Microcut patterned transfer articles

Abstract

The transfer article includes a carrier layer releasable from a release layer including a metal layer or a doped semiconductor layer at a release value of 2 to 50 grams per inch. A functional layer overlies the carrier layer, the functional layer including at least one micro-cut inorganic layer. The micro-cut inorganic layer includes a pattern of cutting tool marks and a plurality of plates bounded by the tool marks, each plate having a thickness of about 3 nanometers to about 2000 nanometers. The transfer article has a thickness of less than 3 micrometers.

Description

Background Art

[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. Using sputtering, for example, stacks of inorganic thin film layers such as metal layers and metal oxide layers can be deposited on a substrate. The materials, thicknesses, and arrangement orders of thin film inorganic layers with different refractive indices can be selected to finely tune the aesthetic appearance and transmission characteristics of an article. For example, an article having a stack of multiple metal layers and metal oxide layers may appear to have different colors when viewed at different viewing angles.

[0002] Articles including stacks of thin film inorganic layers sputter-deposited on a substrate can have a highly desirable aesthetic appearance. However, when the article is applied to a surface, particularly a surface having a complex curvature, the metal layer can be stretched or distorted, forming visible crack-like defects that unnecessarily change the desired aesthetic or light management characteristics of the article. If the metal layer, the substrate to which the metal layer is applied, or both are made of a more stretchable material, when the article is applied to a surface, the metal layer can become thinner in certain areas, causing undesirable changes in the appearance or light management performance of the article.

Summary of the Invention

[0003] Generally, this disclosure relates to a transfer article comprising a dimensionally stable but flexible transfer substrate having a functional layer thereon, which comprises at least one ultrathin inorganic layer. In some examples, the inorganic layer within the functional layer of the transfer article is formed by a sputtering process and has a thickness of about 3 nanometers (nm) to about 2000 nm. Subsequently, the transfer article comprising the stable transfer substrate and at least one thin inorganic layer is brought into contact with a microstructured tool to form a pattern of cutting tool marks on the inorganic layer that faithfully corresponds to the pattern of the cutting edge of the tool. The precise pattern of tool marks forms a first array of plates between the tool marks, and the interconnected boundary regions between the tool marks form a corresponding second array, which is the inverse of the first array.

[0004] In some exemplary embodiments, the microcut inorganic layer articles of the present disclosure provide a transferable conductive layer having a thickness of about 1 micrometer, which can be used as a touch sensor or antenna for a wide range of applications such as 5G. In some exemplary embodiments, the microcut inorganic layer provides a fine-wire conductive mesh material that can be manufactured without multiple post-plating steps. In another exemplary embodiment, a transfer article comprising a diffusely reflective microcut inorganic layer is stretched to at least one dimension and applied to a non-planar or structured surface. The network of plates and scattered boundary regions in the microcut inorganic layer adapts to stretching and straining during the application process and expands by various amounts as needed to conform to the surface. When applied to a surface, the transfer article forms a microcut article having a precise arrangement of plates small enough to provide adjustable reflectivity performance with consistent color and a mirror-like aesthetic appearance at a selected viewing angle relative to its main surface.

[0005] The pattern of cutting tool marks in a micro-cut inorganic layer is a faithful reproduction of the pattern on the microstructuring tool. Therefore, the precise placement of the plate and boundary regions allows for more accurate control of the aesthetic appearance and conductivity of articles containing stacks of inorganic material when the article is stretched in one or more directions and applied to or bonded to a composite surface to form a laminated article. Micro-cutting an inorganic layer makes it transparent to electromagnetic signals within a desired frequency range, thereby enabling the creation of articles useful in communication devices.

[0006] In one embodiment, a transfer article comprising a transfer substrate having a functional layer thereon is transferred to a low modulus substrate having an elastic modulus range of about 50 MPa to about 1000 MPa and comprising at least one ultrathin inorganic layer. While on the low modulus substrate, at least one inorganic layer in the stack of inorganic thin film layers is precisely micro-cut and patterned relative to the tool. By transferring the inorganic thin layer to the low modulus substrate, the pressure required to complete the patterning process is reduced, and the resolution of the tool marks is increased such that the tool marks and plates scattered between them are unresolved to the human eye at a normal viewing distance.

[0007] In one embodiment, the present disclosure relates to a transfer article comprising: a carrier layer peelable from a release layer containing a metal layer or a doped semiconductor layer with a peel value of 2 to 50 grams / inch; and a functional layer covering the carrier layer, wherein the functional layer comprises at least one microcut inorganic layer. The microcut inorganic layer comprises a pattern of cutting tool marks and a plurality of plates bounded by the tool marks, each of which has a thickness of about 3 nanometers to about 2000 nanometers. The transfer article has a thickness of less than 3 micrometers.

[0008] In another aspect, the disclosure relates to a method for manufacturing a patterned article. The method comprises removing a transfer article from a release layer selected from a metal layer or a doped semiconductor layer. The transfer article comprises a carrier layer covering the release layer, wherein the release value between the release layer and the carrier layer is 2 to 50 grams / inch, and a functional layer covering the carrier layer. The functional layer comprises at least one inorganic layer. The method further comprises bringing the carrier layer into contact with a microstructuring tool comprising at least one cutting edge, the tool forming a cutting pattern in at least one inorganic layer, the cutting pattern forming a corresponding pattern of a plurality of plates in the inorganic layer, each of which has a thickness of about 3 nanometers to about 2000 nanometers, and the patterned article having a thickness of less than 3 micrometers.

[0009] In another embodiment, the present disclosure relates to an article comprising a first acrylate layer and a functional layer having a first main surface on the first acrylate layer. The functional layer comprises a stack of metal layers and metal oxide layers, at least one of the metal layers having a cutting pattern that forms a corresponding pattern of a plurality of independent plates bounded by cuttings, and the precision-cut metal layer is about 5 nanometers to about 100 nanometers thick. A second acrylate layer is on the second main surface of the functional layer. A first adhesive layer is on the first acrylate layer, and a first polymer film layer is on the first adhesive layer. An optically transparent second adhesive layer is on the second acrylate layer, and a second polymer film layer is on the second adhesive layer.

[0010] Details of one or more embodiments of the present invention are shown in the accompanying drawings and the following description. Other features, purposes, and advantages of the present invention will become apparent from the specification and drawings and the claims. [Brief explanation of the drawing]

[0011] [Figure 1] This is a schematic cross-sectional view of one embodiment of a transfer article according to the present disclosure. [Figure 2] This is a schematic cross-sectional view of the transfer article shown in Figure 1 on the adhesive layer. [Figure 3] This is a schematic diagram of a roll-to-roll patterning process suitable for patterning the articles of this disclosure. [Figure 4A] This is a schematic overhead view of one embodiment of the micro-cut surface of the inorganic layer of the article of this disclosure. [Figure 4B] Figure 4A is a cross-sectional view of the article. [Figure 5] This is a schematic overhead view of one embodiment of the micro-cut surface of the inorganic layer of the article of this disclosure. [Figure 6] This is a schematic overhead view of one embodiment of the micro-cut surface of the inorganic layer of the article of this disclosure. [Figure 7] This is a photograph of a matte finish article formed according to Comparative Example 4. [Figure 8] This is a photograph of a mirror-finished article formed according to Example 4.

[0012] Similar symbols in the diagram indicate similar elements. [Modes for carrying out the invention]

[0013] Referring to Figure 1, the transfer article 10 includes an optional release layer substrate 12 that overlaps with the release layer 14. The carrier layer 16 contacts the release layer 14 along the release surface 17. The functional layer 18 includes a first main surface 19 that contacts the carrier layer 16. In various embodiments, the functional layer 18 may include a stack of one or more layers selected to provide the transfer article 10 with some functional properties, including but not limited to aesthetic properties, reflective or transmissive properties, environmental properties, and antimicrobial properties. The functional layer 18 may include at least one inorganic layer 20 that can be located at any point within the functional layer 18, and in some embodiments, it may include one or more organic layers interspersed with at least one inorganic layer 20.

[0014] In the embodiment of Figure 1, the functional layer 18 includes a polymer film layer 24 which may be the same as or different from the carrier layer 16. In the embodiment of Figure 1, an optional adhesive layer 22 is superimposed on the polymer film layer 24 (if present). In some examples, the optional adhesive layer 22 can be used to attach the transfer article 10 to a target surface or to another article (not shown in Figure 1).

[0015] In various embodiments, the combination of the carrier layer 16 and the functional layer 18 has a thickness of less than approximately 3 micrometers, or less than 2 micrometers, or less than 1 micrometer, or less than 0.5 micrometers, or less than 0.25 micrometers, or less than 0.1 micrometers.

[0016] The optional release layer substrate 12 may include any material capable of supporting the release layer 14, and preferred examples include, but are not limited to, polymer materials and metals. In some embodiments, the release layer substrate 12 may be heat-shrinkable and can be shrunk at a given temperature. A suitable release layer substrate 12 can be selected from any organic polymer layer that is treated to be heat-shrinkable by any suitable means. In one embodiment, the release layer substrate 12 is a semicrystalline or amorphous polymer that can be oriented at a temperature above its glass transition temperature Tg and then cooled to become heat-shrinkable. Examples of useful semicrystalline polymer films include, but are not limited to, polyolefins such as polyethylene (PE), polypropylene (PP), and syndiotactic polystyrene (sPS); polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyethylene-2,6-naphthalate; fluoropolymers such as polyvinylidene difluoride and ethylene:tetrafluoroethylene copolymer (ETFE); polyamides such as nylon 6 and nylon 66; and polyphenylene oxide and polyphenylene sulfide. Examples of amorphous polymer films include polymethyl methacrylate (PMMA), polyimide (PI), polycarbonate (PC), polyethersulfone (PES), atactic polystyrene (aPS), polyvinyl chloride (PVC), norbornene-based cyclic olefin polymers (COP), and cyclic olefin copolymers (COC). Some polymer materials are available in both semi-crystalline and amorphous forms. Semi-crystalline polymers, such as those listed above, can also be made thermally shrinkable by heating and cooling to their peak crystallization temperature.

[0017] In some embodiments, biaxially or uniaxially stretched polyethylene terephthalate (PET) with a thickness of approximately 0.002 inches (0.05 mm) is considered to be a convenient choice for the release layer substrate 12, similar to biaxially stretched polypropylene (BOPP) film. Biaxially stretched polypropylene (BOPP) is commercially available from multiple suppliers, including ExxonMobil Chemical Company (Houston, TX), Continental Polymers (Swindon, UK), Kaisers International Corporation (Taipei City, Taiwan), and PT Indopoly Swakarsa Industry (ISI) (Jakarta, Indonesia).

[0018] In various exemplary embodiments, the release layer 14 can include a metal layer or a doped semiconductor layer. In the embodiment shown in FIG. 1, the carrier layer 16 is in direct contact with the release layer 14 and the functional layer 18. In the embodiment shown in FIG. 1, the optional release layer substrate 12 is in direct contact with the release layer 14, but in other embodiments, additional layers may be present between the release layer substrate 12 and the release layer 14 (not shown in FIG. 1).

[0019] In some embodiments, the peel value along the peel surface 17 between the release layer 14 and the carrier layer 16 is less than 50 g / inch (20 g / cm), 40 g / inch (16 g / cm), 30 g / inch (12 g / cm), 20 g / inch (8 g / cm), 15 g / inch (6 g / cm), 10 g / inch (4 g / cm), 9 g / inch (3.5 g / cm), 8 g / inch (3 g / cm), 7 g / inch (2.8 g / cm), 6 g / inch (2.4 g / cm), 5 g / inch (2 g / cm), 4 g / inch (1.6 g / cm), or 3 g / inch (1.2 g / cm). In some embodiments, the peel value between the release layer 14 and the carrier layer 16 is greater than 1 g / inch, 2 g / inch, 3 g / inch, or 4 g / inch. In some embodiments, the peel value between the release layer 14 and the carrier layer 16 is 1-50 g / inch, 1-40 g / inch, 1-30 g / inch, 1-20 g / inch, 1-15 g / inch, 1-10 g / inch, 1-8 g / inch, 2-50 g / inch, 2-40 g / inch, 2-30 g / inch, 2-20 g / inch, 2-15 g / inch, 2-10 g / inch, or 2-8 g / inch.

[0020] The transfer article 10 is used to transfer the carrier layer 16 and the functional layer 18 thereon, thereby allowing the release layer 14 and / or release layer substrate 12 to be reused. In one example, the transfer article 10 may be applied to a surface to be used, with the functional layer 18 positioned between the carrier layer 16 and the surface to be used. After the transfer article 10 has been applied to the surface to be used, the release layer 14 and substrate 12, if present, may be removed from the transfer article 10. The carrier layer 16 and functional layer 18 are then left on the surface to be used. In some embodiments, an optional adhesive layer 22 may help the functional layer 18 adhere more effectively to the surface to be used.

[0021] In some embodiments, the release layer 14 may include a metal layer selected from individual elemental metals, two or more metals as a mixture, intermetallic compounds or alloys, semimetals or metalloids, metal oxides, metal and mixed metal oxides, metal and mixed metal fluorides, metal and mixed metal nitrides, metal and mixed metal carbides, metal and mixed metal carbonitrides, metal and mixed metal oxynitrides, metal and mixed metal borides, metal and mixed metal oxyborides, metal and mixed metal silicides, diamond-like carbon, diamond-like glass, graphene, and combinations thereof. In some embodiments, although not intended to be limiting, the release layer 14 may advantageously be formed from Al, Zr, Cu, NiCr, NiFe, Ti, or Nb and may have a thickness of about 3 nm to about 3000 nm.

[0022] In some embodiments, the release layer 14 can include a doped semiconductor layer. In some embodiments, although not intended to be limiting, the doped semiconductor layer may advantageously be formed from Si, B-doped Si, Al-doped Si, P-doped Si having a thickness between about 3 nm and about 3000 nm. A particularly suitable doped semiconductor layer for the release layer 14 is Al-doped Si, and the Al composition percentage is about 10%.

[0023] In various exemplary embodiments, the release layer 14 can be prepared by evaporation, reactive evaporation, sputtering, reactive sputtering, chemical vapor deposition, plasma-enhanced chemical vapor deposition, and atomic layer deposition.

[0024] The carrier layer 16 can be made from any material that peels off easily from the release layer 14, and in various embodiments, for example, this may include silicone, fluorinated materials, acrylates, acrylamides, and mixtures and combinations thereof. In some embodiments, the carrier layer 16 may include acrylates or acrylamides. Acrylates and acrylamides can be formed by a wide variety of techniques, including flash deposition, deposition, and subsequent crosslinking of volatile acrylate and methacrylate (hereinafter referred to as "(meth)acrylate") monomers, or acrylamide or methacrylamide (hereinafter referred to as "(meth)acrylamide") monomers, preferably volatile acrylate monomers. In various embodiments, a suitable (meth)acrylate monomer or (meth)acrylamide monomer has a vapor pressure sufficient to be evaporated in an evaporator, condensed into a liquid or solid coating in a deposition coater, and deposited as a spin-on coating or the like.

[0025] Examples of suitable monomers include hexanediol diacrylate, ethoxyethyl acrylate, cyanoethyl (mono)acrylate, isobornyl (meth)acrylate, octadecyl acrylate, isodecyl acrylate, lauryl acrylate, beta-carboxyethyl acrylate, tetrahydrofurfuryl acrylate, dinitrile acrylate, pentafluorophenyl acrylate, nitrophenyl acrylate, 2-phenoxyethyl (meth)acrylate, 2,2,2-trifluoromethyl (meth)acrylate, diethylene glycol diacrylate, triethylene glycol di(meth)acrylate, tripylene glycol diacrylate, and tetraethylene glycol. Diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, polyethylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A epoxy diacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propylated trimethylolpropane triacrylate, tris(2-hydroxyethyl)-isocyanurate triacrylate, pentaerythritol triacrylate, phenylthioethyl acrylate, naphthyloxyethyl acrylate, neopentyl glycol diacrylate, MIRAMER Examples include, but are not limited to, M210 (available from Miwon Specialty Chemical Co., Ltd. (Korea)), KAYARAD R-604 (available from Nippon Kayaku Co., Ltd. (Tokyo, Japan)), epoxy acrylate commodity code RDX80094 (available from RadCure Corp. (Fairfield, NJ)), and mixtures thereof. The polymer layer may also contain a variety of other curable materials, such as vinyl ether, vinyl naphthalene, acrylonitrile, and mixtures thereof.

[0026] Tricyclodecanedimethanol diacrylate can be used as one of the acrylate materials in the component layers of the functional layer, and in some embodiments, it can be applied, for example, by condensed organic coating followed by UV, electron beam, or plasma-initiated free radical polymerization. In some examples, the carrier layer 16 has a thickness of about 10 nm to 10,000 nm, or about 10 nm to 5,000 nm, or about 10 nm to 3,000 nm.

[0027] The polymer film layer 24 may contain any polymer material and may be the same as or different from the carrier layer 16. In some embodiments, the polymer film layer 24 is acrylate or acrylamide and may be selected from any of the materials described above as suitable for the carrier layer 16.

[0028] In some embodiments, the functional layer 18 is an aesthetic optical layer that can have reflective, anti-reflective, partial absorption, polarization, retarding, diffraction, scattering, or transmission properties over the target electromagnetic wavelength. The functional layer includes at least one or more inorganic layers 20, which in various embodiments include metal layers and metal oxide layers that may have the same or different thicknesses and refractive indices selected to provide a predetermined optical effect over the target electromagnetic wavelength.

[0029] In various embodiments, the functional layer 18 has a thickness of less than approximately 5 microns, less than approximately 2 microns, less than approximately 1 micron, or less than approximately 0.5 microns.

[0030] In various embodiments, though not intended to be limiting, the inorganic layer 20 within the functional layer 18 may include metals selected from individual elemental metals, two or more metals as mixtures, intermetallic compounds or alloys, metalloids or metalloids, metal oxides, metal and mixed metal oxides, metal and mixed metal fluorides, metal and mixed metal nitrides, metal and mixed metal carbides, metal and mixed metal carbonitrides, metal and mixed metal oxynitrides, metal and mixed metal borides, metal and mixed metal oxyborides, metal and mixed metal silicides, diamond-like carbon, diamond-like glass, graphene, and combinations thereof. In some embodiments, though not intended to be limiting, the inorganic layer 20 is selected from Ag, Al, Ge, Au, Si, Ni, Cr, Co, Fe, Nb, and mixtures, alloys, and oxides thereof. In some embodiments, the inorganic layer 20 of the functional layer 18 includes layers of metal oxides such as SiAlOx, NbOx, and mixtures and combinations thereof, with metal layers interspersed between them.

[0031] In some embodiments, the inorganic layer or multiple inorganic layers 20 are applied by sputtering, deposition, or flash deposition and have a thickness of about 3 to about 200 nm, or about 3 to about 100 nm, or about 3 nm to about 50 nm, or about 3 nm to about 20 nm, or about 3 nm to about 15 nm, or about 3 nm to about 10 nm, or about 3 nm to about 5 nm.

[0032] In some embodiments, the functional layer 18 comprises a stack of multiple metal layers, where at least some of the metal layers in the stack are separated by metal oxide layers, polymer layers, or mixtures and combinations thereof. In various embodiments, each metal layer in the stack may have substantially the same thickness, or the metal layers in the stack may have different thicknesses. In some embodiments, but not limited thereto, each inorganic layer in the multiple inorganic layers has a thickness of about 5 nm to about 100 nm. In various embodiments, the stack of inorganic layers may comprise about 2 to about 100 layers, or about 2 to 10 layers, or about 2 to 5 layers.

[0033] In one exemplary embodiment, the functional layer 18 comprises a plurality of inorganic layers, which may be the same or different metal layers or metal oxide layers, separated by an acrylate layer and having the same or different thicknesses. In some embodiments, the acrylate layer within the functional layer 18 may be the same or different from the carrier layer 16 and polymer film layer 24 in the transfer article and may have the same or different thicknesses.

[0034] In some embodiments, the functional layer 18 may include one or more optional barrier layers 25, 27 along its main surfaces 19, 21, or on the exposed surfaces of the inorganic layer 20, or both, as schematically shown in Figure 1. The one or more barrier layers 25, 27 may include individual elemental metals, two or more metals as a mixture, intermetallic compounds or alloys, metalloids or metalloids, metal oxides, metal and mixed metal oxides, metal and mixed metal fluorides, metal and mixed metal nitrides, metal and mixed metal carbides, metal and mixed metal carbonitrides, metal and mixed metal oxynitrides, metal and mixed metal borides, metal and mixed metal oxyborides, metal and mixed metal silicides, diamond-like carbon, diamond-like glass, graphene, and combinations thereof.

[0035] In some embodiments, the barrier layers 25 and 27 may be selected from metal oxides, metal nitrides, metal oxynitrides, and metal alloys of oxides, nitrides, and oxynitrides. In some embodiments, the barrier layers 15 and 27 may contain metal oxides selected from silicon oxide such as silica, aluminum oxide such as alumina, titanium oxide such as titania, indium oxide, tin oxide, indium tin oxide (ITO), hafnium oxide, tantalum oxide, zirconium oxide, zinc oxide, niobium oxide, and combinations thereof. In some embodiments, examples of metal oxides for the barrier layers 25 and 27 include aluminum oxide, silicon oxide, aluminum silicon oxide, aluminum silicon nitride, and aluminum silicon oxynitride, CuO, TiO2, ITO, ZnO, zinc aluminum oxide, ZrO2, and yttria-stabilized zirconia. Preferred nitrides include Si3N4 and TiN.

[0036] In some exemplary embodiments, the barrier layers 25, 27 can typically be prepared by reactive evaporation, reactive sputtering, chemical evaporation, plasma chemical evaporation, and atomic layer deposition. Preferred methods include vacuum preparation such as reactive sputtering, plasma chemical evaporation, and atomic layer deposition.

[0037] The barrier layers 25 and 27 can be conveniently applied as thin layers. For example, a barrier layer material, such as aluminum silicon oxide, can provide good barrier properties as well as good interfacial adhesion to other layers in the stack, such as the acrylate layer. Such layers can be conveniently applied by sputtering, with a thickness of about 3 to 100 nm being convenient, and a thickness of about 27 nm being particularly preferred. In some embodiments, the barrier layer has a density of 0.2, 0.1, 0.05, 0.01, 0.005, or 0.001 g / m². 2 It may have a water vapor transmission rate of less than 1 / day, and therefore provides good environmental resistance to the inorganic layer 20.

[0038] An optional adhesive layer 22 on the transfer article 10 may include a viscoelastic or elastomeric adhesive having a low modulus of elasticity of 50 MPa to about 1000 MPa, or about 100 MPa to about 500 MPa. Suitable viscoelastic or elastomeric adhesives include those described in U.S. Patent Application Publication No. 2016 / 0016338 (Radcliffe et al.), such as pressure-sensitive adhesives (PSA), rubber-based adhesives (e.g., rubber, urethane), and silicone-based adhesives. Examples of viscoelastic or elastomeric adhesives include thermoactivated adhesives that are non-tacky at room temperature but temporarily become tacky and bond to the substrate when the temperature rises. Thermoactivated adhesives are activated at an activation temperature and, above this temperature, have viscoelastic properties similar to PSA. Viscoelastic or elastomeric adhesives may be substantially transparent and optically clear.

[0039] Either the viscoelastic adhesive or the elastomer adhesive 22 may be a viscoelastic, optically transparent adhesive. The elastomer material may have an elongation at break of more than about 20 percent, more than about 50 percent, or more than about 100 percent.

[0040] The viscoelastic adhesive layer or elastomeric adhesive layer 22 may be applied directly as a substantially 100 percent solid adhesive, or it may be formed by coating with a solvent-based adhesive and allowing the solvent to vaporize. The viscoelastic adhesive or elastomeric adhesive may also be a hot-melt adhesive that melts, is applied in a molten state, and then cooled to form the viscoelastic or elastomeric adhesive layer. Suitable viscoelastic or elastomeric adhesives include elastomeric polyurethane or silicone adhesives and viscoelastic optically transparent adhesives CEF22, 817x, and 818x, all available from 3M Company (St. Paul, MN). Other useful viscoelastic or elastomeric adhesives include styrene block copolymers, (meth)acrylic block copolymers, polyvinyl ethers, polyolefins, and poly(meth)acrylate-based PSAs. In some embodiments, the adhesive layer 22 may include a UV-curing adhesive.

[0041] Referring again to Figure 1, the carrier layer 16 can be removed from the release layer 14 along the release surface 17. The transfer article 100 obtained in the embodiment of Figure 2 includes a carrier layer 116, a functional layer 118 having at least one inorganic layer 120, a polymer film layer 124, and an adhesive layer 122 forming a patternable structure 150 (Figure 2). In some embodiments, the surface 121 of the carrier layer 116 facing air after removal from the release layer 14 can be in contact with a tool to change the shape of at least one inorganic layer 120. In some embodiments, depending on the material and thickness selected for the inorganic layer 120 in the functional layer 118, the carrier layer 116 may not be required to support the functional layer 118, and the functional layer 118 may be in contact with a tool to change the shape of at least one inorganic layer 120. A relatively soft, low modulus adhesive layer 122 or functional layer 118 beneath the carrier layer 116 allows for lower pressure during the process of patterning at least one inorganic layer 120.

[0042] In another embodiment, after transfer, the carrier layer 116 is applied to the intermediate substrate before the patterning process is performed. For example, as shown in Figure 2, the carrier layer 116 may be applied to the low modulus layer 130 such that the carrier layer 116 comes into contact with the low modulus layer 130 to create a patternable structure 150. The low modulus layer 130 can include any material having an elastic modulus of about 50 MPa to about 1000 MPa, or about 100 MPa to about 500 MPa. In some embodiments, the low modulus layer 130 is an adhesive layer, and in some embodiments, it may be a pressure-sensitive adhesive, a bonding adhesive, etc. In various embodiments, the low modulus layer 130 is an acrylic adhesive or an acrylic pressure-sensitive adhesive.

[0043] In various embodiments, the article 150 in Figure 2 may optionally include a polymer film layer on either or both of the adhesive layer 122 and the low modulus layer 130 (not shown in Figure 2).

[0044] With or without the low modulus layer 130, the patternable structure 150 of Figure 2 may be brought into contact with a microstructuring tool to alter the shape of at least one inorganic layer 120. The patternable structure 150 can be brought into contact with a tool using a wide variety of techniques, including, for example, rotary cutting, single nip cutting, spot cutting, whole cutting, engraving, and microcutting. In some embodiments, but not limited thereto, the patternable structure 150 may be brought into contact with a rotary cutting tool having multiple cutting edges.

[0045] For example, as schematically shown in Figure 3, in process 200, the patternable structure 150 is moved in parallel in direction A, passed over the roller 160, and brought into contact with the microstructured rotary cutting tool 170. In various embodiments, the roller 160 may or may not be driven by itself. In various exemplary embodiments, the roller 160 may be made of a rigid material such as steel, or a flexible material such as rubber or a polymer.

[0046] The cutting tool 170 includes a pattern 172 having a plurality of cutting edges 174. The cutting edges 174 extend outward from the surface 176 on the cutting tool 170 and cut into the functional layer 118 to form a pattern 180 of cutting tool marks 182. In some embodiments, the tool marks 182 are cutting lines formed in at least one inorganic layer 120 of the functional layer 118.

[0047] The shape and arrangement of the cutting edge 174 on the cutting tool 170 can vary widely, and the shape of the cutting tool marks 182 in the inorganic layer 120 is a faithful reproduction of the shape and arrangement of the cutting edge 174. In various embodiments, the cutting tool marks may be arranged in a regular or irregular array on the surface 176 of the tool 170, and similarly, the tool marks formed by the cutting edge 174 may be located throughout the inorganic layer 120 or within specific areas of the inorganic layer 120, with some areas of the inorganic layer not containing tool marks.

[0048] Referring here to Figure 4A, a partial overhead view of an embodiment of the transfer article 300 includes a patterned inorganic layer 220 having a main surface 229 processed by a tool to form a pattern 290 of a plurality of independent cuts 280. The cuts 280 can have any desired shape derived from the shape of the cutting edge of the tool, but in the embodiment of Figure 4A, they have a linear shape and are arranged in a plurality of substantially parallel lines. Each pair of cuts 280 is terminated at opposing ends by a termination region 281. In various embodiments, the cuts 280 are 1 mm on the surface 229 2 Approximately 0.3 to 2000 pieces per unit, or 1 mm 2 Approximately 1 to 1000 pieces per unit, or 1 mm 2 Approximately 10 to 500 pieces per unit, or 1 mm 2 There are approximately 50 to 100 winning items.

[0049] Multiple parallel cuts 280 are separated by multiple independent boundary regions 282 that form a discontinuous, regular array 292 on the surface 229. The boundary regions 282 are independent and separated at their intersections by terminal regions 281, however, in some embodiments, the boundary regions 282 may be sufficiently continuous with each other to form a conductive mesh-like web on the surface 229. In various embodiments, the boundary regions 282 may occupy about 1% to about 99.9% or about 10% to about 90% of the surface 229.

[0050] The cutting lines 280 border a plate 284 that forms a discontinuous, regular array 294 on the surface 229. The shape of the plate 284 may vary widely depending on the shape of the cutting edge of the tool used to form the cutting section 280, and may be regular or irregular, as shown in Figure 4A. In the embodiment of Figure 4A, the plate 284 is a separate structure, but the shape and dimensions of the plate vary widely depending on the configuration of the cutting tool used to form the cutting lines 280. For example, if multiple parallel cutting lines 280 do not intersect each other, the plate may be a large structure that extends in several patterns to the edge of the surface 229.

[0051] In the exemplary embodiment of Figure 4A, the plate 284 has a rectangular parallelepiped shape and can have any average intercenter spacing d of less than about 2000 micrometers, or less than about 500 micrometers, or less than about 250 micrometers, or less than about 150 micrometers, or less than about 100 micrometers. In some embodiments, the plate 284 has dimensions in the xy plane of the inorganic layer that are greater than the z direction perpendicular to the xy plane of the inorganic layer, but such arrangement is not required. In various embodiments, the plate 284 may occupy about 1% to about 99.9% or about 10% to about 90% of the surface 229. In various embodiments, the exposed surface 285 of the plate 284 may be substantially flat or it may be undulating.

[0052] In some embodiments (not shown in Figure 4A), the exposed surface of plate 284, or other portions of surface 229, or both, may include a microstructured pattern superimposed thereon. In one exemplary embodiment, the pattern may include tool marks having a period of less than about 750 micrometers. In various embodiments, plate 284 may occupy substantially the same plane, or it may be located in different or fluctuating planes.

[0053] Referring here to Figure 4B, the cross-sectional view of article 300 in Figure 4A includes a carrier layer 216 beneath a functional layer 218 having a patterned inorganic layer 220 on it (other layers within the functional layer 218 are omitted for clarity). The inorganic layer 220, including the main surface 299, has a thickness t of about 1 nm to about 250 nm, or about 3 nm to about 200 nm, or about 5 nm to about 100 nm, or about 10 nm to about 50 nm. In various embodiments, the cut portion 280 may extend through the entire thickness t of the inorganic layer 220, or into the underlying carrier layer 216, or through the entire thickness of both the inorganic layer 220 and the carrier layer 216.

[0054] As shown in Figure 4B, the surface 229 of the inorganic layer is substantially planar after the assembly of the cut portion 282, and the boundary region 282 and the array of plates 284 in the microcut article 300 occupy substantially the same plane on the carrier layer 216.

[0055] Referring to another exemplary embodiment in Figure 5, a partial overhead view of an embodiment of the transfer article 400 includes an inorganic layer 320 having a main surface 329 processed by a tool to form a pattern 390 of a plurality of independent cuts 380. The cuts 380 have a linear shape and are arranged in a plurality of substantially parallel lines. Each pair of cuts 380 is terminated at opposing ends by a termination region 381. The parallel cuts 380 are separated by a plurality of independent boundary regions 382 that form a discontinuous, regular array 392 on the surface 329. The boundary regions 382 are independent and separated by the termination region 381, but in some embodiments the boundary regions 382 may be sufficiently continuous with each other to form a conductive mesh-like web on the surface 329.

[0056] The cut portion 380 borders a plurality of independent plates 384 that form a discontinuous, regular array 394 on the surface 329. The shape of the plates 384 can vary widely and may be regular or irregular, as shown in Figure 4B. Although the shape of the plates 384 can vary widely, as the plurality of parallel cut portions 380 are formed further apart, the portion of the surface 329 occupied by the boundary region 382 increases, and the portion of the surface occupied by the plates 384 decreases, forming a columnar structure on the surface 329.

[0057] Referring here to Figure 6, a partial overhead view of another embodiment of the transfer article 500 includes a patterned inorganic layer 420 having a main surface 429 processed by a tool to form a pattern 490 of continuous cuts 480. The cuts 480 have a linear shape and are arranged in a plurality of substantially parallel lines that do not intersect each other. The plurality of parallel cuts 480 are separated by a continuous boundary region 482 that forms a continuous, regular array 492 on the surface 429. The continuous boundary region 482 forms a mesh-like web on the surface 329, which may optionally be conductive.

[0058] The cutting line 480 borders a plurality of independent plates 484 that form a discontinuous, regular array 494 on the surface 429. As described above, the shape of the plates 484 may vary widely, be regular, or be irregular.

[0059] In one exemplary embodiment, if the inorganic layer 420 includes a metal layer or a metal oxide layer, the microcut article of the present disclosure has at least one of the following effects: antimicrobial effect, antimicrobial effect, or antibiofilm effect. Insofar as the inorganic layer 420 exhibits at least 1 log reduction, at least 2 log reduction, at least 3 log reduction, and at least 4 log reduction against Staphylococcus aureus and Streptococcus mutans after 24 hours of contact, a wide variety of metal oxides MO x This can be used for the following purposes. The log reduction value is measured according to the ISO test method ISO 22196:2011 "Measurement of antibacterial activity on plastics and other non-porous surfaces," with appropriate modifications to the test method to suit the test material.

[0060] Suitable antimicrobial metals and metal oxides for the inorganic layer 420 include, but are not limited to, silver, silver oxide, copper oxide, gold oxide, zinc oxide, magnesium oxide, titanium oxide, chromium oxide, and mixtures, alloys, and combinations thereof. In some embodiments, though not intended to be limiting, the metal oxide of the inorganic layer 420 is selected from AgCuZnOx, Ag-doped ZnOx, Ag-doped ZnO, Ag-doped TiO2, Al-doped ZnO, and TiOx.

[0061] In various embodiments, the inorganic layer 420 contains any antimicrobial effective amount of metal, metal oxide MO x , or mixtures and combinations thereof may be included. In various embodiments, though not intended to be limiting, the metal oxide layer 420 may be 100 cm 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.

[0062] In another embodiment, the inorganic layer 420 may have dielectric properties that allow electromagnetic signals to pass through over a selected frequency range, which may be useful in 5G communication devices. For example, if a patterned inorganic layer 420 has a tanδ of 0.12 when measured in a 9.5 GHz split-post dielectric resonator cavity, as described in IPC standard TM-650 2.5.5.13, the layer may be more permeable to communication signals transmitted between mobile devices compared to their non-microcut state. In some embodiments, the microcut inorganic layer 420 may have a real dielectric constant of about 33 and a complex dielectric constant of about 4.

[0063] In another embodiment, the shape and size of the plate 484 and the continuous boundary 482 can be configured to provide transmittance to near-infrared signals, thereby enabling the formation of a highly adaptable near-IR sensor cover structure on the surface. In yet another embodiment, the plate and the crevasses and cracks 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.

[0064] In other embodiments, the shape and size of the plate 484 and the continuous boundary 482 can provide useful color changes, reflectivity, transmittance, or other aesthetic effects for the inorganic layer 420, 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 and at least partially transmittance at wavelengths above about 830 nm.

[0065] For example, when exposed to ambient conditions, some of the plates 484 may oxidize over time, and this detectable color change can be used to evaluate, for example, the shelf life of the product. If color change is undesirable, one or more protective barrier layers, for example, of metal oxide, can be superimposed on one or both surfaces of the microcut metal surface. In another embodiment, the metal layer may be configured such that the plates 484 produce a discoloration effect when exposed to light over a selected wavelength range, for example, when the article is stretched two-dimensionally or three-dimensionally over a surface having composite curvature.

[0066] The apparatus of this disclosure is further described in the following non-limiting embodiments. [Examples]

[0067] These examples are illustrative and not intended to limit the scope of the appended claims. All parts, percentages, ratios, etc., in the examples and elsewhere in this specification are based on weight unless otherwise indicated. [Table 1]

[0068] The micro-cutting tool was prepared according to the following specifications: The tool was fabricated by diamond cutting grooves 12 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 diamond edge. The diamond edge with the tip had a 60-degree angle.

[0069] 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 edge features gave the nickel sheet a raised edge.

[0070] 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. [Table 2]

[0071] Test method Microcut confirmation test Light leakage from fracturing in film articles was observed using a VHX-6000 series Keyence digital microscope with a 100x objective lens (Keyence Corporation of America (Itasca, IL)) in visible light transmission mode. Fracturing was visible as a higher visible light transmission region surrounded by an unfractured surface with lower visible light transmittance.

[0072] Preparation Example 1 Aste-coated transfer stack 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, with the addition of a second evaporator and curing system positioned between a plasma pretreatment station and a first sputtering system, and using the evaporator described in U.S. Patent No. 8,658,248. The coater was screwed to an aluminum-coated biaxially oriented polypropylene film release layer of variable length roll (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). The release layer was then advanced at a constant line speed of 32 fpm (9.8 m / min).

[0073] A carrier 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 produce 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 (sccm) per minute, 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 with a thickness of 180 nm.

[0074] A silver reflector layer was deposited on top of the carrier 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 layer of silver.

[0075] A layer of aluminum silicon oxide was deposited on a silver layer by alternating current (AC) reaction sputtering. The cathode had a Si (90%) / Al (10%) target and was obtained from Soleras Advanced Coatings US (Biddeford, ME). The voltage to the cathode during sputtering was controlled by a feedback control loop, which monitored the voltage and controlled the oxygen flow. The system was operated at 32 kW 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 Publications 2020 / 0016879 and 2020 / 0136086, the aluminum surface of the TorayFAN PMX2 film and the first organic layer separated with a peel force of 180 at 7.2 g / inch (0.283 g / mm).

[0076] Preparation Example 2 Weather-resistant aluminum-based MIM transfer stack The coater was screwed to a variable-length roll of aluminumized polyethylene (PET) film release layer (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). A release layer with a coated carrier 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 carrier layer. A 60 nm thick layer of Al was deposited using a conventional DC sputtering process employing argon gas and operating at a power of 2 kW. The cathode Al target was obtained from ACI Alloys (San Jose, CA).

[0077] A polymer film layer, which was a second acrylate layer produced from a monomer solution by spraying and vapor deposition of SARTOMER SR833S + 3% CN 147 (obtained from Sartomer USA (Exton, PA)) was applied on top of the reflective Al layer. The second acrylate layer was applied using a mixture flow rate to a sprayer of 0.67 mL / min, a gas flow rate of 60 sccm, and an evaporator temperature of 260°C. Once condensed on the Al layer, the coated acrylate 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 stack.

[0078] 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 rotating Si(90%) / Al(10%) target and was obtained from Soleras Advanced Coatings US. The voltage to the cathode during sputtering was controlled by a feedback control loop, which monitored the voltage and controlled the oxygen flow. The system was operated at a power of 16 kW to deposit a 12 nm thick aluminum silicon oxide layer on the second acrylate layer.

[0079] 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 employing argon gas and operating at a power of 2 kW.

[0080] A second inorganic barrier layer was applied on top of the second reflective layer in the same manner as the first inorganic barrier layer.

[0081] 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% Dynasilan 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 condensed on 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 with a thickness of 290 nm. As described in 79204US002 and 79250US002, the aluminum surface of the Toray MT60 film and the first organic layer separated with a peel force of 180 at 7.2 g / inch (0.283 g / mm).

[0082] Comparative Example 1 Transfer-based non-cut articles The adhesive surface of the 8518 film was laminated onto the second reflective layer surface of the transfer stack from Preparation Example 2. The TORAYFAN PMX2 release liner was removed, leaving the air-facing (outside the carrier layer) transfer stack on the 8518 film surface. Next, the SV480 film was laminated onto the air-facing carrier layer using a hand roller.

[0083] The complete structure was uniaxially stretched by hand in the mechanical direction to 30% elongation. Stretching caused the brittle transfer stack structure to fracture into multiple independent flakes on the order of 500 microns, as measured using a digital Keyence VHX-6000 microscope with built-in software measurement tools. These large, independent flakes were identifiable by visual inspection under ambient light conditions at a field of view distance of 10 cm from the sample surface. The observed large flakes and the random fragmentation spacing between them were not aesthetically pleasing.

[0084] Example 1 Transfer-based micro-cut articles Preparation Example 1 was roll-to-roll laminated onto Microcut Tool 1 at 200°F (93°C), and the backing material was applied using a 68 Shore A rubber laminator at 200°F (93°C) with a nipple lamination force of 40 lbs / linear inch (7.2 kg / cm), an input tension of 3 lbs / inch (0.5 kg / cm), and an output (after microcut) tension of 1 lb / inch (0.18 kg / cm), and the surface was microcut. The adhesive surface of the 8518 film was laminated onto the oxide layer of Preparation Example 1. The TORAYFAN PMX2 release liner was removed, leaving an air-facing (outside the carrier layer) transfer stack on the 8518 film surface. A "microcut confirmation test" confirmed the presence of microcuts and that they coincided with the tool edge contact area of ​​Microcut Tool 1. A 4-micrometer wide ribbon was observed in the deposited layer of Preparation Example 1.

[0085] Comparative Example 2 Transfer-based non-microcut articles Preparation Example 2 was roll-to-roll laminated onto Microcut Tool 1 at 200°F, and the backing was applied by a 68 Shore A rubber laminator at 200°F using a nipple lamination force of 40 lbs / linear inch, an input tension of 3 lbs / inch (0.5 kg / cm), and an output (after microcut) tension of 1 lb / inch (0.18 kg / cm), and the surface was microcut. The adhesive surface of the 8518 film was laminated onto the third acrylate layer of Preparation Example 2. The TORAYFAN MT60 release liner was removed, leaving an air-facing (outside the carrier layer) transfer stack on the 8518 film surface. A "microcut confirmation test" confirmed that the microcuts were not consistently present, particularly near the intersection where the 45° lane cuts converge, and did not substantially coincide with the tool edge contact area of ​​Microcut Tool 2.

[0086] Example 2 Transfer-based micro-cut articles Preparation Example 2 was roll-to-roll laminated onto Microcut Tool 2 at 200°F (93°C), and the backing was applied using a 68 Shore A rubber laminator at 200°F (93°C) with a nipple lamination force of 40 lbs / linear inch (7.2 kg / cm), an input tension of 3 lbs / inch (0.5 kg / cm), and an output (after microcut) tension of 1 lb / inch (0.18 kg / cm), and the surface was microcut. The adhesive surface of the 8518 film was laminated onto the third acrylate layer of Preparation Example 2. The TORAYFAN MT60 release liner was removed, leaving an air-facing (outside the carrier layer) transfer stack on the 8518 film surface. A "microcut confirmation test" confirmed the presence of microcuts and that they coincided with the tool edge contact area of ​​Microcut Tool 2. A 4-micrometer wide ribbon was observed in the deposited layer of Preparation Example 2.

[0087] Comparative Example 3 Transfer-based non-microcut articles Preparation Example 2 was roll-to-roll laminated onto Microcut Tool 3 at 200°F (93°C), and the backing was applied using a 68 Shore A rubber laminator at 200°F (93°C) with a nipple lamination force of 40 lbs / linear inch (7.2 kg / cm), an input tension of 3 lbs / inch (0.5 kg / cm), and an output (after microcut) tension of 1 lb / inch (0.18 kg / cm), and the surface was microcut. The adhesive surface of the 8518 film was laminated onto the third acrylate layer of Preparation Example 2. The Toray MT60 release liner was removed, leaving an air-facing (outside the carrier layer) transfer stack on the 8518 film surface. A "microcut confirmation test" confirmed that the microcuts were not consistently present, particularly near the intersection where the 45° lane cuts converge, and did not substantially coincide with the tool edge contact area of ​​Microcut Tool 3.

[0088] Example 3 Transfer-based micro-cut articles Preparation Example 2 was roll-to-roll laminated onto the microcut tool 4 at 200°F (93°C), and the backing was applied using a 68 Shore A rubber laminator at 200°F (93°C) with a nipple lamination force of 40 lbs / linear inch (7.2 kg / cm), an input tension of 3 lbs / inch (0.5 kg / cm), and an output (after microcut) tension of 1 lb / inch (0.18 kg / cm), and the surface was microcut. The adhesive surface of the 8518 film was laminated onto the third acrylate layer of Preparation Example 2. The TORAYFAN MT60 release liner was removed, leaving an air-facing (outside the carrier layer) transfer stack on the 8518 film surface. A "microcut confirmation test" confirmed the presence of microcuts and that they coincided with the tool edge contact area of ​​the microcut tool 4. A 10-micrometer wide ribbon was observed in the deposited layer of Preparation Example 2.

[0089] Comparative Example 4 Transfer-based micro-embossed articles The adhesive surface of the 8518 film was laminated onto the second reflective layer surface of the transfer stack from Preparation Example 2. The TORAYFAN PMX2 release liner was removed, leaving the air-facing (outside the carrier layer) transfer stack on the 8518 film surface.

[0090] The carrier layer was micro-embossed with a micro-embossing tool 1 with a steel roller, and the surface was micro-embossed by applying a backing material using a 68 Shore A rubber laminator with a nip lamination force of 90 pounds / linear inch (16 kg / cm). The micro-embossed tool film was discarded. The "micro-fracture confirmation test" confirmed the presence of micro-fractures on the tested surface. OCA was laminated onto the carrier layer. SV480 was laminated onto the OCA, and the SV480 adhesive surface was wrapped around a 3D PETG mold. Visible cracks were not visible to humans at 10 cm intervals. The film was aesthetically pleasing and had a matte finish, as shown in Figure 7.

[0091] Example 4. Transfer-based micro-cut article In Example 3, OCA was laminated onto the carrier layer. SV480 was laminated onto the OCA, and SV480 adhesive was wrapped around the 3D PETG mold. Visible microcut lines were visible to humans at 10 cm intervals. As shown in Figure 8, the film was aesthetically pleasing and had a mirror-like appearance.

[0092] Various embodiments of the present invention have been described. These embodiments and other embodiments are within the scope of the following claims. The following are exemplary embodiments. [Item 1] A transfer article, A carrier layer that can be peeled off from a release layer containing a metal layer or a doped semiconductor layer with a peel value of 2 to 50 grams / inch, A functional layer covering the carrier layer, wherein the functional layer includes at least one microcut inorganic layer, and the microcut inorganic layer is The pattern of the cutting tool mark, A plurality of plates bounded by the tool marks, each of which has a thickness of about 3 nanometers to about 2000 nanometers, including The transfer article is a transfer article having a thickness of less than 3 micrometers. [Item 2] The transfer article according to item 1, wherein at least a portion of the plurality of plates does not contain cracks extending through their thickness. [Item 3] The transfer article according to item 1, wherein the plurality of plates include substantially flat exposed surfaces. [Item 4] The transfer article according to item 1, wherein the plurality of plates include an exposed surface with an uneven surface. [Item 5] The transfer article according to item 1, wherein the cutting tool marks include substantially straight cut portions, and the cut portions extend through a predetermined thickness of the inorganic layer. [Item 6] The transfer article according to item 1, wherein the plurality of plates have dimensions in the xy plane of the inorganic layer that are greater than the dimensions in the z direction perpendicular to the xy plane of the inorganic layer. [Item 7] The transfer article according to item 6, wherein the plurality of plates are independent and have a regular shape. [Item 8] The transfer article according to item 7, wherein the plurality of plates have a square or rectangular shape when viewed from above the xy plane of the inorganic layer. [Item 9] The transfer article according to item 1, wherein the plurality of plates occupy approximately 1% to approximately 99% of the surface area of ​​the inorganic layer. [Item 10] The transfer article according to item 1, wherein the cutting tool marks include a plurality of substantially parallel linear cuts, and the plurality of parallel linear cuts are separated by a plurality of boundary regions. [Item 11] The transfer article according to item 10, wherein the plurality of boundary regions are interconnected. [Item 12] The transfer article according to item 11, wherein the plurality of boundary regions occupy approximately 1% to approximately 99% of the surface area of ​​the inorganic layer. [Item 13] The transfer article described in item 1, wherein the plurality of plates include a rectangular column. [Item 14] The transfer article according to item 13, wherein the plurality of plates have substantially similar thicknesses. [Item 15] The transfer article according to item 1, wherein the carrier layer comprises acrylate or acrylamide. [Item 16] The transfer article according to item 15, wherein the carrier layer comprises an acrylate. [Item 17] The transfer article according to item 1, further comprising a low modulus layer covering the functional layer, wherein the low modulus layer has a modulus of elasticity of about 50 MPa to about 1000 MPa. [Item 18] The transfer article according to item 17, wherein the low modulus layer is an adhesive layer. [Item 19] The transfer article according to item 1, wherein the functional layer comprises a plurality of inorganic layers separated by an insulating layer, and at least one of the plurality of metal layers and metal oxide layers is the microcut inorganic layer. [Item 20] The transfer article according to item 19, wherein the insulating layer includes a metal oxide layer. [Item 21] The transfer article according to item 1, further comprising an adhesive layer covering the functional layer. [Item 22] The transfer article according to item 1, wherein the microstructured inorganic layer further includes a pattern superimposed thereon, the pattern including tool marks having a period of less than approximately 750 microns. [Item 23] A method for manufacturing patterned articles, Removing a transfer article from a release layer selected from a metal layer or a doped semiconductor layer, wherein the transfer article is A carrier layer covering the aforementioned release layer, wherein the peel value between the release layer and the carrier layer is 2 to 50 grams / inch. A functional layer covering the carrier layer, wherein the functional layer includes at least one inorganic layer, and includes removal. A manufacturing method comprising bringing the carrier layer into contact with a microstructuring tool including at least one cutting edge, wherein the tool forms a cutting pattern in the at least one inorganic layer, the cutting pattern forms a corresponding pattern of a plurality of plates in the inorganic layer, each of the plates having a thickness of about 3 nanometers to about 2000 nanometers, and the patterned article having a thickness of less than 3 micrometers. [Item 24] The method according to item 23, wherein the plurality of plates are independent and have a regular shape. [Item 25] The method according to item 23, wherein the plurality of plates have a square or rectangular shape when viewed from above the xy plane of the inorganic layer. [Item 26] The method according to item 23, wherein the plurality of plates occupy approximately 1% to approximately 99% of the surface area of ​​the inorganic layer. [Item 27] The method according to item 21, wherein the plurality of plates include an uneven surface. [Item 28] The method according to item 21, wherein the tool includes at least two cutting edges. [Item 29] The method according to item 28, wherein the at least two cutting edges are configured to form a cutting pattern comprising a plurality of linear, substantially parallel cutting portions separated by a plurality of boundary regions. [Item 30] The method according to item 29, wherein the plurality of boundary regions are interconnected. [Item 31] The method according to item 29, wherein the plurality of boundary regions occupy approximately 1% to approximately 99% of the surface area of ​​the inorganic layer. [Item 32] The method according to item 23, further comprising laminating the functional layer of the transfer article onto a layer of a low modulus material having an elastic modulus of less than about 1000 MPa to form a patternable structure. [Item 33] The method according to item 28, wherein the layer of the low modulus material includes an adhesive. [Item 34] The first acrylate layer, A functional layer having a first main surface on the first acrylate layer, comprising a stack of metal layers and metal oxide layers, wherein at least one of the metal layers includes a cutting pattern that forms a corresponding pattern of a plurality of independent plates bounded by the cutting portion, and the precision-cut metal layer is about 5 nanometers to about 100 nanometers thick, A second acrylate layer on the second main surface of the functional layer, A first adhesive layer on the first acrylate layer, and a first polymer film layer on the first adhesive layer, A second adhesive layer on the second acrylate layer, which is optically transparent, and a second polymer film layer on the second adhesive layer, An article that is equipped with [something]. [Item 35] The article according to item 34, wherein at least one of the metal layers within the functional layer is located between barrier layers. [Item 36] The article according to item 34, wherein the metal oxide layer is selected from NbOx, SiAlOx, and mixtures and combinations thereof. [Item 37] The article according to item 34, wherein the article is reflective at wavelengths of 400 to 750 nm and at least partially transparent at wavelengths greater than approximately 830 nm. [Item 38] The article according to item 34, wherein at least some of the metal layers contain silver or silver oxide. [Item 39] The article according to item 34, wherein the second polymer film contains PETg. [Item 40] The article according to item 34, wherein at least a portion of the plurality of plates are located out of the plane of the functional layer, and the article has a tanδ maximum value of 0.12 when measured in a QWED split post dielectric resonator cavity at 9 GHz to 10 GHz. [Item 41] The article according to item 40, wherein the article has a maximum real dielectric constant of 30. [Item 42] The article according to item 34, wherein the functional layer comprises a stack of acrylate layers and one of a plurality of metal layers and a plurality of metal oxide layers, the plurality of metal layers and the plurality of metal oxide layers having different thicknesses. [Item 43] The article described in item 34, wherein at least a portion of the article is conductive.

Claims

1. A transfer article, A release layer including a metal layer or a doped semiconductor layer, A carrier layer that can be peeled off from the aforementioned peeling layer with a peeling value of 0.079 to 1.97 kg / m (2 to 50 grams / inch), A functional layer covering the carrier layer, wherein the functional layer includes at least one microcut inorganic layer, and the microcut inorganic layer is A plurality of plates bounded by a predetermined cutting pattern, each of which has a thickness of 3 nanometers to 2000 nanometers, including: The aforementioned transfer article has a thickness of less than 3 micrometers. The peel value is a peel force of 180 as measured by the method described in U.S. Patent Application Publication No. 2020 / 0016879 and U.S. Patent Application Publication No. 2020 / 0136086. Transfer articles.

2. A method for manufacturing patterned articles, Removing a transfer article from a release layer selected from a metal layer or a doped semiconductor layer, wherein the transfer article is A carrier layer covering the release layer, wherein the peel value between the release layer and the carrier layer is 0.079 to 1.97 kg / m (2 to 50 grams / inch), A functional layer covering the carrier layer, wherein the functional layer includes at least one inorganic layer, and includes removal. The method includes bringing the carrier layer into contact with a microstructuring tool including at least one cutting edge, wherein the tool forms a cutting pattern in the at least one inorganic layer, the cutting pattern forms a corresponding pattern of a plurality of plates in the inorganic layer, each of the plates having a thickness of 3 nanometers to 2000 nanometers, and the patterned article having a thickness of less than 3 micrometers. The peel value is a peel force of 180 as measured by the method described in U.S. Patent Application Publication No. 2020 / 0016879 and U.S. Patent Application Publication No. 2020 / 0136086. Manufacturing method.

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