Microcut patterned article and method of making 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 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 can be suitable for roll-to-roll manufacturing. Sputtering can be used to deposit stacks of inorganic thin film layers, such as metal and metal oxide layers, onto a substrate. The materials, thicknesses, and sequence of the thin inorganic layers with different refractive indices can be selected to fine-tune the aesthetic appearance and transmission properties of the article. Summary of the Invention

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

[0003] In some aspects of the present disclosure, a patterned article is provided. The patterned article includes a carrier layer having a microstructured first major surface and an oppositely facing second major surface. The first major surface includes a plurality of upper and lower edges spaced apart along a thickness direction 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 portion but not on the 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.

[0004] In some aspects of the present specification, a method for manufacturing a patterned article is provided. The method includes the steps of: preparing a transfer article, the transfer article including a carrier layer having a first major surface and a second major surface facing opposite directions, and including a functional layer disposed on the first major surface; preparing a tool including a plurality of microstructures, each microstructure including at least one cutting edge; placing 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 pattern of cuts in the functional layer and a plurality of structures in the carrier layer that define the upper and lower portions of the first major surface. The lower portion is disposed between the upper portion and the second major surface. A first portion of the functional layer is disposed on the upper portion of the first major surface, and a second portion of the functional layer is disposed on the lower portion of the first major surface. The first portion and the second portion of the functional layer are spaced apart from each other along the pattern of cuts.

[0005] In some aspects herein, a patterned article is provided that includes a multilayer film. The multilayer film includes a first polymer layer, a functional layer including oppositely facing first and second major surfaces, the first major surface being disposed on the first polymer layer, and a second polymer layer disposed on the second major surface of the functional layer. The functional layer includes a multilayer stack including 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 pattern of cuts that form either (i) a pattern of spaced apart individual plates that correspond to the pattern of cuts and are defined by the cuts, with no portions of the metal layer being located between the nearest adjacent plates, or (ii) a continuous pattern that corresponds to removing from the metal layer the pattern of spaced apart individual plates that correspond to the pattern of cuts.

[0006] These and other aspects will become apparent from the following detailed description, but in no way should this brief summary be construed as limiting the claimed subject matter. [Brief description of the drawings]

[0007] [Figure 1] 1 is a schematic cross-sectional view of a carrier layer according to some embodiments. [Diagram 2] 1 is a schematic cross-sectional view of a patterned article including a functional layer according to some embodiments. [Diagram 3] 1 is a schematic cross-sectional view of a patterned article comprising a first functional layer and a second functional layer according to some embodiments. [Figure 4] 1 is a schematic cross-sectional view of a patterned article comprising a first functional layer and a second functional layer according to some embodiments. [Figure 5A] FIG. 2 is a schematic cross-sectional view of another patterned article comprising a first functional layer and a second functional layer according to some embodiments. [Figure 5B] FIG. 5B is a schematic cross-sectional view of a patterned article corresponding to the patterned article of FIG. 5A with the second functional layer removed, according to some embodiments. [Figure 6] 1 is a schematic cross-sectional view of a functional layer according to some embodiments. [Figure 7] 1 is a schematic cross-sectional view of a functional layer according to some embodiments. [Figure 8] 1 is a schematic cross-sectional view of a functional layer according to some embodiments. [Figure 9] 1A-1C are schematic top views of patterned functional layers exhibiting line edge roughness according to some embodiments. [Figure 10A] 1 is a schematic cross-sectional view of a patterned article including an overcoat, according to some embodiments. [Figure 10B] 1 is a schematic cross-sectional view of a patterned article including an overcoat, according to some embodiments. [Figure 11]FIG. 2 is a schematic top view of a patterned article comprising a first functional layer and a second functional layer according to some embodiments. [Figure 12] FIG. 2 is a schematic top view of a patterned article comprising a first functional layer and a second functional layer according to some embodiments. [Figure 13] FIG. 2 is a schematic top view of a patterned article comprising a first functional layer and a second functional layer according to some embodiments. [Figure 14] 1 is a schematic top view of a patterned article including a functional layer, according to some embodiments. [Figure 15] 1 is a schematic top view of a patterned article including a functional layer, according to some embodiments. [Figure 16] 1 is a schematic top view of a patterned article including a functional layer, according to some embodiments. [Figure 17] 1 is a schematic cross-sectional view of a transfer article according to some embodiments. [Figure 18] 1 is a schematic diagram of a method for manufacturing a patterned article, according to some embodiments. [Figure 19] 1 is a schematic cross-sectional view of a microstructure of a tool for manufacturing a patterned article according to some embodiments. [Figure 20] 1 is a schematic cross-sectional view of a patterned article comprising a multilayer film, according to some embodiments. [Figure 21] FIG. 1 is a schematic perspective view of an exemplary substrate having a curved surface. [Figure 22] FIG. 1 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 DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] In the following description, reference is made to the accompanying drawings, which form a part hereof, and in which are shown by way of illustration various embodiments. The drawings are not necessarily to scale. It is to be understood that other embodiments are contemplated and may be made without departing from the scope or spirit of the specification. Accordingly, the following detailed description is not to be taken in a limiting sense.

[0009] In some aspects, the present disclosure generally relates to a transfer article comprising a dimensionally stable but flexible transfer substrate having a functional layer thereon comprising at least one (e.g., ultra-thin) inorganic layer. In some embodiments, the inorganic layer(s) in the functional layer of the transfer article are formed by a sputtering process, e.g., having a thickness of 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 closely corresponds to the pattern of the cutting edges of the tool. The precise pattern of cut edges may form an array of plates and mesh patterns, and the plates and mesh patterns 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 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 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 including the micro-cut inorganic layer, which may be diffusely reflective, is stretched in at least one dimension and applied to a non-flat or structured surface. For example, the network of plates in the micro-cut inorganic layer may stretch to various degrees to accommodate the stretching and strain during the application process and conform to the surface. The patterned article, when applied to a surface, forms a micro-cut article with a precise arrangement of plates small enough to provide tunable reflective performance with consistent color and mirror-like aesthetic appearance at selected viewing angles relative to its major surface.

[0011] Because the pattern of cut edges in the microcut inorganic layer can be a faithful reproduction of the pattern on the microstructured tool, precise placement of the plates allows for more precise control of the aesthetic appearance and / or electrical conductivity of an article comprising a laminate of inorganic materials when the article is stretched in one or more directions and applied or adhesively bonded to a composite surface to form a laminate article. Microcutting the inorganic layer can make it transparent to electromagnetic signals in a desired frequency range, thereby producing articles that are useful, for example, in communication devices.

[0012] FIG. 1 is a schematic cross-sectional view of a carrier layer 110 according to some embodiments. FIG. 2 and FIG. 3 are schematic cross-sectional views of patterned articles 100 and 100' according to some embodiments. In some embodiments, the patterned articles 100, 100' include a carrier layer 110 including a microstructured first major surface 112 and an oppositely facing second major surface 114. The first major surface 112 defines a top portion 125 and a bottom portion 127 of the first major surface 112 spaced apart along a thickness direction (z direction with reference to the illustrated xyz coordinate system) of the carrier layer 110, the bottom portion 127 including a plurality of top edges 121 and bottom edges 123 disposed between the top portion 125 and the second major surface 114. In some embodiments, the top portions 125 and bottom portions 127 are arranged in first and second regular patterns, respectively (e.g., a mesh pattern and a regular pattern of spaced apart plates, as further described elsewhere herein). Patterned article 100, 100' includes a first functional layer 130 disposed on the bottom (127) but not the top (125) of first major surface 112. First functional layer 130 includes at least one first micro-cut inorganic layer 131 including a plurality of cut edges 133 substantially coextensive with the plurality of bottom edges 123. First functional layer 130 may be a single first micro-cut inorganic layer 131 or may include multiple layers as further described elsewhere herein.

[0013] In some embodiments, patterned article 100' further includes a second functional layer 230 disposed on the upper (125) but not the lower (127) portion of first major surface 112, the second functional layer 230 including at least one second micro-cut inorganic layer 231 including a plurality of cut edges 233 substantially coextensive with the plurality of top edges 121. Second functional layer 230 may be a single second micro-cut inorganic layer 231 or may include multiple layers as further described elsewhere herein.

[0014] In some embodiments, the cut edges 133 and / or the cut edges 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 the cut edges 233 can have a linear shape and can be arranged in a plurality of substantially parallel (e.g., parallel to within 20 degrees, or 10 degrees, or 5 degrees) line segments (see, e.g., FIGS. 11-16 ), or in a plurality of substantially parallel first line segments (e.g., parallel to the x direction in FIGS. 11-15 ) and substantially parallel second line segments (e.g., parallel to the y direction in FIGS. 11-15 ) that are substantially perpendicular (e.g., perpendicular to within 20 degrees, or 10 degrees, or 5 degrees) to the first line segments. In various embodiments, the cut edges 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) can be about 0.3 to about 2000 / mm 2 , about 1 to about 1000 / mm 2 , about 10 to about 500 / mm 2 , about 20 to about 200 / mm 2 , or about 50 to about 100 / mm 2 on the first major surface 112.

[0015] A microstructure is generally a structure having at least two orthogonal dimensions (e.g., height and width) each in the range of about 0.1 micrometer to about 2000 micrometers. A microcut layer generally refers to a layer having cuts defining elements of the layer with at least one dimension in the plane of the layer in the range of about 0.1 micrometer to about 2000 micrometers. A layer can be microcut using a tool having microstructures, each microstructure having at least one cutting edge. Such tools can be manufactured using conventional microfabrication processes (e.g., diamond cutting the microstructures into 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. Pat. Nos. 7,140,812 (Bryan et al.) and 8,443,704 (Burke et al.). Microcutting generally produces a sharp cut edge having a width (e.g., corresponding to tip width Wt shown generally in FIG. 19) that is substantially smaller (e.g., at least 2 times, or at least 4 times, or at least 8 times smaller) than the smallest lateral dimension of the element formed by the microcutting (e.g., width W1 shown generally in FIG. 19). Such cuts are sometimes referred to as microcuts. For example, cut edge 133 and / or cut edge 233 can be microcut edges.

[0016] A functional layer that includes at least one micro-cut layer may be referred to as a micro-cut functional layer. In some embodiments, each layer in functional layers 130 and 230 is a micro-cut layer that has substantially the same pattern of cuts as the corresponding micro-cut inorganic layer.

[0017] A cut edge (e.g., cut edge 133 and 233) of a layer (e.g., inorganic layer 131 and 231) disposed on the top (125) or bottom (127) of first major surface 112 may refer to an edge between a sidewall of the layer and a major surface of the layer that faces the top (125) or bottom (127) of first major surface 112. Alternatively, a cut edge of a layer may refer to a side edge of the layer that extends between the upper and lower major surfaces of the layer. A plurality of edges (e.g., 133, 233) may be described as being substantially coextensive with another plurality of edges (e.g., 123, 121) if, in a top 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. In some embodiments, at least 70%, at least 80%, at least 90%, or at least 95% of the total length of each of the plurality of ends extends along at least 70%, at least 80%, at least 90%, or at least 95% of the total length of the other plurality of ends.

[0018] In various embodiments, the functional layer (e.g., functional layer 130 or 230) can include a stack of one or more layers selected to provide an article including the functional layer with some functional property, which can include, for example, electromagnetic properties, which can include, for example, electrically conductive properties or reflective or transmissive properties, aesthetic properties, environmental properties, or antimicrobial properties.

[0019] In some embodiments, the patterned article 100' is configured to allow the second functional layer 230 to be transferred from the carrier layer 110 to the first adhesive layer 267 (see, e.g., FIG. 18 ), while leaving the first functional layer 130 disposed on the carrier layer 110. For example, after the second functional layer 230 is transferred, the patterned article 100' may correspond to the patterned article 100. In some embodiments, the patterned article 100 is configured to allow the first functional layer 230 to be transferred from the carrier layer 110 to the adhesive layer 268 (see, e.g., FIG. 18 ). In some embodiments, the patterned article 100' is a transfer article configured to allow the second functional layer 230 to be transferred from the carrier layer 110 to the first adhesive layer 267, while leaving the first functional layer 130 disposed 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 herein, the carrier layer 110 may include a release coating to facilitate transfer of the first functional layer 130 and the second functional layer 230 .

[0020] In some embodiments, the first major 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 can have an average thickness that is about the same (e.g., within 10%, 5%, or 3%) as the average thickness t0 of the first functional layer 130. The average height h0 may be greater than the average thickness t0 as shown generally in FIGS. 2 and 3, about the same as the average thickness t0 as shown generally in FIG. 4, or less than the average thickness t0 as shown generally in FIGS. 5A and 5B. In some embodiments, the average separation (h0) of the upper and lower portions (125) and (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 separation (h0) of the upper (125) and lower (127) portions 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 separation (h0) of the upper (125) and lower (127) portions 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'. 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 layers. Figure 5B is a schematic cross-sectional view of patterned article 104', which may correspond to patterned article 104, except that functional layer 230'' has been removed. In the patterned article 102, the functional layers 130' and 230' each have an average thickness that is approximately the same as the average separation (h0) of the upper (125) and lower (127) portions along the thickness direction (z-direction) of the carrier layer 110. In the patterned article 104, the functional layers 130' and 230' each have an average thickness that is greater than the average separation (h0) of the upper (125) and lower (127) portions along the thickness direction (z-direction) of the carrier layer 110.

[0021] In some embodiments, when the patterned article 100 is placed on the flat surface 174, the upper (125) and lower (127) surfaces of the first major surface 112 are positioned on first planes 176 and 178, respectively, 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 (h0) of the upper (125) and lower (127) portions along the thickness direction (z-direction) of the carrier layer 110 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 (h0) of the upper (125) and lower (127) portions along the thickness direction (z-direction) of the carrier layer 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 can be in a 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 has a thickness in a 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 can be, for example, greater than 0.5 micrometers.

[0023] 6-8 are schematic cross-sectional views of functional layers 330, 330′, and 330″, any of which may correspond to functional layers 130 or 230 (e.g., in some embodiments, functional layers 130 and 230 may be obtained by microcutting functional layers 330, 330′, or 330″, as further described elsewhere herein). Functional layer 330 includes layers 331a, 331b, and 331c and has oppositely facing first outermost major surface 303 and second outermost major surface 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. The functional layer 330' includes a functional layer 330 having oppositely facing first and second outermost major surfaces 303' and 305' disposed between a first layer 431a and a 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. A polymer layer may be understood to be an organic polymer layer unless otherwise indicated. The functional layer 330'' includes the first layer 431a and the second layer 431b and at least layers 331a-331f disposed between the first layer 431a and the second layer 431b. In some embodiments, the functional layer includes multiple 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, the functional layer (or, for example, the first functional layer 130 and / or the second functional layer 230) can include at least one organic layer and at least one inorganic layer. For example, the patterned article can include a first functional layer that includes at least one first micro-cut inorganic layer and further includes at least one micro-cut organic layer that can be substantially coextensive with the first micro-cut inorganic layer. The patterned article can further include a second functional layer that includes at least one second micro-cut inorganic layer and further includes at least one micro-cut organic layer that can be substantially coextensive with the second micro-cut inorganic layer. The patterning techniques described herein can be applied to a functional layer that includes 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 the organic layer(s) and the inorganic layer(s) are patterned in separate (e.g., etching) steps. For example, the functional layer can include a metal layer disposed between polymer layers. The inclusion of a polymer layer with a metal layer in the functional layer has been shown, for example, to improve 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 of 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 with a metal nitride layer. Other suitable functional layers are described, for example, in WO 2020 / 240419 (Gotrik et al.).

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

[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 the metals described herein for the metal layer may be used in the oxide or nitride layer. Since silicon is a semimetal, as the term is used herein, silicon oxide is considered to be a metal oxide and silicon nitride is considered to be a metal nitride.

[0028] In some embodiments, a functional layer (e.g., functional layer 130, 230, 330, 330′, or 330″, or another functional layer described elsewhere herein) includes at least one micro-cut metal layer. In some embodiments, the at least one micro-cut metal layer includes or is formed of silver. For example, layer 331b can be a silver layer, and each of layers 331a and 331b can be a metal oxide layer. The oxide-protected silver layer is useful, for example, in plasmonic applications. In some embodiments, the micro-cut functional layer includes an oxide-protected silver layer between polymer layers (e.g., layers 431a and 431b). The methods herein can enable functional layers including an oxide-protected silver layer and including a polymer layer to be patterned by micro-cutting, according to some embodiments. It has been found difficult to create a patterned functional layer including an oxide-protected silver layer and a polymer layer using conventional techniques (e.g., dry or wet lithography).

[0029] The line edge roughness of the cut edges can be substantially less than that obtained from conventional patterning processes such as, for example, lift-off lithography. FIG. 9 is a schematic top view of a patterned functional layer showing line edge roughness, according to some embodiments. A roughness parameter Ra may be used for the line edge roughness. For example, the edge 747 has a line edge roughness Ra that can be described as the average of the absolute values ​​of the displacement of the edge 747 from the average position 888 of the edge 747. In some embodiments, the average line edge roughness Ra of the plurality of cut edges and / or the pattern of cuts can be less than 1 micrometer, less than 500 nm, or less than 100 nm, for example, as low as 10 nm. In some embodiments, the patterned article includes at least one first micro-cut inorganic layer (e.g., disposed on a lower portion of the microstructured major surface) including a plurality of cut edges having an average line edge roughness Ra of less than 1 micrometer or within the ranges described elsewhere herein. In some embodiments, the patterned article also includes at least one second micro-cut inorganic layer (e.g., disposed on top of the microstructured primary surface) that includes a plurality of cut edges having an average line edge roughness Ra of less than 1 micrometer or in the ranges described elsewhere herein. In some embodiments, the patterned article includes at least one micro-cut metal layer, each micro-cut metal layer having a pattern of cuts. In some embodiments, for each micro-cut metal layer, the pattern of cuts has an average line edge roughness Ra of less than 1 micrometer or in the ranges described elsewhere herein.

[0030] The various layers of functional layers 330, 330', and 330" may be applied by, for example, reactive vapor deposition, (e.g., reactive) sputtering, chemical vapor deposition, plasma-enhanced chemical vapor deposition, and / or atomic layer deposition. Suitable methods for forming the functional layers are described, for example, in U.S. Patent Application Publication No. 2012 / 0208033 (Weigel et al.), as well as U.S. Patent Nos. 4,696,719 (Bischoff); 4,722,515 (Ham); 4,842,893 (Yializis et al.); 4,954,371 (Yializis), 5,018,048 (Shaw et al.); 5,032,461 (Shaw et al.); 5,097,800 (Shaw et al.); Nos. 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.).

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

[0032] 11-13 are schematic top views of a patterned article including a plurality of spaced apart plates 444 and a continuous pattern 448 (e.g., a mesh pattern) spaced apart from one another along the pattern of cuts 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 micro-cut inorganic layer 231 includes a plurality of spaced apart plates 444. In some such embodiments, or in other embodiments, at least one first micro-cut inorganic layer 131 includes a mesh pattern. In some embodiments, at least one second micro-cut inorganic layer 231 includes a mesh pattern 448. In some such embodiments, or in other embodiments, the at least one first micro-cut inorganic layer 131 includes a plurality of spaced apart plates 444. In various embodiments, the exposed surfaces of the plates 444 may be substantially flat or may be contoured.

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

[0034] Figure 15 is a schematic top view of mesh pattern 448, which may correspond, for example, to a patterned article (e.g., patterned article 100) after second functional layer 230 arranged in a spaced plate pattern has been removed, or may correspond to second functional layer 230 arranged in a mesh after 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 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 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 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 in 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 between the plates 444 (along the x direction and / or along the y direction) 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 square since a square is a special case of a rectangle. The plate 444 can have any other suitable shape such as circular or elliptical. In a general shape, Wa can be interpreted as the length of the shortest in-plane line that extends across the entire shape and passes through the centroid 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] 16 is a schematic top view of a plurality of spaced apart strips 544 extending along the same first direction (y-direction). The strips 544 may correspond to the first functional layer 130 or the second functional layer 230, or may correspond to at least one first micro-cut inorganic layer or at least one second micro-cut inorganic layer. In some embodiments, at least one first micro-cut inorganic layer 131 includes a plurality of spaced apart strips 544 extending along the same first direction (y-direction). In some embodiments, at least one second micro-cut inorganic layer 231 includes a plurality of spaced apart strips 544 extending along the same first direction (y-direction). The strips 544 may be considered to be plates with a large aspect ratio (e.g., Wb / Wa>5 or Wb / Wa>10).

[0037] In some embodiments, in a top view (along the negative z-direction), the lower portion 127 has a total area that is 50 percent or less of the total area of ​​the first major surface 112. For example, the mesh pattern 448 of FIG. 12 may be disposed on the lower portion 127. As another example, the plate 444 of FIG. 13 may be disposed on the lower portion 127. The total area of ​​the first major surface 112 in a top view includes the areas of the upper portion 125 and the lower portion 127, but does not include the area of ​​the vertical sidewalls. In some embodiments, in a top view, the lower portion has a total area that is 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 major surface. In some such embodiments, or in other embodiments, in a top view, the lower portion 127 has a total area that is 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 major surface. In some embodiments, the second functional layer 230 is transferred from the carrier layer 110 leaving the first functional layer 130 disposed on the lower portion 127, which may then be transferred to another layer. In some embodiments, it may be desirable for an article including a first functional layer (e.g., disposed on the lower portion 127 or transferred to another layer) to be optically transparent. In some such embodiments, or in other embodiments, it may be preferred that, in a top view, the lower portion 127 has a total area that is less than 10% of the total area of ​​the first major surface 112. For example, in a top view, the lower portion 127 may have a total area that is about 8% or less of the total area of ​​the first major 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 micro-cut inorganic layer 131 and / or the second micro-cut inorganic layer 231 are crack-free or substantially crack-free. A layer may be described as substantially crack-free if the cracks are not visible to humans at a distance of 10 cm (by a naked eyed person with normal vision (20 / 20 vision) under normal room lighting conditions, which may be described in the UNE-EN 12464-1:2012 standard). A crack is different from a cut because a cut leaves a mark (e.g., a tool mark) that is different from the mark of a crack. In some embodiments, the first inorganic layer 131 and / or the second inorganic layer 231 include multiple cut (e.g., micro-cut) edges and do not include cracks that extend between different cut edges.

[0039] In some embodiments, the patterned article is a transfer article configured to be capable of transferring the first functional layer 130 and / or the second functional layer 230 from the carrier layer 110 to an adhesive layer (see, e.g., 267 or 268 in FIG. 18). FIG. 17 is a schematic cross-sectional view of a transfer article 200 including a pre-patterned carrier layer 210 that may be used in making a patterned article and may correspond to the carrier layer 110, as further described elsewhere herein. The transfer article 200 includes a carrier layer 210 including a functional layer 430 (e.g., corresponding to the functional layer 130 or 230, or another functional layer described elsewhere herein), and a substrate 226 and a release coating 228 disposed on the substrate 226 and facing the functional layer 430 (or, e.g., 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 shown generally in FIG. 17. In some embodiments, the substrate 226 includes or is formed of polyethylene terephthalate (PET) or biaxially oriented polypropylene (BOPP). The PET may be, for example, uniaxially or biaxially oriented. In some embodiments, the release coating 228 is or includes a metal layer or a doped semiconductor layer. The metal layer may conveniently be formed of 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 of Si, B-doped Si, Al-doped Si, 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 release value between the release coating 228 and the functional layer 430 is between 2 and 50 grams per inch. In some embodiments, the carrier layer 110 or 210 is or includes aluminum coated PET or aluminum coated BOPP.The release layer may be prepared, for example, by vapor deposition, reactive vapor deposition, sputtering, reactive sputtering, chemical vapor deposition, plasma-enhanced chemical vapor deposition, or atomic layer deposition. Other suitable release-coated substrates are described, for example, in WO 2020 / 240419 (Gotrik et al.).

[0040] The substrate 226 of the carrier layer 210 may be or may include a low modulus layer (e.g., a layer having 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 a 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. The low modulus layer may reduce the pressure required to complete the patterning process, e.g., improving the fidelity of the reproduction of the pattern of the cutting edge of a microcutting tool. In other embodiments, the substrate 226 is, for example, a monolithic PET or BOPP film.

[0041] 18 is a schematic cross-sectional view of a method of manufacturing patterned article 300 (e.g., corresponding to patterned article 100 or another patterned article described elsewhere herein) or patterned article 300' (e.g., corresponding to patterned article 100' or another patterned article described elsewhere herein), and a method of transferring a functional layer of the resulting patterned article 300, 300' to another layer to form patterned articles 301 and 302. Interrupts 776 and 777 are included to indicate that the processes to the left and right of interruptions 776, 777 can 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 776 is omitted (or performed as a separate process) and the method is a method of manufacturing patterned article 300. In some embodiments, the portion to the right of interruption 777 is omitted (or performed as a separate process) and the method is a method of 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, a method for making patterned articles 300, 300', 301, and / or 302 (or 100, 100', or another patterned article described elsewhere herein) is provided. The method can include providing a transfer article 200, which includes a carrier layer 210 having oppositely facing first and second major surfaces 212, 214 and a functional layer 430 disposed on the first major surface 212. The method may further include providing a tool 333 including a plurality of microstructures 335, each microstructure including at least one cutting edge 337, positioning the transfer article 200 and the tool 333 adjacent to one another 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 scores the transfer article 200 to form the pattern of cuts 433 in the functional layer 430 and to form in the carrier layer a plurality of structures 255 that define the upper and lower portions 225 and 227 of the first major surface 212. The lower portion 227 is disposed between the upper portion 225 and the second major surface 214. A first portion 630 of the functional layer 430 is disposed on the upper portion 225 of the first major surface 212, and a second portion 730 of the functional layer 430 is disposed on the lower portion 227 of the first major surface 212. The first portion 630 and the second portion 730 of the functional layer 430 are spaced apart from one another along a pattern of cuts 433. The first portion 630 and the second portion 730 of the functional layer 430 may correspond to, for example, the second functional layer 230 and the first functional layer 130, respectively. The at least one cutting edge 337 can be a single continuous cutting edge when the second portion 730 comprises a circular or elliptical plate, or the at least one cutting edge 337 can include at least two opposing cutting edges (e.g., opposing first and second cutting edges, and opposing third and fourth cutting edges), for example, when the second portion is a rectangular plate.

[0043] The step of contacting the transfer article 200 with the tool 333 so that the tool 333 embosses and cuts the transfer article 200 to form a pattern of cuts 433 in the functional layer 430 and a plurality of structures 255 in the carrier layer that define the upper and lower portions 225 and 227 of the first major surface 212 can be performed at elevated temperatures (e.g., 80-120°C) and / or increased tool forces (e.g., 500-20,000 pounds per foot of tool width), which has been found to result in improved cutting and separation between the upper and lower portions.

[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 while leaving the second portion 730 of the functional layer 430 disposed 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 FIG. 18 indicate the direction of movement of the tool 333 and the various rollers and films 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 be a generally cylindrical tool. In some embodiments, the method includes transferring the first portion 630 to the first adhesive layer 267 to form a patterned article 301 including a layer 277 disposed on the first adhesive layer 267 opposite the transferred first portion 630. The layer 277 may be, for example, a release layer. A roller 342 may be utilized in this step. In some embodiments, the method includes transferring the second portion 730 to the second adhesive layer 268 to form a patterned article 302 including a layer 278 disposed on the second adhesive layer 268 opposite the transferred second portion 730. The layer 278 may be, for example, a release layer. A roller 343 may be utilized in this step.

[0046] 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-331f) and / or functional layer includes at least one organic layer (e.g., at least one of layers 431a and 431b).

[0047] As further described elsewhere herein, in some embodiments, one of the upper portion 225 or the lower portion 227 includes a mesh pattern 448, and the mesh pattern 448 has an average line width Wc in the range of 0.5 micrometers to 50 micrometers, or Wc can be in another range described elsewhere herein. In some embodiments, in top view, the lower portion 227 has a total area that is less than 50 percent of the total area of ​​the first major surface 212, or the total area of ​​the lower portion 227 can be in any range described elsewhere herein. In some embodiments, the functional layer 430 has a thickness in the range of 100 nm to 2000 nm, and the patterned article 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 plurality of microstructures 335 has an average width W1 in the range of, for example, 0.5 to 10 micrometers. In some embodiments, the plurality of microstructures 335 has 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] 19 is a schematic cross-sectional view of a tool microstructure 535. The microstructure may correspond to the microstructure 335 of the tool 333, for example. The microstructure 535 has opposing cutting edges 437 adapted to cut an element having a width W1 into the layer. The cutting edges 437 have a tip width Wt that may be two times 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] Patterned articles 301 and / or 302 can be used to produce additional patterned articles by removing layer 277 or 278 and adhering the exposed surface of adhesive layer 267 or 268 to another surface. Alternatively, or in addition, further patterned articles can be produced by adhering additional layers to patterned articles 301 and / or 302.

[0050] FIG. 20 is a schematic cross-sectional view of a patterned article 501 according to some embodiments. The patterned article 501 includes a multilayer film 500, which includes a first polymer layer 431a and a functional layer 530 including oppositely facing first and second major surfaces 503 and 505 (e.g., corresponding to 303 and 305), where the first major surface 503 is disposed on the first polymer layer 431a, the functional layer 530 including a multilayer stack (e.g., corresponding to the portion of 330 or 330'' between layers 431a and 431b) including 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., a different one of 331a, 331b, 331c), and a second polymer layer 431b disposed on the second major surface of the functional layer. Each micro-cut metal layer may have an average thickness in the range of 5 nanometers to 500 nanometers, or 10 nanometers to 250 nanometers, and includes a pattern of cuts 433 that forms either (i) a pattern of spaced-apart individual plates 444 (or 544) defined by the cuts that corresponds to the pattern of cuts 433 and where no portion of the metal layer is substantially located between nearest adjacent plates 444a and 444b (e.g., after cutting the functional layer, any metal initially in spaces 548 between plates 444a and 444b can be removed except for small amounts of metal, such as metal flakes or traces of metal that are left behind when the metal initially in spaces 548 is removed), or (ii) a continuous pattern 448 that corresponds to removing from the metal layer the pattern of spaced-apart individual plates 444 that correspond to the pattern of cuts 433. The at least one metal oxide layer or metal nitride layer can be at least one metal oxide micro-cut layer or metal nitride micro-cut layer and can have substantially the same pattern of cuts as the at least one micro-cut metal layer.

[0051] 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 one of the adhesive layers 267 and 268 shown in FIG. 18, and the first polymer film layer 521 may correspond to one of the layers 277 and 278 shown in FIG. 18, or the layers 277 or 278 may be release liners that are 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., at least 80% luminous transmittance and 10% or less haze, 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 prior to applying the multilayer film to a substrate. Layers 522, 512, and / or 521 may be optionally omitted.

[0052] FIG. 21 is a schematic perspective view of a substrate 550, and FIG. 22 is a schematic perspective view of a patterned article 1000 including a multilayer film 500 disposed on a portion 555 of a major surface 551 of the substrate 550. In some embodiments, the patterned article 1000 includes a substrate 550 and a multilayer film 500 disposed on at least a portion 555 of the major surface 551 of the substrate and substantially conforming to the portion 555. The portion 555 of the major surface 551 may be a non-flat surface and / or may be curved about two mutually orthogonal axes (e.g., an x′ axis and a y′ axis). A shape curved about two mutually orthogonal axes may alternatively or additionally be referred to as a shape having a compound 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 major surface 551 of the substrate 550. For example, multilayer film 500 may initially be a generally flat film, as shown diagrammatically in Figure 20. To conform such a film to a non-flat surface, such as portion 555, that is curved about two mutually perpendicular axes (e.g., a spherical surface), the film is stretched and shaped so that it can conform to portion 555, as shown diagrammatically in Figures 21 and 22.

[0053] In some embodiments, when the functional layer (e.g., 130, 230, 330, 330', 330'', 430) comprises a metal layer or a metal oxide layer, the patterned articles herein can have at least one of an antimicrobial effect, an antibacterial effect, or an antibiofilm effect. A wide variety of metal oxide MOx can be used for such applications, so long as the metal oxide layer exhibits at least 1 log microbial reduction, at least 2 log reduction, at least 3 log reduction, at least 4 log reduction against S. aureus and S. mutans after 24 hours of contact. Log reduction values ​​are measured according to ISO test method ISO 22196:2011 "Measurement of antibacterial activity on plastics and other non-porous surfaces" with appropriate modifications to accommodate 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 can include any antimicrobially effective amount of a metal, metal oxide MOx, or mixtures and combinations thereof. In various embodiments, the metal oxide layer can be, for example, 100 cm 2 The composition may contain less than 100 mg, less than 40 mg, less than 20 mg, or less than 5 mg of MOx per unit area.

[0056] In some embodiments, the functional layer can have dielectric properties and can be transparent to electromagnetic signals over a selected frequency range, which can be useful, for example, in 5G or other communication devices. For example, as described in IPC Standard TM-650 2.5.5.13, if the patterned functional layer has a tan δ of about 0.12 or less when measured in a 9.5 GHz split-post dielectric resonator cavity, the layer can be more transparent to communication signals transmitted between mobile devices compared to their non-microcut state. In some embodiments, the microcut functional layer can 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 plates 444 and / or mesh pattern 448 can be configured to provide transparency to near-infrared signals, which can enable the formation of a highly conformable near-IR sensor cover structure on a surface. In some embodiments, the plates and interspersed spaces therebetween can be configured to provide reflectivity to near-infrared signals and transparency to visible light. For example, such a configuration can form a highly conformable visible light sensor cover.

[0058] In some embodiments, the shape and size of the plates 444 and / or mesh pattern 448 can provide color change, reflectivity, transparency, or other aesthetic effects to the functional layer, which can provide a useful decorative film that can be applied to complex or composite surfaces, such as, for example, a vehicle exterior or interior. For example, in some embodiments, a transfer article including a micro-cut inorganic layer is reflective at visible wavelengths of 400-750 nm or 400-700 nm and at least partially transparent at wavelengths greater than about 830 nm. For example, upon exposure to ambient conditions, some plates 444 can oxidize over time, and this detectable color change can be used to evaluate, for example, the useful life of a product. If color change is not desired, one or both surfaces of the micro-cut metal layer can be overlaid with one or more protective barrier layers, for example, of metal oxides. In some embodiments, the metal layer can be configured such that the plate produces a color-changing effect when exposed to light over a selected wavelength range, such as, for example, when the article is stretched in two or three dimensions over a surface having a compound curvature. EXAMPLES

[0059] The examples are for illustrative purposes and are not intended to limit the scope of the appended claims. All parts, percentages, ratios, etc. in the examples and elsewhere herein are by weight unless otherwise indicated.

[0060] [Table 1]

[0061] A microcutting and embossing tool was prepared according to the following specifications: The tool was made by diamond cutting deep grooves 12 micrometers (μm) deep into a cylindrical roll using conventional machining methods. The grooves were cut at 45 degrees and -45 degrees to the circumferential direction of the roll. The pitch between the grooves was 300 μm. The resulting tool was cross-grooved forming a diamond-shaped raised area with 45 degree cross-grooves. Half of the pattern was cut with a tool having a 0.15 μm tip on the diamond end. The tipped diamond end had an included angle of 60 degrees.

[0062] The pattern was then removed from the roll by peeling the thin layer of copper from the cylindrical surface having the groove pattern described above. This thin copper sheet was then Ni plated using a conventional Ni electroplating method to form a negative of the cut groove pattern. The nickel sheet electroplated from the pattern having the edge features resulted in raised edges on the nickel sheet.

[0063] The nickel shims were then background smooth and welded together to form a roll sleeve. The sleeve was then mounted onto a temperature controlled mandrel and the mandrel was placed into the laminator.

[0064] [Table 2]

[0065] Test Method Microcut confirmation test A VHX-6000 series Keyence digital microscope (Keyence Corporation of America, Itasca, Ill.) with a 100x objective was used in visible light transmission mode to observe light leakage from breaks in the film article. Breaks were visible as areas of higher visible light transmission surrounded by unbroken surfaces of lower visible light transmission.

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

[0067] A first acrylate layer, tricyclodecane dimethanol diacrylate (obtained under the tradename SARTOMER SR833S from Sartomer USA, Exton, PA), was applied to the release layer by ultrasonic spraying and flash deposition to produce a coating width of 12.5 inches (31.8 cm). The liquid monomer flow 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 at 500°F (260°C). The process drum temperature was 14°F (-10°C). This monomer coating was then cured immediately downstream with an electron beam curing gun operating at 7.0 kV and 10.0 mA to yield a 180 nm thick acrylate.

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

[0069] On top of the silver layer, an oxide layer of silicon aluminum oxide was deposited by alternating current (AC) reactive sputtering. The cathode had a target of Si(90%) / Al(10%) and was obtained from Soleras Advanced Coatings US (Biddeford, ME). The voltage of the cathode during sputtering was controlled by a feedback control loop to monitor the voltage and control the oxygen flow. The system was operated at 32 kW of power to deposit a 12 nm thick silicon aluminum oxide layer on the silver reflector. The aluminum surface of the TorayFAN PMX2 film and the first organic layer are separated with a 180 peel force of about 7.2 g / in (0.283 g / mm), similar to that described in US Patent Application Publication Nos. 2020 / 0016879(A1) (Gotrik et al.) and 2020 / 0136086(A1) (Gotrik et al.).

[0070] Preparation Example 2. Weather-resistant Al-based MIM transfer laminate The coater was loaded with a variable length roll of aluminized polyethylene (PET) film release layer (980 microinch (0.0250 mm) thick, 14 inch (35.6 cm) wide) (obtained under the trade name TORAYFAN MT60 from Toray Plastics (America) (North Kingstown, RI). 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 top of the first acrylate layer. A 60 nm thick layer of Al was deposited using a conventional DC sputtering process using argon gas and operating at 2 kW of power. 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 generated from a monomer solution by spraying and vapor deposition of SARTOMER SR833S+3% CN 147 (obtained from Sartomer USA, Exton, PA). The acrylate layer was applied using a mixture flow rate to the sprayer of 0.67 mL / min, a gas flow rate of 60 sccm, and an evaporator temperature of 260° C. Once condensed onto the Al layer, the coated acrylate was cured with an electron beam operating at 7 kV and 10 mA to provide a layer 290 nm thick. This second acrylate layer provided the insulating layer of the functional metal-insulator-metal (MIM) transfer stack.

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

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

[0074] A second inorganic barrier layer was applied over the second reflective layer in a manner similar to 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 by spraying and evaporating SARTOMER SR833S+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 vaporizer 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 layer 290 nm thick. Similar to that described in U.S. Patent Application Publication Nos. 2020 / 0016879(A1) (Gotrik et al.) and 2020 / 0136086(A1) (Gotrik et al.), the aluminum surface and first organic layer of the Toray MT60 film separate with a 180 peel force of about 7.2 g / in (0.283 g / mm).

[0076] Example 1. Transfer-based microcut and embossed articles. Preparation Example 1 was roll-to-roll laminated at 240° F. against microcut and embossing tool 1 and backing with a steel roll laminator at 240° F. using a nip lamination force of 500 lbs / linear inch, an input tension of 3 lbs / inch, and an output (after microcut and embossing) tension of 1 lb / inch. Atomic force microscopy measured the embossed areas of the third acrylate layer to be 600 nm below the surface of the surrounding non-embossed areas of the third acrylate layer. Atomic force microscopy measured the line edge roughness of the cut edges of the non-embossed areas to be about 200 nm.

[0077] Example 2. Transfer of non-embossed areas The first OCA film was quickly (<1 sec) laminated to the non-embossed third acrylate layer of Example 1. The OCA was quickly (<1 sec) removed to bring the third acrylate in contact and the multilayer attached to the OCA surface. The remaining micro-cut and embossed TORAYFAN MT60 release liner was set aside.

[0078] The "micro-cut confirmation test" confirmed that micro-cuts with 10 μm gaps were preset between the multi-layers transferred onto the OCA surface. No accidental or inadvertent breaks were observed inside the transferred multi-layer areas.

[0079] Example 3. Transfer of embossed areas The adhesive surface of the 8518 was then laminated to the remaining micro-cut and embossed TORAYFAN MT60 release liner from Example 2. The 8518 was slowly removed from the TORAYFAN MT60 and the micro-cut and embossed features were applied. A "micro-cut confirmation test" confirmed that 10 μm multi-layer features were present on the 8518 surface. Occasional breaks were noted along the 10 μm wide multi-layers present on the 8518 surface.

[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, FIG. 3) were observed.

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

[0082] Example 6. Example 3 was completed using Example 5 instead of Example 2. 4 μm wide multilayer features were present on the 8518 surface. The line edge roughness of the cut edge of the non-embossed area was measured to be about 600 nm by atomic force microscopy.

[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, FIG. 3) were observed.

[0084] Example 8. Example 2 was completed using Example 7 instead of Example 1. When compared to Example 2, there were far fewer inadvertent breaks observed inside the transferred multi-layer area.

[0085] Terms such as "about" will be understood by those of skill in the art in the context in which they are used and described herein. Unless otherwise clear to those of skill in the art in the context in which they are used and described herein, the use of "about" as applied to quantities describing feature sizes, quantities, and physical properties will be understood to mean within 10 percent of a particular value. A quantity given as about, approximately a particular value may be exactly that particular value. For example, unless otherwise clear to those of skill in the art in the context in which they are used and described herein, an amount having a value of about 1 means that the amount has a value between 0.9 and 1.1, and may even be 1.

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

[0087] Descriptions of elements in the figures should be understood to apply equally to corresponding elements in other figures unless otherwise indicated. Although specific embodiments have been illustrated and described herein, those skilled in the art will appreciate that the specific embodiments illustrated and described may be replaced by various alternative and / or equivalent embodiments without departing from the scope of the present disclosure. The present application is intended to cover any adaptations, or variations, or combinations of the specific embodiments discussed herein. Accordingly, the present disclosure is intended to be limited only by the claims and the equivalents thereof.

Claims

1. a carrier layer including a microstructured first major surface and an oppositely facing second major surface, the first major surface including a plurality of upper and lower edges spaced apart along a thickness of the carrier layer and defining respective upper and lower portions of the first major surface, the lower portions being disposed between the upper and second major surfaces; a first functional layer disposed on the lower portion but not the upper portion of the first major surface, the first functional layer including at least one first micro-cut inorganic layer including a plurality of cut edges substantially coextensive with the plurality of bottom edges; A patterned article comprising:

2. 2. The patterned article of claim 1, further comprising a second functional layer disposed on the upper but not the lower portion of the first major surface, the second functional layer comprising at least one second micro-cut inorganic layer including a plurality of cut edges substantially coextensive with the plurality of upper edges.

3. 3. The patterned article of claim 2, wherein the second functional layer is configured to be transferable from the carrier layer to a first adhesive layer while leaving the first functional layer disposed on the carrier layer, thereby allowing the first functional layer to be transferable from the carrier layer to the second adhesive layer.

4. The patterned article of claim 2 , wherein the at least one second micro-cut inorganic layer comprises a plurality of spaced apart plates.

5. The patterned article of claim 1 , wherein the at least one first micro-cut inorganic layer comprises a mesh pattern.

6. 2. The patterned article of claim 1, wherein when the patterned article is placed on a flat surface, the upper and lower portions of the first major surface are each disposed in a first plane spaced apart from each other along the thickness direction of the carrier layer.

7. 7. The patterned article of claim 1, wherein an average separation between the upper and lower portions along the thickness direction of the carrier layer is in the range of 0.3 micrometers to 10 micrometers.

8. 1. A method for making a patterned article, comprising the steps of: A transfer article, a carrier layer having oppositely facing first and second major surfaces; A functional layer disposed on the first major surface; providing a transfer article comprising: providing a tool comprising a plurality of microstructures, each microstructure comprising at least one cutting edge; positioning the transfer article and the tool adjacent to one another such that the functional layer faces the plurality of microstructures; contacting the transfer article with the tool such that the tool embosses and scores the transfer article to form a pattern of cuts in the functional layer and a plurality of structures in the carrier layer that define upper and lower portions of the first major surface; 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, and the first and second portions of the functional layer are spaced apart from each other along the pattern of the cuts. method.

9. The method of claim 8 , wherein the functional layer comprises at least one inorganic layer.

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

11. The method of any one of claims 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 a first adhesive layer while leaving the second portion of the functional layer disposed on the carrier layer, thereby allowing the second portion of the functional layer to be transferred from the carrier layer to a second adhesive layer.

12. The method of any one of claims 8 to 10, wherein one of the upper portion or the lower portion comprises a mesh pattern having an average line width in the range of 0.5 micrometers to 50 micrometers.

13. The method of any one of claims 8 to 10, wherein, in a top view, the lower portion has a total area that is less than 40 percent of a total area of ​​the first major surface.

14. 1. A patterned article comprising a multilayer film, the multilayer film comprising: a first polymer layer; A functional layer including oppositely facing first and second major surfaces, the first major surface being disposed on the first polymer layer, the functional layer including a multi-layer stack including 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 a pattern of cuts: (i) a pattern of spaced apart discrete plates corresponding to the pattern of cuts and defined by the cuts with no portion of the metal layer being located substantially between nearest adjacent plates; or (ii) a continuous pattern corresponding to removing from said metal layer a pattern of spaced apart discrete plates corresponding to said pattern of cuts; A functional layer including a pattern of cuts forming any one of the above. a second polymer layer disposed on the second major surface of the functional layer; and A patterned article comprising:

15. 15. The patterned article of claim 14, further comprising a substrate, wherein the multilayer film is disposed over at least a portion of a major surface of the substrate and substantially conforms to at least a portion of the major surface of the substrate, and wherein the portion of the major surface is curved about two mutually perpendicular axes.

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