TW201823035A - Composites comprising layers of nanoobjects and coating, preferably clear coating - Google Patents

Abstract

Described are single or multiple layer composites, comprising a first layer of certain coating compositions or cured reaction products thereof, and an electrically conductive, transparent layer comprising a plurality of electrically conductive nanoobjects. The invention further relates to coated articles comprising base articles and coatings, where the coatings are single or multiple layer composites. The invention also relates to methods of making said single or multiple layer composites and said coated articles, as well as to the use of certain coating compositions for making scratch-resistant, transparent and electrically conductive single or multiple layer composites.

Description

 a composite comprising a nanolayer and a coating (preferably a clear coating)  

The present invention relates to a single layer or multilayer composite comprising a first coating layer of a certain coating composition or a cured reaction product thereof and a conductive transparent layer comprising a plurality of conductive nanostructures. The invention further relates to coated articles comprising a substrate article and a coating, wherein the coatings are single or multi-layer composites. The invention also relates to methods of making the single or multilayer composite and the coated article, as well as to the use of certain coating compositions for the manufacture of scratch resistant, transparent and electrically conductive single or multilayer composites.

A conductive transparent layer comprising a plurality of conductive nanostructures (for example, a layer comprising a metal (specifically silver (Ag)) nanowire) is suitable for various purposes. For example, the layers can be used to manufacture the following: transparent electrodes, flat panel displays, liquid crystal displays (LCDs), touch screens, electrochromic windows, solar cells, transparent or thin film heaters, Smart glass/glasses, smart watches (including activity trackers), electronic wristbands, electronic fabrics, in general, battery friction electric nano energy generators and current collectors.

Due to its small size, the conductive transparent layer comprising a plurality of conductive nano-body and/or substrate carrying it can be susceptible to chemicals, heat, compared to, for example, a significantly increased specific surface area of the corresponding bulk material. And / or mechanical stress or damage effects. This mechanical stress or damage can be caused, for example, by exposure to a hard object or by continued exposure to mechanical forces. Such exposure may occur during or after the process of making the layers comprising conductive nanobody, such as during conventional use of products comprising such layers and/or substrates carrying them. Continued exposure to mechanical forces is common, for example, for transparent electrode systems in touch screen applications. Mechanical damage or sustained mechanical stress on the layer comprising the conductive nanobody and/or the substrate carrying it, which is typically present as a scratch, can affect the proper functioning of such layers or products comprising them. For example, such mechanical damage to a layer comprising a conductive nanobody can result in a deterioration of its electrical conductivity and/or its optical properties. Mechanical damage to substrates carrying such layers containing conductive nanostructures can also result in degradation of the optical properties of the layers.

In the patent US 8,049,333, a transparent conductor is described which comprises a conductive layer comprising a network of nanowires which can be embedded in a matrix. The conductor may additionally comprise a hard coating for providing particularly scratch resistant protection. Suitable hardcoat layers can include synthetic polymers.

C.-H. Liu et al. (Nanoscale Research Letters 2011, 6:75) describe transparent and conductive films based on Ag nanowires. Using a nail polish, the Ag nanowire film exhibits better stability under both scratching and bending.

Document WO 2014/137352 A1 describes a process for providing a metal substrate with corrosion resistance.

Document US 2014/0277318 A1 relates to implantable electrodes comprising a conductive polymeric coating.

The use of a curable mixture comprising a decane compound and a phosphoric acid diester or a diphosphate diester as a coupling reagent is described in the document DE 10 2006 024 823 A1 (equivalent to US 2009/0223631 A1).

Document WO 2006/122730 A1 describes coating materials based on isocyanate-based amine-based reactive reactants for molding coatings and methods for producing same.

The main object of the present invention is to provide a single layer or a multilayer composite comprising a conductive transparent layer, the conductive transparent layer comprising a plurality of conductive nano-body, wherein the conductive transparent layer comprising a plurality of conductive nano-layers effectively protects Protected from mechanical damage, in detail scratch-resistant. It is an additional object of the present invention to provide such single or multi-layer composites in a clear and clear appearance. Yet another additional object of the present invention is to provide such single or multi-layer composites in a flexible form, in particular in a flexible form that allows for mechanical manipulation without damaging the composites.

Another object of the present invention is to provide coated articles comprising such single or multi-layer composites.

It is yet another object of the present invention to provide a method of making such single or multilayer composites.

It is yet another object of the present invention to provide new uses for the manufacture of certain coating compositions for scratch resistant, transparent and electrically conductive single or multi-layer composites.

The invention and its preferred embodiments are defined in the scope of the patent application. The invention and its specific examples and preferred embodiments are also described and illustrated in detail herein below. Preferred embodiments and/or preferred aspects of the present invention can be as described herein and other specific examples and/or aspects of the present invention, in particular, and other preferred embodiments and/or Or a combination of preferred aspects. Preferred embodiments and/or preferred embodiments of the present invention, together with other preferred embodiments and/or preferred aspects of the present invention, will generally also yield preferred embodiments and/or preferred aspects of the invention.

The drawings schematically show the following: Figure 1: shows an example of a single layer or multilayer composite of the invention, wherein the first layer (1) and the conductive transparent layer (2) comprising a plurality of conductive nanostructures are identical (1) 2) and the concentration of the conductive nano-body in the first layer has a gradient in a direction perpendicular to the interface of the layer.

Figure 2: shows an example of a single layer or multilayer composite of the present invention, wherein the first layer (1) and the conductive transparent layer (2) comprising a plurality of conductive nanostructures are the same (1, 2) and in the first layer The concentration of the conductive nano-body is the same in all directions of the layer, that is, the conductive nano-body is uniformly dispersed in the first layer.

Figure 3: shows an example of a single layer or multilayer composite of the present invention, wherein the first layer (1) and the conductive transparent layer (2) comprising a plurality of conductive nanostructures are different and separated by a substrate layer (3) .

If not stated otherwise, the single layer or multilayer composite of the present invention is described or illustrated herein or is specifically described or illustrated in this respect as a specific example, aspect, and/or characteristic of the present invention. The cloth article, the method of making the single layer or multilayer composite of the present invention, and/or the use details of certain coating compositions of the present invention will also be applicable as necessary.

If not stated otherwise, a single or multi-layer composite, coated article, method of manufacture, or present herein, as described herein, "contains" or "includes" certain specific examples, elements, characteristics, and/or parameters. In the case of the use of the invention, this broader definition will also include, in each case, a disclosure of a narrower alternative to "consisting of such specific examples, elements, features and/or parameters".

It has now been found that the main object and other objects of the present invention are achieved by a single layer or a multilayer composite comprising: i) a first layer comprising: a coating composition comprising: (a At least one binder (A) having a reactive group, the binder (A) being a hydroxyl group-containing compound (A), (b) at least one crosslinking agent (B) capable of crosslinking by Reacting with the reactive groups of the binding agent (A), the crosslinking agent (B) is a compound (B) having a free and/or blocked isocyanate group, and (c) at least one catalyst (C), which is used For crosslinking a decyl group, the catalyst (C) is a phosphoric acid compound, more specifically phosphoric acid or phosphonic acid, which has a pKb And a bicyclic amine terminated having a boiling point > 100 ° C, wherein one or more of the components (A) and / or (B) and / or at least one additional component of the coating composition comprises a hydrolyzable alkyl group, or cured thereof The reaction product, and ii) a conductive transparent layer comprising a plurality of conductive nanostructures, wherein the first layer and the conductive transparent layer (hereinafter also referred to as "nanobody layer") are the same or different.

The specific coating compositions used in the present invention and the cured products thereof are known per se. Specific coating compositions are disclosed, for example, in the documents EP 2 225 299 B1, WO 2009/077180, and US Pat. No. 8,808, 805, the disclosures of each of each of

In the coating composition according to the present invention, at least one catalyst (C) for crosslinking a decyl group is a phosphoric acid compound, preferably phosphoric acid, which has a pKb 3 and bicyclic amine capping with a boiling point >100 °C. Preferably, the coating composition of the present invention, wherein the catalyst (C) is selected from the group consisting of having pKb 3 and a group consisting of a bicyclic amine-terminated substituted phosphomonoester and a phosphodiester having a boiling point of >100 ° C, preferably selected from the group consisting of having pKb 3 and a group consisting of a bicyclic amine-terminated acyclic phosphodiester and a cyclic phosphodiester having a boiling point of >100 °C. More preferably, the catalyst (C) is selected from the group consisting of an amine-terminated ethylhexyl partial ester and an amine-terminated phenyl partial ester, and even more preferably, the catalyst (C) is selected from the group consisting of Group of amine terminated bis(ethylhexyl) phosphates. In a particularly preferred variant of the invention, the blocked bicyclic amine present in the catalyst (C) is diazabicyclooctane.

Further, a coating composition of the present invention is preferred, wherein one or more of the coating compositions at least partially contain one or more of the same or different structural units of formula (I) -X-Si-R" _x G ₃ -x (I)

Wherein G is the same or different hydrolyzable group, more specifically (i.e., highly preferably) G is an alkoxy group (OR'), X is an organic group, more specifically 1 to 20 carbons The total number of atoms is a straight-chain and/or branched chain alkyl or cycloalkyl group. Excellent X is an alkyl group having a total number of 1 to 4 carbon atoms, and R" is an alkyl group, a cycloalkyl group, an aryl group. Or an aralkyl group, which may be heteroatomized by a non-adjacent oxygen, sulfur or NR _a group, wherein R _a is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, preferably R" is an alkyl group, More specifically, it has a total number of 1 to 6 carbon atoms, and x is 0 to 2, preferably 0 to 1, and more preferably x is 0.

In one or more groups G, the substituent R' is preferably an alkyl group having a total number of 1 to 6, preferably 1 to 4 carbon atoms. The alkoxy groups OR' in one or more of the groups G are the same or different. Preferred is a group G in which the alkoxy groups OR' are the same.

A more detailed description and definition of suitable coating compositions, preferred embodiments thereof, and methods of making coatings (preferably clear coatings) from such coating compositions are described in EP 2 225 299 B1, WO 2009/077180 and / or given in US 8,808,805. Preferred coating compositions for use in the monolayer or multilayer composite of the present invention are defined in the technical schemes 3, 4, 6, 7, 8, 9, 10, 11, 12 and 13 of EP 2 225 299 B1, The definitions are incorporated herein by reference. Also preferred is a cured reaction product (i.e., a coating) of a preferred coating composition as defined above.

Coatings (preferably clear coatings) made from such coating compositions are considered to be the cured reaction products of the coating compositions. Preferred coating compositions for use in accordance with the present invention are commercially available from BASF under the trademark "iGloss".

The term "nanobody" as used herein is intended to mean an object in which one, two or three of its outer dimensions are in the nanometer order. Definitions used herein to further describe and interpret terms relating to nanotechnology are referred to the standard technical specification ISO/TS 27687:2008 (first edition). "Nanoscale" as used herein is therefore intended to encompass a range of sizes from about 1 to 100 nm. Nanoscale dimensions can be determined for the purposes of the present invention by means of penetration electron microscopy ("TEM") as known in the art. For example, the thickness of the layer comprised by the single layer or multilayer composite of the present invention can be determined from TEM images of cross sections of samples from the layer or the composite, respectively. Nanoscale dimensions are also known for the purposes of the present invention as determined by scanning electron microscopy ("SEM") (e.g., by field emission scanning electron microscopy). Samples for studying cross-sections can be prepared by means of focused ion beam ("FIB") techniques as is known in the art. The nanobody as used herein is electrically conductive and preferably comprises or consists of a material having a higher electrical conductivity, preferably having a conductivity of not less than 1 x 10 S/m at 20 ° C. material.

The nanobody may be selected from the group consisting of nanoparticle, nanoplate, nanosheet, nanofiber, nanotube, nanorod, nanosphere, nanometer for the purpose of the present invention. Belt and nanowire. The nanowire is preferred, in particular, wherein the nanobody comprises or consists of a metal or an alloy thereof. Nanotubes are preferred, in particular, wherein the nanobody contains or consists of carbon.

The term "nanoparticle" as used herein is intended to mean a nanobody in which all three outer dimensions are in the nanometer order, while the length of the longest axis of the nanobody and the length of the shortest axis are significantly different.

The term "nanoplate" as used herein is intended to mean that one of its outer dimensions is in the nanometer scale, while the two other outer dimensions may be significantly larger (eg, three or more times larger) It is not necessary to present a nano-sized nano-body. The minimum external dimension is considered to be the thickness of the nanoplate. Another common term commonly used to refer to a nano-body having only one size in the nanometer range is "nano-sheet".

The term "nanofiber" as used herein is intended to mean a nanobody in which two similar outer dimensions of the nanometer scale and a third dimension are significantly larger. Two similar external dimensions are considered to be less than three times the size difference, and a significantly larger outer dimension is considered to be three times different from the other two and may not be nanometer. This maximum outer dimension corresponds to the length of the nanofibers. Nanofibers can be flexible or rigid.

The term "nanotube" as used herein is intended to refer to hollow nanofibers.

The term "nano rod" as used herein is intended to refer to a nano-body having a similarly larger outer dimension of the nanometer scale and a significantly larger third dimension that is rigid (ie, inflexible). Nanorods can be considered as solid (or hard) nanofibers.

The term "nanosphere" as used herein is intended to mean a substantially equal proportion of nanoparticle, i.e., nanoparticle having an aspect ratio of all three orthogonal outer dimensions of approximately one. The aspect ratio refers to the ratio of the longest dimension to the shortest dimension of the object (usually height: the ratio of length).

The term "nanobelt" as used herein is intended to mean a nanobody having two similar outer dimensions in the nanometer scale while the third outer dimension (length) is significantly larger. The nanoribbon has a cross section of an approximately rectangular shape that vertically expands the third outer dimension (length).

The term "nanowire" as used herein is intended to mean a conductive or semi-conductive nanofiber, preferably a conductive nanofiber.

The term "conducting" as used herein generally has the meaning that a material having this property is capable of allowing current to flow when a suitable voltage is applied. The conductive transparent layer comprised by the single layer or multilayer composite of the present invention comprises a plurality of conductive nanostructures. The conductive nanostructures contribute in part to, preferably, and better fully establish the conductive properties of the conductive transparent layer. The nature of the conductive nanobody, its number and arrangement in the electrically conductive transparent layer must be chosen in such a way as to allow for an increase and/or determination of the conductivity of the electrically conductive transparent layer.

As used in the present invention, with respect to the conductive nano-body, preferably a conductive metal nano-body, "conducting" preferably has the following meaning: each nano-body has (the material separately made into a conductive nano-body) The electrical conductivity is not less than 1 × 10 ⁵ S/m at 20 ° C, preferably in the range of 1 × 10 ⁵ to 1 × 10 ⁹ S / m at 20 ° C.

Regarding the conductive transparent layer containing a plurality of conductive nano-body, the conductivity can be optimally provided in the term "sheet resistance" (see below for details). Preferably, the conductive transparent layer comprising a plurality of conductive nano-body has a four-point probe or a non-contact thin layer on each surface of the conductive transparent layer comprising a plurality of conductive nano-body The sheet resistance in the range of 10 to 150 ohm/sq, more preferably 10 to 60 ohm/sq, measured by a resistance measuring system (inductance measurement). Preferably, the thin layer of the single or multi-layer composite of the present invention is more preferably measured according to standard procedure ASTM F1844-97 (2016) by non-contact sheet resistance measurement as defined in more detail below. resistance. Conductivity is present in one or more directions and/or regions of the conductive transparent layer, and typically exists in the layer at least in the direction of the layer itself and/or in one or more regions parallel to the surface of the layer itself in.

With regard to the single layer or multilayer composite of the present invention, conductivity can be similarly best provided in its term "sheet resistance" (see below for details). Preferably, the single layer or multilayer composite of the present invention has a non-contact sheet resistance measurement system as defined in more detail below on the surface of the first layer of the single or multilayer composite (as defined in more detail below) Inductance measurement) The sheet resistance measured in the range of 10 to 150 ohm/sq, more preferably 10 to 60 ohm/sq. Preferably, the sheet resistance of the single layer or multilayer composite of the present invention is measured by non-contact type sheet resistance measurement according to standard procedure ASTM F1844-97 (2016).

The conductive nanobody of the present invention (in detail, the nanowire) may comprise one or more metals (also referred to as "metal nanowires" or "metal nanowires" if applicable) and/or one or more non- A metal material (including a mixture of one or more metals (eg, Ag) and one or more non-metal (eg, carbon) materials) or consists of.

Suitable one or more metal systems comprising or consisting of the conductive metal nanobody of the present invention are selected from the group consisting of cobalt (CO), copper (Cu), gold (Au). ), iron (Fe), molybdenum (Mo), nickel (Ni), palladium (Pd), silver (Ag), tin (Sn), tungsten (W) and, where possible, two or more An alloy of these metals. Preferred metals are Ag, Au, Cu and Ni and any alloy composed of two or more than two of these metals. Pure metals are preferred over alloys. The best is Ag.

Suitable non-metallic materials for the conductive nano-body are carbon, in particular in the form of graphene and/or in the form of carbon nanotubes.

Metallic nano-body (detailed metal nanowire, more specifically the Ag nanowire) is preferred for all aspects of the invention (single or multilayer composite, coated article, method of manufacture and use) Conductive nanobody.

Preferably, the conductive nano-body defined above is a metal nanowire, more preferably having an average length in the range of 10 μm to 50 μm in each case, preferably an average length in the range of 15 μm to 40 μm. More preferably, it has an average length in the range of 20 μm to 30 μm (for example, a length of about 25 μm) (there is no coating or absorbent on the outer surface thereof), and in each case has an average diameter in the range of 10 nm to 100 nm, A metal nanowire having an average diameter in the range of 15 nm to 80 nm, more preferably an average diameter (for example, a diameter of about 30 nm) in the range of 20 nm to 50 nm.

In general, the conductive nanobody as described herein and the methods for preparing the same are known in the art (see, for example, US 7,922,787 or US 8,049,333 and the references cited herein in each case) . In addition, many of these conductive nano-body bodies are commercially available, in particular metal nanowires such as Au or Ag nanowires. Typical commercial performances are, for example, alcohols or aqueous dispersions such as Ag or Au nanowires, in which suitable preservatives, such as polyvinylpyrrolidone or polyethylene, coated or absorbed onto the surface of the nanowires can be used. alcohol.

Non-metallic conductive nano-body such as carbon nanotubes and methods and uses for preparing same are known in the art, see, for example, US 6,232,706, R. Chavan et al., International Journal of Pharmaceutical Sciences Review and Research, Vol. 13/1 (2012) 125-134 or K. Saeed et al., Carbon Letters, Vol. 14/3 (2013) 131-144. Carbon nanotubes are also commercially available, for example from Sigma-Aldrich, see, for example, the manual "Material Matters" by Sigma-Aldrich, Vol. 4, No. 1 (2009).

Preferred is a single layer or multilayer composite according to the invention (or a preferred single layer or multilayer composite according to the invention as defined herein) comprising: i) a first layer, The invention comprises: a coating composition comprising: (a) at least one binder (A) having a reactive group, the binder (A) being a hydroxyl group-containing compound (A), and (b) at least one crosslinking agent (B), which is capable of reacting with the reactive groups of the binding agent (A) by cross-linking, the crosslinking agent (B) being a compound (B) having a free and/or blocked isocyanate group, and (c) at least one catalyst (C) for crosslinking a decyl group, the catalyst (C) being a phosphoric acid compound selected from the group consisting of substituted phosphoric acid monoesters and phosphodiesters, preferably selected from non- a group consisting of a cyclic phosphodiester and a cyclic phosphodiester, the phosphate compound 3 and bicyclic amine capping with a boiling point >100 °C.

One or more of the components (A) and/or (B) and/or at least one additional component of the coating composition comprising a hydrolyzable alkylene group, or a cured reaction product thereof, and ii) a conductive transparent layer, A plurality of conductive metal nanocrystals, wherein the metal is preferably selected from the group consisting of cobalt, copper, gold, iron, molybdenum, nickel, palladium, silver, tin, tungsten, and two or more An alloy of two such metals, and wherein the first layer and the conductive transparent layer are the same or different.

Preferably, the "conductive transparent layer" is an electronically conductive transparent layer (as opposed to "ionically conductive"). Similarly, a preferred "electrically conductive nanobody" is an electronically conductive nanobody. Preferably, the "conductive transparent layer comprising a plurality of conductive nano-body" is an electronically conductive transparent layer comprising a plurality of electronically conductive nano-body. Most preferably, in the electronically conductive transparent layer comprising a plurality of electronically conductive nano-portions, at least 90% of the total conductivity of the at least electronically conductive transparent layer is electronically Caused by the presence of conductive nano-body.

As used herein, the terms "transparent", "transparent" or "optically transparent", in particular, the transparency or light transmittance of the layer of the single or multi-layer composite of the present invention preferably has the following meaning: In one case, when measured according to the standard method ASTM D1003-13 (Procedure A), the layer (ie, each transparent layer) (eg, a conductive transparent layer comprising a plurality of conductive nano-body) is in each case in an electromagnetic wave The visible region of the spectrum (i.e., in the range of about 380 nm to 780 nm, more specifically in the range of about 400 nm to 700 nm) has 70% or more, more preferably 75% or more, and still more preferably 80% or more. High, even better, light transmission of 85% or higher and even better 90% or higher.

In a preferred embodiment, the first layer as defined above is transparent and clear, and more preferably the first layer is in the form of a clear clear coating.

In another preferred embodiment, the single layer or multilayer composite of the present invention comprises only a transparent layer and is preferably transparent in itself.

As will be appreciated, the light transmission capabilities of the various layers are particularly the ability of their thickness and their materials. The overall light transmission capability of the transparent single layer or multilayer composite of the present invention is especially the ability to form the thickness, material and/or number of layers thereof. In general, the single layer or multilayer composite of the present invention may comprise one layer, two or more layers (including, for example, three layers, four layers, or five layers). However, in preferred embodiments of the invention in which a transparent single layer or multilayer composite is desired, this will only comprise a transparent layer and only within such number and thickness to allow for transparency throughout the single or multilayer composite. . Preferably, the single layer or multilayer composite of the present invention does not comprise more than one of: (i) the first layer and (ii) a conductive transparent layer comprising a plurality of conductive nanostructures, and if present , the substrate layer.

In a further preferred embodiment, the single layer or multilayer composite of the present invention is flexible. The term "flexible" as used herein means that a material having this property can be bent in all directions (but not necessarily closed) without undergoing damage to its structure while maintaining its optical properties and/or electricity. All or at least part of the characteristics. Those skilled in the art will appreciate the level of mechanical stress that can be reasonably applied when manipulating electronic components such as single or multi-layer composites of the present invention. Preferably, the single or multi-layer composite of the single or multi-layer composite film is preferably in the form of a roll film.

In certain preferred embodiments, the single layer or multilayer composite of the present invention may additionally comprise one or more substrate layers to effectively produce the multilayer composite of the present invention (i.e., at least a two layer composite).

Preferably, the substrate layer as used in the single layer or multilayer composite of the present invention is selected from the group consisting of foils, films, webs, sheets and sheets. More preferably, the substrate layer has a thickness in the range of 5 μm to 250 μm, preferably in the range of 10 μm to 200 μm, more preferably in the range of 50 μm to 100 μm, in each case perpendicular to the interface of the substrate layer. Where a flexible single layer or multilayer composite is desired, the substrate layer is typically also flexible in itself.

Unless otherwise stated, the one or more substrate layers preferably comprise or consist of one or more materials selected from the group consisting of glass, metal, sapphire, bismuth (Si), and plastic.

In particular and preferred embodiments, in detail where the transparent single layer or multilayer composite is desired, the one or more substrate layers comprise or consist of a transparent material. Preferably, the substrate layers are also electrically insulated in such cases. Suitable transparent materials for the substrate layer may, for example, be selected from the group consisting of glass and plastic. Preferred types of glass are, for example, float glass, low iron float glass, heat strengthened glass, and chemically reinforced glass. Optionally, the glass has a low-emissivity/low-e coating, a sun protection coating or any other coating on the surface facing away from the nanolayers ii) described above. The preferred type of plastic is an organic polymer, more preferably those selected from the group consisting of consisting of the following organic polymers: Poly (methyl methacrylate) (of PMMA, commercially available, for example, Plexiglas ^TM), polycarbonate (PC ), polyethylene (PE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), low density polypropylene (LDPP) polyethylene terephthalate (PET) Diol modified polyethylene terephthalate, polyethylene naphthalate (PEN), cellulose acetate butyrate, polylactide (PL), polystyrene (PS), A mixture of polyvinyl chloride (PVC), polyimine (pI), polyoxypropylene (PPO), and any of the foregoing organic polymers. PET and PEN are especially good.

Preferably, the substrate layer as used in one embodiment of the invention (i.e., as used in a single layer or multilayer composite in accordance with the present invention) is flexible. Further, the substrate layer as used in one embodiment of the present invention is preferably transparent. Still further, the substrate layer as used in one embodiment of the present invention preferably has a surface exhibiting suitable hardness, in particular resistance to mechanical stress, and a better scratch resistance. Furthermore, the substrate layer as used in one embodiment of the invention preferably has a lower moisture permeability and/or a higher thermal resistance. The substrate layer as used in one embodiment of the invention preferably comprises or consists of an organic polymer as defined above. The appropriate hardness of the surface of the substrate layer as used in one embodiment of the present invention is in the range of 1H to 9H in each case as measured according to the pen-shaped standard test method for film hardness (ASTM D3363-00), More preferably in the range of 2H to 4H.

As explained above, the single layer or multilayer composite of the present invention comprises the first layer i) and the nano-body layer ii), wherein the first layer and the nano-body layer may be the same or different.

In a preferred embodiment of the single or multi-layer composite, the first layer and the nano-body layer are the same, and - the concentration of the conductive nano-body in the first layer is perpendicular to the interface of the layer There is a gradient in the direction or - the concentration of the conductive nano-body in the first layer is the same in all directions of the layer.

An alternative in which the concentration of the conductive nano-body in the first layer has a gradient is preferred, and is preferably obtained by first producing a nano-body layer and then embedding the nano-body layer in the matrix material, This results in the first layer as a single layer, for example, as further described below. In a preferred option of this alternative, sufficient interconnections (i.e., mutual contact) between individual conductive nano-body or conductive nanowires (preferably metallic nanowires or metal nanowires) The plurality of conductive nano-body bodies defined above, more preferably a plurality of metal nano-body and/or metal nano-wires are respectively arranged in the form of adjacent conductive networks and contact metal nanoparticles or metal nanowires. The rice body layer is such that electrons can flow along the interconnected conductive nano-body or conductive nanowire (preferably metal nano-body or metal nanowire) within the network. When such a network is constructed of a conductive nanowire, it will also be referred to herein as a "nano-line network" (or, individually, a "metal nanowire network"). In a preferred alternative of this alternative, the plurality of conductive nanowires in the conductive transparent layer are embodied by a silver nanowire network ("AgNW").

The alternative in which the concentration of the conductive nano-body in the first layer is the same in all directions of the layer is preferably obtained by using a suitable preparation of the metal nano-body (for example, a suitable preparation of a metal nanowire such as AgNW) At least one suitable component of the coating composition as defined herein is premixed, preferably until a uniform distribution is achieved in the premix, and this (preferably homogeneous) premix is used for further processing, for example, as follows Further description. To promote conductivity in the resulting nanolayer, the concentration of the conductive nanobody in the premix can be adjusted to a suitable value.

In a preferred embodiment of the single layer or multilayer composite of the present invention, the first layer (i)) has a thickness of not more than 30 μm, preferably 0.1 to 0.1 in each case perpendicular to the interface of the first layer. The thickness in the range of 30 μm, more preferably in the range of 0.1 to 10 μm. This specific example is particularly preferred when the first layer and the nanobody layer are the same. This particular example is also preferred when the first layer and the nanobody layer are the same and wherein the concentration of the conductive nano-body in the first layer has a gradient in a direction perpendicular to the interface of the layer.

In some embodiments of the single layer or multilayer composite of the present invention, the first layer (i)) has a thickness of not more than 500 μm, preferably 20 to 150 μm in each case perpendicular to the interface of the first layer. The thickness within the range. This specific example is particularly preferred in the first layer and the nano-body layer.

In the multilayer composite of the present invention, wherein the first layer i) and the nano-body layer ii) are the same and the composite further comprises a substrate layer, such that it extends over the entire surface of the substrate or only on the surface The manner of expansion in the finite area places the combined first layer and the nano-body layer on the surface of the substrate. In a particular case, the plurality of conductive nano-merses in the combined first layer and the nano-body layer form a pattern on the surface of the substrate. The pattern can be selected from any random and non-random structure such as grids, strips, corrugations, spots, and circles.

In another preferred embodiment, the single layer or multilayer composite of the present invention is a multilayer composite, wherein the first layer and the conductive transparent layer comprising a plurality of conductive nano-body are different and wherein the first layer and the first layer The conductive transparent layer is separated from each other by one or more substrate layers. A single layer or multilayer composite of this specific example comprising no more than one layer of each type (the first layer, the conductive transparent layer comprising a plurality of conductive nanostructures and the substrate layer) is preferred.

In an alternative to this specific example, the nanobody layer can be disposed on the surface of the substrate such that it expands over the entire surface of the substrate or only spreads over a limited area of the surface. In a particular case, a plurality of conductive nano-body bodies in the nano-body layer form a pattern on the surface of the substrate. The pattern can be selected from any random and non-random structure such as grids, strips, corrugations, spots, and circles.

The invention also relates to a coated article comprising: - a substrate article, and - a coating on the substrate article, wherein the coating is a single layer or multilayer composite of the invention as defined herein or as Preferred herein are preferred monolayer or multilayer composites of the present invention.

In general, all aspects of the invention discussed herein in the context of the single layer or multilayer composite of the invention are modified as necessary to apply to the coated article according to the invention, as defined by the context, and vice versa.

The coated article can be, for example, an intermediate product at the time of manufacture or, if applicable, a portion of a product or product selected from the group consisting of: a transparent electrode, a flat panel display, a liquid crystal display (LCD), a touch Screens, electrochromic windows, solar cells, transparent or film heaters, smart glass/glasses, smart watches (including activity trackers), electronic wristbands, electronic fabrics, in general, battery triboelectric nanometers Energy generators and current collectors.

The invention further relates to a method of making a single or multi-composite as defined herein or a coated article as defined herein, the method comprising the steps of: - providing or preparing a coating composition, the coating composition The composition comprises: (a) at least one binder (A) having a reactive group, the binder (A) being a hydroxyl group-containing compound (A), and (b) at least one crosslinking agent (B) capable of Reacting with the reactive groups of the binding agent (A) by cross-linking, the crosslinking agent (B) is a compound (B) having a free and/or blocked isocyanate group, and (c) at least one catalyst ( C), which is used for crosslinking a decyl group, the catalyst (C) being a phosphoric acid compound, more specifically phosphoric acid or phosphonic acid, having a pKb 3 and a bicyclic amine end group having a boiling point of >100 ° C, preferably a phosphoric acid compound selected from the group consisting of substituted phosphoric acid monoesters and phosphodiesters, the phosphoric acid compound having pKb And a bicyclic amine terminated having a boiling point > 100 ° C, wherein one or more of the components (A) and / or (B) and / or at least one additional component of the coating composition comprises a hydrolyzable alkyl group, - provided or prepared a mixture comprising a plurality of conductive nanostructures and - applying the coating composition and the mixture to a single (preferably identical) surface of the substrate or at least two different surfaces (preferably in each case) The layer composition and the mixture are applied to the same at least two surfaces), o in a single step after pre-mixing the coating composition with the mixture or o without pre-mixing the coating composition with the mixture In a separate step.

The preferred method for producing a coating (preferably a clear coating) from a coating composition is explained in more detail in the documents EP 2 225 299 B1, WO 2009/077180 and US Pat. No. 8,808,805, the disclosure of which is incorporated herein by reference. Into this article.

In general, all the aspects of the invention discussed herein in the context of the single or multi-layer composites and coated articles of the invention are modified as necessary to apply to the manufacturing method according to the invention, such a context Definition, and vice versa.

In a preferred embodiment of the manufacturing method of the present invention, the coating composition and the mixture comprising the plurality of conductive nano-body are applied to the substrate alone in a separate step without pre-mixing. (ie at least one, preferably the same) surface, wherein:

- in a first coating step, applying the mixture comprising a plurality of conductive nano-body to the surface of the substrate, and - subsequently in the second coating step, the coating composition

o coating onto the mixture on the surface of the substrate or o onto the plurality of conductive nano-body on the surface of the substrate such that a first conductive transparent layer comprising a plurality of conductive nano-body is produced On the substrate, wherein the first layer on the surface of (aa) preferably has a thickness perpendicular to the interface of the layer of not more than 30 μm, preferably in the range of 0.1 to 10 μm, and/or (ba) the first The concentration of the conductive nano-body in the layer has a gradient in a direction perpendicular to the interface of the layer.

The first coating step and the second coating step can be performed as many times as necessary to produce a plurality of first conductive transparent layers comprising a plurality of conductive nano-body as needed. Preferably, each of the first coating step and the second coating step is performed only once such that only one first conductive transparent layer comprising a plurality of conductive nano-body is produced.

In a preferred embodiment of the manufacturing method, a single layer or a multilayer composite may be prepared, wherein the first layer i) and the nano body layer ii) are the same and wherein the first layer and the nano layer are electrically conductive The concentration of the nanobody (preferably metal nanobody) has a gradient in the direction perpendicular to the interface of the layer. Preferably, the electrically conductive nanobody is embedded in the first layer in this case, and that at least a portion of the electrically conductive nano-body is exposed to the surface or interface of the first layer in a manner that provides electrical contact.

When a metal nanobody (better metal nanowire) is used in the method of the invention, the mixture comprising a plurality of metal nanoparticles is preferably provided or prepared in a manner known in the art, for example by An uncoated metal nanoparticle is first deposited on the surface of the substrate such that a metal-to-metal junction between adjacent and overlapping (contacting) metal nanoparticles is formed. Typically, the plurality of metal nanoparticles are applied to the surface of the substrate in the form of a suspension comprising metal nanoparticles (sometimes referred to as an ink) which is dispersed in a carrier liquid. The carrier liquid typically has a boiling point below 120 °C. A typical carrier liquid is, for example, ethanol, isopropanol (propan-2-ol), water or a mixture of any of the foregoing. Thus, in this alternative embodiment, the placement of a plurality of metal nanoparticles on the surface of the substrate is generally carried out by: - applying a suspension of metal nanoparticles dispersed in the carrier liquid to the substrate The surface of the layer forms a wet film on the surface of the substrate, and - the wet film is formed on the surface of the substrate to remove the carrier liquid.

Preferably, the ink is applied to the surface of the substrate by a technique selected from the group consisting of coating and printing techniques. Preferred techniques are selected from the group consisting of: (doctor) knife coating, slit coating, ink jet printing, spin coating, and spray coating (including air spray and electrostatic spray).

The carrier liquid having a boiling point lower than 120 ° C is usually removed from the wet film by evaporation (drying). Preferably, the carrier liquid having a boiling point lower than 120 ° C is removed by exposing the wet film formed on the surface of the substrate to air having a temperature lower than 150 ° C, preferably 20 At temperatures ranging from °C to 120 °C, for example at about 120 °C. In some cases, the carrier liquid is removed at room temperature, i.e., at a temperature ranging from 20 ° C to 23 ° C.

Preferably, the coverage of the surface of the substrate covered by the plurality of metal nanoparticles is in the range of 10% to 65%, preferably 15% to 35%. For calculating the coverage, an image of the surface of the plurality of metal nanoparticles disposed thereon is obtained by optical microscopy or scanning electron microscopy, and by means of being able to distinguish the metal nano within the images The image is analyzed by an image analysis software that calculates the fraction of the surface covered by the metal nano-body and the bare surface of the substrate, as is known in the art. The thickness of the resulting layer comprising a plurality of conductive nano-body (preferably metal nano-body) but not the coating composition as defined above is typically in the range of 10 to 150 nm, preferably in the range of 20 to 100 nm.

After depositing the plurality of metal nano-bodyes on the surface of the substrate, the coating composition is preferably applied to a plurality of previously prepared metal nanoparticles. It is assumed that the deposition of the coating on the plurality of metal nanoparticles does not significantly alter the joint between the adjacent and overlapping (interacting) metal nanoparticles disposed on the surface of the substrate. .

The application of the coating composition to a plurality of metal nanoparticles is preferably carried out according to the general method disclosed in any one of the documents EP 2 225 299 B1, WO 2009/0777180 and/or US 8,808,805, as described above. Discussion.

In the coating composition (in detail, the single layer or multilayer composite or the production method of the present invention) used in accordance with the present invention, the weight fraction of the polyol (A) and the polyisocyanate (B) is preferably selected. The molar equivalent ratio of the unreacted isocyanate group containing the isocyanate compound (B) to the hydroxyl group of the hydroxyl group-containing compound (A) is in the range of 0.9:1 to 1:1.1, preferably in the range of 0.95:1 to 1.05:1. More preferably in the range of 0.98:1 to 1.02:1.

The coating component comprising the hydroxyl-containing compound (A) and optionally other components (as described in more detail in, for example, US Pat. No. 8,808,805) are typically additionally coated with one of the isocyanate-containing compounds (B). The layer components (and, if appropriate, additional optional components as described) are mixed, which is typically carried out shortly before application of the resulting coating composition. In general, the coating component comprising compound (A) typically also comprises catalyst (C) and is also part of the solvent. The solvent suitable for use in the coating composition of the present invention is specifically chemically inert to the compounds (A) and (B) in the coating composition and not (A) and (B) when the coating composition is cured. And the solvents that react with them (see, for example, US 8,808,805 for more details).

The coating composition can be applied to a plurality of metal nanoparticles by any coating method selected from the group consisting of: (doctor) knife coating, slit coating, ink jet printing, Spin coating and spraying (including air spraying and electrostatic spraying).

Any solvent present may then be removed, partially or completely, by evaporation. For example, the solvent can be vaporized by exposure to air or compressed air for a period of 10 to 60 minutes (eg, 20 minutes).

Preferably, after removal of the solvent and, if necessary, additional additional time (usually not exceeding 1 h), the coated coating composition may then be cured or annealed into the finished coating, preferably to a clear Or in a clear coating. Such remaining time is used, for example, to level and de-evaporate the coating film and/or evaporate volatile components such as solvents. The remaining time can be assisted by the application of high temperatures and/or by reduced humidity, provided that no damage or modification is caused to the coating film, such as premature complete crosslinking. Thermal curing of the coating composition, which is generally unimportant for the method of application and common methods known in the art, can be used, such as heating in a forced air oven or irradiation with an infrared lamp. Thermal curing can also be carried out in stages. Another preferred method of curing is curing with near infrared (NIR) radiation. The thermal curing is preferably in the range of from 30 ° C to 200 ° C in each case, more preferably in the range of from 40 ° C to 190 ° C, in particular in the range of from 50 ° C to 180 ° C (eg 140 ° C). It is in the range of 1 min to 10 h, more preferably in the range of 2 min to 5 h, and even more preferably in the range of 3 min to 3 h (for example, a period of 5 min to 60 min, such as 20 min).

In a specific embodiment of the manufacturing method of the present invention, the coating composition and the mixture comprising a plurality of conductive nano-bodyes are applied to at least one surface of the substrate after pre-mixing, wherein: - the first The mixture of conductive nanocrystals is premixed with at least one component of the coating composition, and - the premix is then applied to a single surface or at least two surfaces of the substrate.

In this particular example, a mixture comprising a plurality of conductive nanostructures is typically premixed with component (A) or component (B) of a coating composition as defined herein at a concentration suitable for the purpose. All additional process steps are essentially similar to the process steps described above with respect to other specific examples. In particular, after the premix is applied, there is typically a subsequent step of curing or annealing the coating composition or premix to obtain a finished coating, preferably a clear coating.

In a preferred embodiment of the manufacturing method of the present invention, a first conductive transparent layer comprising a plurality of conductive nano-body is produced on a substrate (see the above for the preferred steps for fabricating the first layer in the method of the present invention) Where the first layer is subsequently stripped from the surface of the substrate. In this context, the first layer is preferably a film and/or detached from the surface comprising the first layer. According to this specific example, the substrate does not retain a portion of the single layer or multilayer composite, but acts as a template. Thus, the substrate can be rigid or flexible, transparent or opaque. Preferably, however, the substrate used in this preferred embodiment has the property of facilitating detachment or stripping of the first layer. A preferred suitable property for this purpose is higher hydrophobicity, in particular the higher hydrophobicity of the substrate surface carrying the first layer. As is known in the art, the higher hydrophobicity of the substrate surface can be characteristic of the substrate itself or the surface of the substrate can be hydrophobized, for example, by applying a self-assembled monolayer ("SAM") of organic molecules to the surface of the substrate. . The organic molecule SAM is assembled by organizing molecules that spontaneously form on the surface and is organized into more or less large ordered domains. For the purposes of the present invention, a suitable substrate (e.g., Si or glass) can be wetted with a suitable reagent for application of SAM to the surface of the substrate. Suitable reagents for applying SAM to the surface of the substrate are, for example, octadecyltrichlorodecane or dodecyltrichloromethane. Thus, the surface of the preferred substrate is hydrophobized, i.e., modified to provide increased hydrophobicity compared to the unmodified surface.

In a preferred embodiment of the method of making a single layer or multilayer composite according to the present invention, the coating composition and the mixture comprising a plurality of conductive nanostructures are combined in a separate step without premixing. Applying to at least two different surfaces of the substrate (preferably two surfaces on opposite sides of the planar substrate), wherein: - in a coating step, applying the mixture comprising a plurality of conductive nanostructures to At least one surface of the substrate, and - in a separate coating step, applying the coating composition to at least one other (ie, different, preferably opposite) surface of the substrate (to prepare a "first layer" ).

Preferably, in the preferred embodiment, the first layer (i)) has a thickness perpendicular to the interface of the layer of no more than 500 μm, preferably in the range of 20 to 150 μm.

Preferably, the coating composition applied in a separate coating step does not comprise any conductive nano-body.

In general, the coating steps of these preferred embodiments can be carried out analogously to the coating steps as described above for the preferred embodiment of the method for making a single or multilayer composite according to the present invention, wherein The coating composition and the mixture comprising a plurality of conductive nano-body are applied to at least one surface of the substrate in a separate step without pre-mixing, but of course the following restrictions are imposed according to this specific example: The coating composition and the mixture comprising a plurality of conductive nanostructures are applied to the same surface of the substrate, but are applied to different surfaces of the same substrate.

The coating step in this preferred embodiment can be carried out in any of the following sequences: first, a mixture comprising a plurality of conductive nanostructures can be first applied to at least one surface of the substrate, and then the coating composition is applied to At least one other surface of the same substrate, or the coating composition may be first applied to at least one surface of the substrate, and then the mixture comprising the plurality of conductive nano-body is applied to at least one other surface of the same substrate, or simultaneously Perform these two steps. In a variation of this preferred embodiment, the coating composition in a separate coating step may additionally or alternatively (a) be applied to the mixture on the surface of the substrate or (b) coated to a plurality of conductive nano-body bodies on the surface of the substrate. Preferably, a mixture comprising a plurality of conductive nano-body and a coating composition are applied to opposite sides of a flat substrate selected from the group consisting of foils, films, webs, sheets and sheets . Preferably, after application to the surface of the substrate, prior to applying the coating composition or a mixture comprising a plurality of conductive nanocrystals to respective other surfaces of the substrate, the first adhesion is included for better adhesion. A plurality of conductive nanobody mixtures or coating compositions, i.e., the coating composition can be cured or annealed as described above and a mixture comprising a plurality of conductive nanostructures can be dried as described above.

The invention also relates to the use of a coating composition, wherein the coating composition comprises: (a) at least one binder (A) having a reactive group, the binder (A) being a hydroxyl-containing compound (A) (b) at least one crosslinking agent (B) capable of reacting with the reactive groups of the binding agent (A) by crosslinking, the crosslinking agent (B) having free and/or sealed a terminal isocyanate group-containing compound (B), and (c) at least one catalyst (C) for crosslinking a decyl group, the catalyst (C) being a phosphoric acid compound, more specifically a phosphoric acid or a phosphonic acid, the phosphate compound With pKb And a bicyclic amine capping having a boiling point of >100 ° C, preferably a phosphoric acid compound selected from the group consisting of substituted phosphoric acid monoesters and phosphodiesters, the phosphoric acid compound having pKb And a bicyclic amine terminated having a boiling point > 100 ° C, wherein one or more of the components (A) and / or (B) and / or at least one additional component of the coating composition comprises a hydrolyzable alkyl group, or cured thereof The reaction product is used to make a scratch-resistant, transparent and conductive single or multi-layer composite.

In general, all aspects of the invention discussed herein in the context of the single or multi-layer composites, coated articles and methods of manufacture of the present invention are modified as necessary for use in accordance with the present invention. Contextually defined, and vice versa.

Preferably, the use according to the invention, wherein the single or multi-layer composite comprises a plurality of electrically conductive nano-forms of a single layer or at least one of the plurality of layers.

Surprisingly, it has been found that a coating composition as defined above or a cured reaction product thereof effectively protects a conductive transparent layer comprising a plurality of conductive nanostructures in a single layer or multilayer composite of the present invention from mechanical stress or mechanical Damage, in particular from scratching, while the optical and electrical properties of the electrically conductive transparent layer comprising a plurality of electrically conductive nanostructures are only partially, preferably not significantly, more preferably completely unaffected or damaged. It has further been found that preferred embodiments of the present invention provide flexible, transparent, electrically conductive single or multiple layers having high scratch resistance and excellent optical and electrical properties under mechanical stresses (e.g., bending, scratching, wiping). Complex.

This finding is particularly surprising for the single layer or multilayer composite of the present invention, wherein the first layer and the conductive transparent layer are the same, and wherein the concentration of the conductive nano-body in the first layer has a direction perpendicular to the interface of the layer. gradient.

Accordingly, the single layer or multilayer composite of the present invention preferably has one or more of the following optical and/or electrical properties, more preferably all of the following optical and/or electrical properties: - in each case When measured according to standard method ASTM D1003-13 (Procedure A), in each case in the visible region of the electromagnetic spectrum (ie, in the range of about 380 nm to 780 nm, and more specifically in the range of about 400 nm to 700 nm) 70% or higher, more preferably 75% or higher, still more preferably 80% or higher, even better 85% or higher, and even better 90% or higher; and when in each In one case, according to ASTM D1003-13 (Procedure A), a haze of 3% or less, more preferably 2% or less, more preferably 1.5% or less; - such as by a non-contact type thin layer A resistance measuring system (inductance measurement), preferably measured according to the standard procedure ASTM F1844-97 (2016), on the surface of the first layer of the single or multi-layer composite of 10 to 150 ohm/sq, A sheet resistance in the range of 10 to 60 ohm/sq.

The measurement of haze and light transmittance by means of a fog meter is defined as "Program A-Fogmeter" in ASTM D1003-13. The value of the given haze and light transmission (corresponding to the illuminance transmittance as defined in ASTM D1003-13) in the context of the present invention is referenced to this procedure.

In general, the parameter haze is an indicator of light diffusion. It refers to the percentage of light that is separated from incident light and scattered during transmission. Unlike "light transmittance (mainly the property of the medium)", "haze" is usually a production concern and is typically caused by surface roughness and embedded particles or compositional heterogeneity in the medium.

According to ASTM D1003-13, in light transmission, haze is the light scattering of the sample by causing a decrease in the contrast of the object observed through the sample, i.e., such that the direction is offset from the incident beam by a specified angle (2.5°). Percentage of transmitted light.

The sheet resistance (sometimes referred to as "sheet resistance") is a measure of the resistance of the thinner body (thin layer), that is, the thickness is uniform. The term "sheet resistance" implies that the current is along the plane of the thin layer and is not perpendicular thereto. For a thin layer having a thickness t, a length L and a width W, the resistance R is given by:

Where R _sh is a sheet resistance. Therefore, the sheet resistance R _{sh is} given by the following equation:

In the equation given above, the bulk resistance R is multiplied by the dimensionless amount (W/L) to obtain the sheet resistance R _sh , so the unit of the sheet resistance is "ohm (Ohm)". To avoid confusion with the bulk resistance R, the value of the sheet resistance is usually indicated as "ohm/square" (Ohm/sq.), because in the specific case of a square thin layer, the following relationship applies: W =L and R=Rsh.

The sheet resistance can be measured by means of a "four point probe" as known in the art. Instructions for use in a four point detector and instructions for performing the associated method are available, for example, from Four Point Probes/Bridge Technology, Chandler Heights AZ, 85127, USA. Preferably, the sheet resistance is measured by a four-point probe method for the purposes of the present invention according to standard procedure ASTM F1711-96 (2016).

However, the sheet resistance is preferably measured by non-contact sheet resistance measurement (also referred to as inductance measurement). In general, this method measures the shielding effect produced by the "eddy current". Due to Faraday's law of induction, eddy currents (also known as "Foucault currents") are current loops induced in a conductor by changing the magnetic field in the conductor. The eddy current flows in a closed loop within the conductor in a plane perpendicular to the magnetic field. It can be induced in adjacent fixed conductors by a time varying magnetic field generated by an alternating current electromagnet or transformer, for example, or by relative motion between the magnet and adjacent conductors. The magnitude of the current in a given loop is proportional to the strength of the magnetic field, the area of the loop, and the rate of change of the flow, and the resistivity of the material is inversely proportional. Thereby a high frequency magnetic field is generated and the sample is placed in the magnetic field. The electrically conductive material acts on a resonant circuit, such as a resistive load, and thus causes a change in power consumption in the oscillator circuit. In one version of this technology, a thin layer of conductive material to be tested is placed between two coils. This non-contact sheet resistance measurement method also allows for the characterization of an encapsulated film or a film having a rough surface. Suitable measuring systems are known and commercially available, for example from Suragus GmbH, Dresden, Germany or from KITEC Microelectronics GmbH, Erding, Germany. Preferably, the sheet resistance is measured by a non-contact sheet resistance measurement method for the purposes of the present invention according to standard procedure ASTM F1844-97 (2016).

Two methods for measuring the sheet resistance provided herein (four-point probe measurement and inductance measurement) are generally equivalent and sheet resistance measured by any of these methods The values are usually essentially the same and the sheet resistance values are within the measurement tolerance.

However, the inductive measurement method is preferred in the case where the conductive medium (for example, the conductive nano-body and/or the conductive transparent layer) is not directly or indirectly contactable, for example, because it is covered by an insulating medium. Therefore, the inductance measurement method is preferable for measuring the sheet resistance of the single layer or multilayer composite of the present invention.

Example:

The following examples are intended to further illustrate and illustrate the invention without limiting its scope.

All experiments and/or measurements as provided herein were performed under normal conditions (laboratory conditions: 20 ° C, 1013 mbar, equivalent to 1013 hPa), unless otherwise stated.

For measurement of transmittance and haze according to ASTM D1003-13 (Procedure A), a UV-Vis spectrometer "Haze-gard I" (by BYK-Gardner apparatus) was used.

For measuring sheet resistance, a non-contact sheet resistance measurement system is used.

Cross-sectional specimens of layers (e.g., single or multi-layer composites in accordance with the present invention) were prepared using a focused ion beam system (FIB, Helios Nanolab 450 F1).

For the surface and/or vertical morphology of the test specimen (for example, a single layer or multilayer composite according to the invention), a field emission scanning electron microscope (FE-SEM, Philips XL30 ESEM-FEG) was used.

Example 1: Preparation of a single layer or multilayer composite of the present invention

Depositing a plurality of Ag nanowires having a length in the range of about 15 to 30 μm (average length of about 25 μm) and a diameter in the range of about 20 to 40 nm (average diameter of about 30 nm) on the surface of a substrate composed of glass The substrate is pretreated by octadecyltrichloromethane (by dip coating the surface of the glass substrate into octadecyltrichloromethane, as is known in the art): - by means of knife coating Forming a wet film on the surface of the substrate by applying a suspension of the silver nanowire as a carrier liquid dispersed in isopropyl alcohol to the surface of the substrate, and - in air, at about 120 ° C At the temperature, the carrier liquid was removed from the wet film formed on the surface of the substrate by evaporation (drying) for about 10 minutes to produce a network of Ag nanowires.

Subsequently, the components of the coating composition "Binddemittel" and "Current" ("Harter") (which is equivalent and/or as in the patent EP 2225299 B1 (incorporated herein by reference) The "coating composition disclosed in "Herstellbeispiele" is similar), in detail, such as the coating composition shown in "Formulierung" (see paragraph [0092]). The composition of the "product" ("Produkt") is mixed with each other and applied to the dried Ag nanowire network using a scraping method, followed by air at a temperature of about 140 ° C in Agna The composition of the coating is cured or annealed on the rice noodle network for about 20 minutes. The thickness of the resulting clear coating can be manipulated by varying the blade height and/or blade speed and/or it can be manipulated by the volume of the coating composition fed into the drawdown device. The resulting clear coating had a thickness of about 5 [mu]m as determined by scanning electron microscopy (SEM).

The resulting coating is finally stripped of the substrate by manually gluing one edge of the coating and pulling it away from the substrate to obtain a conductive, flexible, transparent Ag nanowire electrode as a single layer composite in accordance with the present invention.

Example 2: Scratch test

A sample of the Ag nanowire electrode was prepared according to the method described in Example 1. A sample was manually scratched (with a scratch force in the range of about 1 to 5 N) on the surface of the composite layer coated with the coating composition using a plastic pen. The total number of scratches was 100. Recording (i) light transmittance value, (ii) haze value, and (iii) sheet resistance value of the sample before the first scratch (n = 0) and then after every 20 scratches (applicable method See above). The results of the scratch test are shown in Table 1 below:

The results from Example 2 show that the optical and electrical properties of the composite layer are not significantly affected after repeated scratching on the coated surface.

Example 3: Bending test

A sample of the Ag nanowire electrode was prepared according to the method described in Example 1. The sample is bent using a bending system in which the two ends of the sample anchored on the opposing plate are mounted so as to be movable toward and away from each other to apply bending tension to the sample. The bending radius was 3 mm and the number of bending cycles was 100 times. Record the (i) light transmittance value, (ii) haze value, and (iii) sheet resistance value of the sample before the first bend (n = 0) and then after every 20 bends (see above for applicable methods) Text). The results of the bending test are shown in Table 2 below:

The results from Example 3 show that the optical and electrical properties of the composite layer are not significantly affected after repeated bending of the composite layer.

Example 4: Wipe test

A sample of the Ag nanowire electrode was prepared according to the method described in Example 1. A wiping test was performed on the sample using a fabric immersed in isopropyl alcohol on the surface of the composite layer to which the coating composition had been applied. Record the (i) light transmittance value, (ii) haze value, and (iii) sheet resistance value of the sample before the first wipe (n = 0) and then after every 5 wipes (for the method of application, see Text). The results of the wipe test are shown in Table 3 below:

The results from Example 4 show that the optical and electrical properties of the composite layer are not significantly affected after repeated wiping on the coated surface.

Example 5: Effect of scratch on light characteristics

Two samples of a common PET substrate (film type, thickness about 125 μm) were provided, one of which was coated with a coating composition similar to that described in Example 1 (coating thickness of about 5 μm).

Two samples were then manually scraped using a plastic pen in similar situations (scratch force is about 1 to 5 N in each case). Next, for (i) visible scratching (using an optical microscope), (ii) light transmittance characteristics before and after scratching (see above for the method of measuring light transmittance) and (iii) haze characteristics before and after scratching (measuring fog See the method above for the method of detection.

As a result of these tests, the following was found: after the scratch test, the uncoated PET substrate clearly exhibited a plurality of scratches, while the PET substrate coated with the coating composition as defined above showed almost no display. Scratch.

After the scratch test, the uncoated PET substrate exhibited a significant reduction in light transmission (about 92% to about 90%), while the PET substrate coated with the coating composition as defined above exhibited only light transmittance. Extremely weak.

After the scratch test, the uncoated PET substrate exhibited a significant increase in haze (about 0.75% to about 2.0%), while the PET substrate coated with the coating composition as defined above showed only the extreme haze. Weak increase.

The results from Example 5 demonstrate that the coating composition as used in the present invention effectively protects a flexible, transparent surface (eg, a transparent substrate or a conductive transparent layer comprising a plurality of conductive nanostructures) from mechanical damage, In particular, it is protected from scratching while effectively retaining the light characteristics of the transparent surface.

Example 6: OLED lighting test

A flexible Ag nanowire electrode was prepared according to the method provided in Example 1 and applied as an anode to an organic light emitting diode ("OLED"): a thermal evaporator was used without air exposure (about 10 The base pressure of ^-6 Torr is equivalent to about 1,33×10 ^-4 Pa) 1,4,5,8,9,11-hexaza-linked triphenylhexacarbonitrile (HAT-CN), N, N '-Bis(naphthalen-1-yl)-N, N'-bis(phenyl)benzidine (NPB), ginseng (8-hydroxyquinoline) aluminum (Alq3), 8-hydroxy-hydroxyquinoline lithium (Liq , Al and MoO ₃ layers are sequentially deposited on the prepared flexible Ag nanowire electrode; the thickness of each layer is about 35 nm (HAT-CN), 40 nm (NPB), 50 nm (Alq3), 1.5 nm (Lig), respectively. 100 nm (Al) and 50 nm (MoO ₃ ). In this OLED structure, HAT-CN, NPB, Alq3, Liq, and Al are used as a hole injection layer, a hole transfer layer, a light-emitting layer, an electron injection layer, and a cathode, respectively. MoO _{3 is} used as a cap layer to prevent oxidation of the Al cathode.

The OLED thus obtained is bent in different directions and the brightness of the OLED illumination is visually detected during and after the bending.

It was found that OLED lighting exhibited no significant decrease in brightness during or after bending.

Claims (16)

A single or multi-layer composite comprising: i) a first layer comprising: a coating composition comprising: (a) at least one binder (A) having a reactive group, the binder ( A) is a hydroxyl-containing compound (A), (b) at least one crosslinking agent (B) capable of reacting with the reactive groups of the binding agent (A) by crosslinking, the crosslinking agent (B) a compound (B) having a free and/or blocked isocyanate group, and (c) at least one catalyst (C) for crosslinking a decyl group, the catalyst (C) being a phosphoric acid compound, more specifically phosphoric acid Or a phosphonic acid, the phosphate compound having pKb 3 and a bicyclic amine end cap having a boiling point > 100 ° C, wherein one or more of the components (A) and / or (B) and / or at least one additional component of the coating composition contains a hydrolyzable alkyl group, or it is cured a reaction product, and ii) a conductive transparent layer comprising a plurality of conductive nanostructures, wherein the first layer and the conductive transparent layer are the same or different.  The single layer or multilayer composite of claim 1, wherein the catalyst (C) is selected from the group consisting of substituted phosphoric acid monoesters and phosphodiesters, preferably selected from the group consisting of acyclic phosphodiesters and cyclic phosphates. Group of esters.   A single layer or multilayer composite according to any one of the preceding claims, wherein one or more of the coating compositions at least partially contain one or more of the same or different structural units of formula (I) - X-Si- R" _x G _3-x (I) wherein G is the same or different hydrolyzable group, more specifically G is an alkoxy group (OR'), X is an organic group, more specifically 1 to 20 The total number of carbon atoms is intended to be a straight chain and/or a branched chain extending alkyl or cycloalkyl, and preferably X is an alkyl group having a total number of 1 to 4 carbon atoms, and R" is an alkyl group, a cycloalkyl group, Aryl or aralkyl, which may be heteroatomized by non-adjacent oxygen, sulfur or NR _a groups, wherein R _a is alkyl, cycloalkyl, aryl or aralkyl, preferably R" is an alkane The base, more specifically, has a total number of 1 to 6 carbon atoms, and x is 0 to 2, preferably 0 to 1, and more preferably x is 0.  A single layer or multi-layer composite according to any one of the preceding claims, wherein the conductive nano-body is a metal nano-body, wherein the metal is preferably selected from the group consisting of cobalt, copper, gold. , iron, molybdenum, nickel, palladium, silver, tin, tungsten and alloys composed of two or more of these metals.   A single layer or multilayer composite according to any one of the preceding claims, wherein component (c) of the coating composition comprises at least one catalyst (C) for crosslinking a decyl group, the catalyst (C) being a phosphate compound selected from the group consisting of substituted phosphomonoesters and phosphodiesters, preferably selected from the group consisting of acyclic phosphodiesters and cyclic phosphodiesters having pKb 3 and a bicyclic amine terminated having a boiling point > 100 ° C, and the conductive nano-body is a metal nano-body, wherein the metal is preferably selected from the group consisting of cobalt, copper, gold, iron, molybdenum Nickel, palladium, silver, tin, tungsten and alloys composed of two or more of these metals.  A single layer or multilayer composite according to any one of the preceding claims, wherein the first layer is transparent and clear, preferably the first layer is in the form of a clear clear coating and/or - wherein Single or multi-layer composites are flexible.    A single layer or multilayer composite according to any one of the preceding claims further comprising one or more substrate layers.    A single layer or multilayer composite according to any one of the preceding claims, wherein the first layer and the conductive transparent layer are the same, and wherein - the concentration of the conductive nano-body in the first layer is perpendicular to the layer The interface has a gradient in the direction, or - the concentration of the conductive nano-body in the first layer is the same in all directions of the layer.    A single layer or multilayer composite according to any one of the preceding claims, wherein the first layer has a thickness perpendicular to the interface of the layer of no more than 30 μm, preferably in the range of 0.1 to 30 μm.    The single layer or multilayer composite of claim 1 to 7, wherein the first layer and the conductive transparent layer are different, and wherein the first layer and the conductive transparent layer are separated by one or more substrate layers Separated from each other.    A coated article comprising: - a base article, and - a coating on the base article, wherein the coating is a single layer or multiple layers according to any one of claims 1 to 10 Complex.   A method of producing a single-layer or multi-layer composite according to any one of claims 1 to 10, or a coated article according to claim 11 of the patent application, comprising the steps of: - providing or preparing a coating a layer composition comprising: (a) at least one binder (A) having a reactive group, the binder (A) being a hydroxyl group-containing compound (A), and (b) at least one crosslinking Agent (B) capable of reacting with the reactive groups of the binding agent (A) by cross-linking, the crosslinking agent (B) being a compound (B) having a free and/or blocked isocyanate group, And (c) at least one catalyst (C) for crosslinking a decyl group, the catalyst (C) being a phosphoric acid compound, more specifically phosphoric acid or phosphonic acid, having the pKb 3 and a bicyclic amine capping having a boiling point of >100 ° C, preferably a phosphoric acid compound selected from the group consisting of substituted phosphoric acid monoesters and phosphodiesters, the phosphoric acid compound having pKb 3 and a bicyclic amine end cap having a boiling point > 100 ° C, wherein one or more of the components (A) and / or (B) and / or at least one additional component of the coating composition contains a hydrolyzable alkyl group, - provided or prepared a mixture comprising a plurality of conductive nano-body, and - applying the coating composition and the mixture to a single surface of the substrate or at least two different surfaces after pre-mixing the coating composition with the mixture In a separate step or in a separate step where the coating composition is not premixed with the mixture.  The method of claim 12, wherein the coating composition and the mixture comprising the plurality of conductive nano-body are applied to at least one surface of the substrate in a separate step without pre-mixing, Wherein - in the first coating step, the mixture comprising a plurality of conductive nano-body is applied to the surface of the substrate, and - subsequently in the second coating step, the coating composition is applied to The mixture on the surface of the substrate or coated on the plurality of conductive nano-body on the surface of the substrate, such that a first conductive transparent layer comprising a plurality of conductive nano-body is produced on the substrate, Preferably, (aa) the first layer on the surface has a thickness of not more than 30 μm perpendicular to the interface of the layer, preferably in the range of 0.1 to 10 μm and/or (ba) in the first layer The concentration of the conductive nano-body has a gradient in a direction perpendicular to the interface of the layer.    The method of claim 13, wherein the first layer is subsequently stripped from the surface of the substrate, wherein the first layer is preferably a film and/or the peeling comprises stripping the surface from the surface of the substrate layer.   Use of a coating composition for the manufacture of a scratch-resistant, transparent and electrically conductive monolayer or multilayer composite comprising: (a) at least one binder (A) having reactive groups The binder (A) is a hydroxyl group-containing compound (A), and (b) at least one crosslinking agent (B) capable of reacting with the reactive groups of the binder (A) by crosslinking, which The crosslinking agent (B) is a compound (B) having a free and/or blocked isocyanate group, and (c) at least one catalyst (C) for crosslinking a decyl group, the catalyst (C) being a phosphoric acid compound, More specifically, phosphoric acid or phosphonic acid, which has pKb 3 and a bicyclic amine capping having a boiling point of >100 ° C, preferably a phosphoric acid compound selected from the group consisting of substituted phosphoric acid monoesters and phosphodiesters, the phosphoric acid compound having pKb 3 and a bicyclic amine end cap having a boiling point > 100 ° C, wherein one or more of the components (A) and / or (B) and / or at least one additional component of the coating composition contains a hydrolyzable alkyl group, or it is cured The reaction product.  The use of claim 15 wherein the single layer or multilayer composite comprises the single layer or a plurality of conductive nanobody of at least one of the plurality of layers.