm². 2 It may contain less than 100 mg, less than 40 mg, less than 20 mg, or less than 5 mg of MOx per serving.

[0056] In some embodiments, the functional layer may have dielectric properties that allow electromagnetic signals to pass through over a selected frequency range, which may be useful, for example, in 5G communication devices or other communication devices. For example, as described in IPC standard TM-650 2.5.5.13, if a patterned functional layer has a tanδ of about 0.12 or less when measured in a 9.5 GHz split-post dielectric resonator cavity, the layer may be more transparent to communication signals transmitted between mobile devices compared to their non-microcut state. In some embodiments, the microcut functional layer may have a real dielectric constant of about 33 and a complex dielectric constant of about 4.

[0057] In some embodiments, the shape and size of the plate 444 and / or mesh pattern 448 can be configured to provide transmittance to near-infrared signals, thereby enabling the formation of a highly adaptable near-IR sensor cover structure on a surface. In some embodiments, the plate and the spaces scattered between them can be configured to provide reflectivity to near-infrared signals and transmittance to visible light. For example, such a configuration can form a highly adaptable visible light sensor cover.

[0058] In some embodiments, the shape and size of the plates 444 and / or mesh patterns 448 can provide a functional layer with color change, reflectivity, transmittance, or other aesthetic effects, which can provide a useful decorative film that can be applied to complex or composite surfaces, such as the exterior or interior of a vehicle. For example, in some embodiments, a transfer article containing a microcut inorganic layer is reflective at visible wavelengths of 400–750 nm or 400–700 nm and at least partially transmittance at wavelengths above about 830 nm. For example, when exposed to ambient conditions, some plates 444 may oxidize over time, and this detectable color change can be used to evaluate, for example, the effective life of the product. If color change is undesirable, one or more protective barrier layers, for example, of metal oxides, can be superimposed on one or both surfaces of the microcut metal layer. In some embodiments, the metal layer may be configured such that the plates produce a color change effect when exposed to light across a selected wavelength range, for example, when the article is stretched two-dimensionally or three-dimensionally over a surface having composite curvature. [Examples]

[0059] The examples provided are for illustrative purposes only and are not intended to limit the scope of the attached "Claims." All parts, percentages, ratios, etc., in the examples and elsewhere in this specification are based on weight unless otherwise indicated.

[0060] [Table 1]

[0061] The micro-cut and embossing tools were prepared according to the following specifications: The tool was fabricated by diamond cutting deep grooves 12 micrometers (μm) deep into a cylindrical roll using conventional machining methods. The grooves were cut at 45 and -45 degrees relative to the circumferential direction of the roll. The pitch between the grooves was 300 μm. The resulting tool had intersecting grooves forming a diamond-shaped raised region with 45-degree intersecting grooves. Half of the pattern was cut with a tool having a 0.15 μm tip at the edge of the diamond. The diamond tip had a 60-degree angle.

[0062] Next, the pattern was removed from the roll by peeling off a thin layer of copper from the cylindrical surface having the groove pattern described above. Then, this thin copper sheet was nickel-plated using a conventional nickel electroplating method to form a negative of the cut groove pattern. The nickel sheet electroplated from the pattern with end features gave the nickel sheet raised edges.

[0063] Next, the nickel shims were back-ground to make them smooth, and then welded together to form a roll sleeve. The sleeve was then mounted on a temperature-controlled mandrel, and the mandrel was placed inside a laminator.

[0064] [Table 2]

[0065] Test method Microcut confirmation test Light leakage from fractures in film articles 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. Fractures were visible as higher visible light transmission regions surrounded by unbroken surfaces with lower visible light transmittance.

[0066] Preparation Example 1. Ag-coated transfer laminate The transfer film in this embodiment was fabricated on a roll-to-roll vacuum coater similar to the coater described in U.S. Patent Publication No. 2010 / 0316852(A1) (Condo et al.), using an evaporator described in U.S. Patent No. 8,658,248 (Anderson et al.), with the addition of a second evaporator and curing system positioned between the plasma pretreatment station and the first sputtering system. A roll of aluminum-plated biaxially oriented polypropylene film release layer of varying length (980 microinches (0.0250 mm) thick, 14 inches (35.6 cm) wide) (available from Toray Plastics (America) (North Kingstown, RI) under the trade name TORAYFAN PMX2) was mounted on the coater. The release layer was then advanced at a constant line speed of 32 fpm (9.8 m / min).

[0067] A first acrylate layer, tricyclodecanedimethanol diacrylate (obtained from Sartomer USA (Exton, PA) under the trade name SARTOMER SR833S), was applied to the release layer by ultrasonic spraying and flash deposition to create a coating width of 12.5 inches (31.8 cm). The liquid monomer flow rate to the evaporator was 0.67 mL / min. The nitrogen gas flow rate was 100 standard cubic centimeters per minute (sccm), and the evaporator temperature was set to 500°F (260°C). The process drum temperature was 14°F (-10°C). Subsequently, this monomer coating was cured immediately downstream using an electron beam curing gun operating at 7.0 kV and 10.0 mA to obtain an acrylate layer with a thickness of 180 nm.

[0068] A silver reflector layer was deposited on the first acrylate layer by DC sputtering using a >99% silver cathode target. The system was operated at 3kW with a line speed of 30 fpm (9.1 meters per minute). Two more depositions were then performed at the same power and line speed to fabricate a 90nm silver layer.

[0069] A layer of aluminum silicon oxide was deposited on a silver layer by AC reactive sputtering. The cathode had a Si(90%) / Al(10%) target and was obtained from Soleras Advanced Coatings US (Biddeford, ME). The cathode voltage during sputtering was monitored and the oxygen flow controlled by a feedback control loop. This system was operated at 32 kW of power to deposit a 12 nm thick layer of aluminum silicon oxide on the silver reflector. Similar to those described in U.S. Patent Application Publication No. 2020 / 0016879(A1) (Gotrik et al.) and No. 2020 / 0136086(A1) (Gotrik et al.), the aluminum surface of the TorayFAN PMX2 film separated from the first organic layer with a peel force of approximately 7.2 g / inch (0.283 g / mm) at 180.

[0070] Preparation Example 2. Weather-resistant Al-based MIM transfer laminate A roll of aluminum-plated polyethylene (PET) film release layer of varying length (980 microinches (0.0250 mm) thick, 14 inches (35.6 cm) wide) (obtained from Toray Plastics (America) (North Kingstown, RI) under the trade name TORAYFAN MT60) was mounted on the coater. A release layer having a coated first acrylate layer was prepared according to the procedure described in the first part of Preparation Example 1. An aluminum reflector layer was deposited on the first acrylate layer. A 60 nm thick layer of Al was deposited using a conventional DC sputtering process operating with argon gas and a power of 2 kW. The cathode Al target was obtained from ACI Alloys (San Jose, CA).

[0071] A second acrylate layer was applied on top of the reflective Al layer. The second acrylate layer was produced from a monomer solution of SARTOMER SR833S + 3% CN 147 (obtained from Sartomer USA (Exton, PA)) by spraying and vapor deposition. The acrylate layer was applied using a mixture flow rate of 0.67 mL / min to a sprayer, a gas flow rate of 60 sccm, and an evaporator temperature of 260°C. Once the coated acrylate condensed on the Al layer, it was cured with an electron beam operating at 7 kV and 10 mA to provide a layer with a thickness of 290 nm. This second acrylate layer provided an insulating layer for the functional metal-insulator-metal (MIM) transfer laminate.

[0072] A first inorganic barrier layer was applied on top of the second acrylate layer. The oxide material for the barrier layer was applied by an AC reactive sputtering deposition process using a 40 kHz AC power supply. The cathode had a Si(90%) / Al(10%) rotating target and was obtained from Soleras Advanced Coatings US. The cathode voltage during sputtering was monitored and the oxygen flow controlled by a feedback control loop. The system was operated at 16 kW of power to deposit a 12 nm thick aluminum silicon oxide layer on the second acrylate layer.

[0073] A second reflective layer was deposited on the first inorganic barrier layer in the same manner as the first reflective layer. The second reflective layer was deposited as an 8 nm thick layer of Al using a conventional DC sputtering process with argon gas and operating at 2 kW of power.

[0074] A second inorganic barrier layer was applied on top of the second reflective layer in the same manner as the first inorganic barrier layer.

[0075] A third acrylate layer was deposited on top of the second inorganic barrier layer. This layer was produced from a monomer solution of SARTOMER SR833S + 6% DYNASYLAN 1189 (obtained from Evonik Industries (Essen, DE)) by spraying and vapor deposition. 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 the coated acrylate condensed on the second inorganic barrier layer, it was cured with an electron beam operating at 7 kV and 10 mA to provide a layer with a thickness of 290 nm. Similar to those described in U.S. Patent Application Publication No. 2020 / 0016879(A1) (Gotrik et al.) and No. 2020 / 0136086(A1) (Gotrik et al.), the aluminum surface of the Toray MT60 film separates from the first organic layer with a peel force of 180 at approximately 7.2 g / inch (0.283 g / mm).

[0076] Example 1. Transfer-based article with micro-cut and embossed details. Preparation Example 1 was roll-to-roll laminated to micro-cut and embossing tool 1 at 240°F, and the backing material was attached by a steel roll laminator at 240°F using a nipple lamination force of 500 lbs / linear inch, an input tension of 3 lbs / inch, and an output (after micro-cut and embossing) tension of 1 lb / inch. Atomic force microscopy measured that the embossed area of ​​the third acrylate layer was 600 nm below the surface of the non-embossed area surrounding the third acrylate layer. Atomic force microscopy measured the line edge roughness of the cut edge of the non-embossed area to be approximately 200 nm.

[0077] Example 2. Transfer of non-embossed area The first OCA film was rapidly (<1 second) laminated onto the unembossed third acrylate layer of Example 1. The OCA was rapidly (<1 second) removed to bring the contacted third acrylate and the laminated multilayer onto the OCA surface. The remaining TORAYFAN MT60 release liner, which had been micro-cut and embossed, was set aside.

[0078] The "microcut confirmation test" confirmed that microcuts with a 10 μm gap were pre-set between the multilayer layers transferred onto the OCA surface. Accidental ruptures due to carelessness were observed inside the transferred multilayer regions.

[0079] Example 3. Transfer of embossed area Next, the adhesive surface of 8518 was laminated onto the remaining TORAYFAN MT60 release liner from Example 2, which had been micro-cut and embossed. 8518 was slowly removed from the TORAYFAN MT60, and the micro-cut and embossed features were applied. A "micro-cut confirmation test" confirmed the presence of a 10 μm multilayer feature on the surface of 8518. Accidental fractures were observed along the 10 μm wide multilayer present on the surface of 8518.

[0080] Example 4. Example 1 was repeated using micro-cutting and embossing tool 2. Example 4 was observed under an atomic force microscope (AFM), and functional layers of different heights (see, for example, Figure 3) were observed.

[0081] Example 5. Example 2 was completed using Example 4 instead of Example 1. A 4 μm gap existed between the multilayer layers transferred onto the OCA surface.

[0082] Example 6. Example 3 was completed using Example 5 instead of Example 2. A 4 μm wide multilayer feature region was present on the 8518 surface. By atomic force microscopy, the line edge roughness of the cut edge of the non-embossed region was measured to be approximately 600 nm.

[0083] Example 7. Example 1 was repeated along with Preparation Example 2. Example 7 was observed under an atomic force microscope (AFM), and functional layers of different heights (see, for example, Figure 3) were observed.

[0084] Example 8. Example 2 was completed using Example 7 instead of Example 1. Compared to Example 2, there were far fewer instances of accidental fracture observed inside the transferred multilayer region.

[0085] Terms such as “about” will be understood by those skilled in the art in the context in which they are used and described herein. Where the use of “about” in relation to the size, quantity, and physical properties of a feature is not otherwise obvious to those skilled in the art in the context in which it is used and described herein, “about” will be understood to mean within 10 percent of a particular value. A quantity given as about or approximately of a particular value may be exactly that particular value. For example, where it is not otherwise obvious to those skilled in the art in the context in which it is used and described herein, 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 may also be 1.

[0086] All references, patents, or patent applications cited above are incorporated herein by reference in their entirety. In the event of any inconsistency or contradiction between any part of the incorporated references and this application, the information in the foregoing description shall prevail.

[0087] Unless otherwise indicated, the descriptions of elements in the figures should be understood to apply equally to corresponding elements in other figures. While specific embodiments are illustrated and described herein, it will be understood by those skilled in the art that these specific embodiments may be replaced by various alternative and / or equivalent embodiments without departing from the scope of this disclosure. This application is intended to encompass all adaptations, modifications, or combinations of the specific embodiments discussed herein. Therefore, this disclosure is intended to be limited only by the claims and their equivalents. The following are exemplary embodiments. [Item 1] A carrier layer comprising a microstructured first main surface and a second main surface facing the opposite direction, wherein the first main surface includes a plurality of upper and lower ends spaced apart along the thickness direction of the carrier layer, defining the upper and lower parts of each of the first main surfaces, the lower part being located between the upper part and the second main surface, A first functional layer disposed on the lower part of the first main surface, rather than the upper part, and comprising at least one first microcut inorganic layer having a plurality of cut edges having substantially the same extent as the plurality of lower ends, A patterned article having the following features. [Item 2] The patterned article according to item 1, further comprising a second functional layer, the second functional layer located on the upper part of the first main surface rather than the lower part, and comprising at least one second microcut inorganic layer having a plurality of cut edges having substantially the same extent as the plurality of upper edges. [Item 3] A patterned article according to item 2, wherein the second functional layer can be transferred from the carrier layer to the first adhesive layer, leaving the first functional layer positioned on the carrier layer, and thereby the first functional layer can be transferred from the carrier layer to the second adhesive layer. [Item 4] The patterned article according to item 2 or 3, wherein the at least one second microcut inorganic layer comprises a plurality of spaced plates. [Item 5] The patterned article according to any one of items 1 to 4, wherein the at least one first microcut inorganic layer includes a mesh pattern. [Item 6] The patterned article according to any one of items 1 to 5, wherein when the patterned article is placed on a flat surface, the upper and lower parts of the first main surface are respectively located on first planes that are spaced apart from each other along the thickness direction of the carrier layer. [Item 7] A patterned article according to any one of items 1 to 6, wherein the average separation distance between the upper and lower parts of the carrier layer along the thickness direction is in the range of 0.3 micrometers to 10 micrometers. [Item 8] A method for manufacturing patterned articles, A transfer article, A carrier layer having a first main surface and a second main surface facing opposite directions, A functional layer disposed on the first main surface, A step of preparing a transfer article comprising, The steps include preparing a tool comprising multiple microstructures, each microstructure having at least one cutting end, The steps include arranging the transfer article and the tool adjacent to each other so that the functional layer faces the plurality of microstructures, The steps include bringing the transfer article into contact with the tool so that the tool embosses and cuts the transfer article to form a cut pattern in the functional layer and forms a plurality of structures in the carrier layer that define the upper and lower parts of the first main surface, The lower part is positioned between the upper part and the second main surface, the first portion of the functional layer is positioned on the upper part of the first main surface, the second portion of the functional layer is positioned on the lower part of the first main surface, and the first and second portions of the functional layer are separated from each other along the pattern of the cuts. method. [Item 9] The method according to item 8, wherein the functional layer includes at least one inorganic layer. [Item 10] The method according to item 8 or 9, wherein the functional layer comprises at least one organic layer. [Item 11] The method according to any one of items 8 to 10, 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, leaving the second portion of the functional layer positioned on the carrier layer, thereby enabling the transfer of the second portion of the functional layer from the carrier layer to the second adhesive layer. [Item 12] The method according to any one of items 8 to 11, wherein one of the upper or lower parts includes a mesh pattern having an average line width in the range of 0.5 micrometers to 50 micrometers. [Item 13] The method according to any one of items 8 to 12, wherein, in the top view, the lower part has a total area of ​​less than 40 percent of the total area of ​​the first main surface. [Item 14] A patterned article comprising a multilayer film, wherein the multilayer film is The first polymer layer, A functional layer comprising a first main surface and a second main surface facing opposite directions, wherein the first main surface is disposed on the first polymer layer, and the functional layer comprises a multilayer laminate comprising at least one microcut metal layer and at least one metal oxide layer or metal nitride layer, each microcut metal layer having an average thickness in the range of 5 nanometers to 500 nanometers and a cut pattern, (i) A pattern of spaced-out individual plates defined by the cut, corresponding to the pattern of the cut, wherein the portion of the metal layer is not substantially located between the nearest adjacent plates, or (ii) A continuous pattern corresponding to removing the pattern of spaced individual plates corresponding to the cut pattern from the metal layer. A functional layer including a cut pattern that forms one of the following, A second polymer layer disposed on the second main surface of the functional layer, A patterned article having the following features. [Item 15] A patterned article according to item 14, further comprising a base material, wherein the multilayer film is positioned on at least a portion of the main surface of the base material and substantially conforms to the at least portion of the main surface of the base material, and the portion of the main surface is curved about two mutually orthogonal axes.

Claims

1. A carrier layer comprising a microstructured first main surface and a second main surface opposite the first main surface, wherein the first main surface includes a plurality of upper and lower ends, the upper and lower ends being spaced apart along the thickness direction of the carrier layer and defining a plurality of upper and lower parts of the first main surface, the lower parts being positioned between the upper parts and the second main surface, A first functional layer disposed on the lower part of the first main surface, rather than the upper part, and comprising at least one first microcut inorganic layer including a plurality of cut edges having substantially the same extent as the plurality of lower ends, A patterned article comprising, The patterned article further comprises a second functional layer located on the upper part of the first main surface rather than the lower part, and comprising at least one second microcut inorganic layer including a plurality of cut edges having substantially the same extent as the plurality of upper edges, The patterned article is configured such that the second functional layer can be transferred from the carrier layer to the first adhesive layer while leaving the first functional layer positioned on the carrier layer, thereby enabling the first functional layer to be transferred from the carrier layer to the second adhesive layer. Patterned items.

2. The patterned article according to claim 1, wherein the at least one second microcut inorganic layer comprises a plurality of spaced plates.

3. The patterned article according to claim 1, wherein the at least one first microcut inorganic layer includes a mesh pattern.

4. The patterned article according to claim 1, wherein when the patterned article is placed on a flat surface, the upper and lower parts of the first main surface are respectively located on first planes that are spaced apart 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 separation distance between the upper and lower parts of the carrier layer along the thickness direction is in the range of 0.3 micrometers to 10 micrometers.

6. A method for manufacturing patterned articles, A transfer article, A carrier layer having a first principal surface and a second principal surface facing opposite directions, A functional layer disposed on the first main surface, A step of preparing a transfer article comprising, The steps include preparing a tool comprising multiple microstructures, each microstructure having at least one cutting end, The steps include arranging the transfer article and the tool adjacent to each other so that the functional layer faces the plurality of microstructures, The steps include bringing the transfer article into contact with the tool so that the tool embosses and cuts the transfer article to form a cut pattern in the functional layer and forms a plurality of structures in the carrier layer that define a plurality of upper and a plurality of lower parts of the first main surface, The lower part is positioned between the upper part and the second main surface, the first portion of the functional layer is positioned on the upper part of the first main surface, the second portion of the functional layer is positioned on the lower part of the first main surface, and the first and second portions of the functional layer are separated from each other along the pattern of the cuts. 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, leaving the second portion of the functional layer on the carrier layer, thereby enabling the transfer of the second portion of the functional layer from the carrier layer to the second adhesive layer. method.

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

8. The method according to 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 one of the upper or lower parts includes a mesh pattern having an average line width in the range of 0.5 micrometers to 50 micrometers.

10. The method according to any one of claims 6 to 8, wherein in the top view, the lower part has a total area of ​​less than 40 percent of the total area of ​​the first main surface.

11. A patterned article comprising a multilayer film, wherein the multilayer film is The first polymer layer, A functional layer comprising a first main surface and a second main surface facing opposite directions, wherein the first main surface is disposed on the first polymer layer, and the functional layer comprises a multilayer laminate comprising at least one microcut metal layer and at least one metal oxide layer or metal nitride layer, each microcut metal layer having an average thickness in the range of 5 nanometers to 500 nanometers and a cut pattern, (i) A pattern of spaced-out individual plates defined by the cut, corresponding to the pattern of the cut, wherein the portion of the metal layer is not substantially located between the nearest adjacent plates, or (ii) A continuous pattern corresponding to removing the pattern of spaced individual plates corresponding to the cut pattern from the metal layer. A functional layer including a cut pattern that forms one of the following, A second polymer layer disposed on the second main surface of the functional layer, Equipped with, The patterned article further includes a base material, A patterned article wherein the multilayer film is placed on at least a portion of the main surface of the substrate and substantially conforms to the at least portion of the main surface of the substrate, and the portion of the main surface is curved around two mutually orthogonal axes.

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