Metal-polymer hybrid materials with high refractive index

Abstract

The coatable metal-polymer hybrid composition comprises a polyoxometallate and a siloxane-based polyamine. Upon coating, the coatable composition forms a layer that is optically transparent and has a refractive index of 1.42 or higher. The amino groups of the polyoxometallate and the siloxane-based polyamine form crosslinks through acid-base interactions. The layer may also contain a fluid.

Description

Technology Field

[0001] A metal-polymer hybrid material having a relatively high refractive index and a coatable composition containing the metal-polymer hybrid material are disclosed in this specification. Background Technology

[0002] Increasingly, optical devices are becoming more complex and involve more functional layers. As light travels through the layers of an optical device, it can be altered by the layers in a wide variety of ways. For example, light can be reflected, refracted, or absorbed. In many cases, layers included in an optical device for non-optical reasons have an adverse effect on optical properties. For example, if a support layer that is not optically clear is included, the absorption of light by the non-optical support layer can have an adverse effect on the light transmittance of the entire device.

[0003] One common challenge with multilayer optical devices is that when layers with different refractive indices are adjacent to each other, light refraction can occur at their interfaces. In some devices, this light refraction is desirable, but in others, it is undesirable. To minimize or eliminate this light refraction at the interface between two layers, efforts have been made to minimize the difference in refractive index between the two layers forming the interface. However, as a wider range of materials are used in optical devices, matching refractive indices can become increasingly difficult. Organic polymer films and coatings frequently used in optical devices have a limited range of refractive indices. As materials with higher refractive indices are increasingly used in optical devices, it has become increasingly difficult to manufacture organic polymer compositions that possess a suitable refractive index while still retaining desirable characteristics of organic polymers, such as ease of processing and flexibility.

[0004] A metal-polymer hybrid material having a relatively high refractive index, a coatable composition containing the metal-polymer hybrid material, and an article that can be made of the metal-polymer hybrid material are disclosed in this specification.

[0005] In some embodiments, the metal-polymer hybrid composition comprises a polyoxometallate and a siloxane-based polyamine, and the composition is a coatable composition that forms a layer upon coating, the layer being optically transparent with a refractive index of 1.42 or higher. The amino groups of the polyoxometallate and the siloxane-based polyamine form crosslinks through acid-base interactions. In some embodiments, the composition further comprises a fluid.

[0006] In another embodiment, the metal-polymer hybrid composition comprises a polyoxometallate and a siloxane-based monoamine. The composition is a coatable composition that forms a layer upon coating, and the layer is optically transparent and has a refractive index of 1.42 or higher. The amino groups of the polyoxometallate and the siloxane-based monoamine form acid-base interactions.

[0007] Articles are also disclosed. In some embodiments, the article comprises a substrate having a first main surface and a second main surface, a metal-polymer hybrid layer adjacent to at least a portion of the second main surface of the substrate, and an inorganic barrier layer in contact with the metal-polymer hybrid layer. The metal-polymer hybrid layer comprises a layer prepared from a coatable composition, the coatable composition comprising a polyoxometallate and at least one siloxane-based polyamine. In some embodiments, the coatable composition further comprises a solvent, a fluid, or a combination thereof. The layer has a thickness of 50 nanometers to 16 micrometers, is optically transparent, and has a refractive index of 1.42 or higher.

[0008] A method for manufacturing an article is also disclosed. In some embodiments, the method comprises the steps of providing a substrate having a first main surface and a second main surface, providing a coatable composition, and disposing of the coatable composition on at least a portion of the second main surface of the substrate to form a layer; the layer has a thickness of 50 nanometers to 16 micrometers, is optically transparent, and has a refractive index of 1.42 or higher. The coatable composition comprises a polyoxometalate and at least one siloxane-based polyamine. In some embodiments, the coatable composition further comprises a solvent, a fluid, or a combination thereof. Brief explanation of the drawing

[0009] The present application can be more fully understood by considering the following detailed description of various embodiments of the present invention in conjunction with the accompanying drawings. FIG. 1 illustrates a cross-sectional view of one embodiment of an article of the present invention. FIG. 2 illustrates a cross-sectional view of a device of the present invention. In the following description of the exemplary embodiments, reference is made to the accompanying drawings, in which various embodiments in which the present invention may be practiced are illustrated as examples. It should be understood that such embodiments may be utilized and that structural changes may be made without departing from the scope of the present invention. The drawings are not necessarily drawn to a fixed scale. Identical reference numerals used in the drawings refer to identical components. However, it will be understood that the use of reference numerals to refer to components in a given drawing is not intended to limit those components in other drawings labeled with the same reference numeral. Specific details for implementing the invention

[0010] As optical devices become increasingly complex, meeting the requirements for the materials used in them is becoming increasingly difficult. In particular, while organic polymer materials are widely used in optical devices, the requirements for these polymer materials are becoming more stringent.

[0011] For example, thin organic polymer films are desirable for a wide range of applications in optical devices, such as as adhesives, protective layers, and spacer layers. As articles become more complex, the physical requirements for these layers have increased. For instance, as optical devices have become more compact and often contain more layers, the need for thinner layers has increased. At the same time, because these layers are thinner, they also need to be more precise. For instance, to be effective as a spacer, a thin spacer layer (1 micrometer thick) needs to be flat and free of gaps and holes to provide proper separation. This requires the organic layer to be deposited in a precise and consistent manner.

[0012] Additionally, these layers must not only provide their physical roles (adhesion, protection, separation, etc.), but also provide necessary optical properties. Among the properties that are becoming increasingly important is the refractive index. When light travels through the layers of a multilayer article, it comes into contact with the interfaces between the layers. If the refractive indices of the layers differ, the light may be refracted. Therefore, to minimize such refraction, it is desirable to match the refractive indices of the layers within the multilayer article.

[0013] Since many layers within optical devices have a higher refractive index than typical organic polymer layers, significant efforts have been made to develop organic polymer layers with higher refractive indices. However, these organic polymer layers often have disadvantages.

[0014] Numerous techniques have been described for preparing polymer layers with high refractive index using organic polymer layers. Typically, these methods have involved using high refractive index monomers, using high refractive index additives, or a combination of these methods. Each method has advantages and disadvantages. In general, high refractive index monomers suitable for preparing high refractive index polymers, such as aromatic monomers, are often expensive and frequently have high viscosity, making it difficult to prepare coatingable compositions containing these monomers. Additionally, the use of high refractive index additives, such as metal oxide nanoparticles, can increase viscosity, making it difficult to prepare coatingable compositions, and can also reduce the flexibility of the layer and increase its brittleness, making it less suitable as a thin optical layer.

[0015] Another problem regarding high-refractive-index organic polymer layers is that the fabrication of optical devices may involve high-energy processing steps, such as plasma etching processes. Organic polymer layers are susceptible to damage from plasma etching. Therefore, organic polymer layers have a number of disadvantages, and there remains a need for polymer layers that do not have these disadvantages.

[0016] Techniques used to produce polymer layers with high refractive index include organometallic polymer materials, for example, those described in U.S. Patent Application Publication No. 2015 / 0349295 (Boesch et al.). Boesch describes a device using a dyad as a barrier coating, wherein the dyad comprises a first layer (decoupling layer) which is an organic-inorganic hybrid material and a second layer which is an inorganic barrier layer. The organic-inorganic hybrid decoupling layer comprises an organic matrix having an organometallic polymer or inorganic nanoparticles, wherein the inorganic material increases the refractive index to better match the refractive index of the inorganic barrier layer.

[0017] The organometallic polymers used in the layers described by Boesch contain metal atoms that are bonded to or react with organic polymers to form organometallic polymers. Some of these polymers are prepared from monomers, such as (meth)acrylate monomers, to which metal atoms are bonded. An exemplary embodiment of Boesch uses a monomer blend comprising an acrylate monomer chemically bonded to a Zr atom. The monomer mixture was spin-coated, heated, and UV-cured.

[0018] The generally high viscosity of Boesch’s curable compositions and the fact that the coating needs to be heated and cured after coating can be disadvantageous for the formation of many layered articles, particularly those where pyrolytic or UV-degradable substrates may be used. Furthermore, heating and curing cause variations in the thickness of the coated layer, which can render these coatings unsuitable when a precise thickness is required. Additionally, the application of heat and radiation can adversely affect the optical properties of the layer. Therefore, it would be desirable to have a coatable composition capable of forming a thin polymer layer without requiring heating or curing.

[0019] In the present disclosure, a coatable composition is described that self-assembles into a cross-linked network without the need to cure the composition by the application of heat or radiation. In some embodiments, the coatable composition comprises a polyoxometallate and a siloxane-based polyamine that form a layer by forming cross-links through acid-base interactions upon coating. In some embodiments, the layer is a gel that further comprises a fluid. The layer is optically transparent and has a refractive index of 1.42 or higher. Articles comprising a layer prepared from the coatable composition, and methods for manufacturing such articles are also disclosed herein. A coatable composition comprising a polyoxometallate and a siloxane-based monoamine is also disclosed.

[0020] Unless otherwise indicated, all numerical values ​​expressing feature sizes, quantities, and physical properties used in this specification and claims should be understood as being modified by the term “approximately” in all cases. Accordingly, unless otherwise indicated, numerical parameters described in the above specification and appended claims are approximations that may vary depending on the desired properties to be obtained by a person skilled in the art using the teachings disclosed in this specification. References to numerical ranges by endpoint include all numbers included within the range (e.g., 1 through 5 include 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5) and any range within that range.

[0021] As used in this specification and the appended claims, the singular forms (“a,” “an,” and “the”) include embodiments having multiple references unless the content clearly indicates otherwise. For example, references to “layers” include embodiments having one, two, or more layers. As used in this specification and the appended claims, the term “or” is generally adopted to include “and / or” in its meaning unless the content clearly indicates otherwise.

[0022] As used herein, the term "adjacent" refers to two layers adjacent to each other. The adjacent layers may be in direct contact with each other, or an interposed layer may exist. There is no empty space between the adjacent layers.

[0023] As used herein, the term "coating possible" refers to a composition that can be coated onto a surface. Coating can be performed by a wide range of techniques well known in the art.

[0024] As used herein, the term "gel" refers to a composition comprising a cross-linked polymer matrix and a liquid or fluid.

[0025] The terms "room temperature" and "ambient temperature" are used interchangeably and have their ordinary meanings, namely referring to a temperature of 20 to 25°C.

[0026] The term "organic" as used herein to refer to a cured layer means that the layer is made from organic materials and is free of inorganic materials.

[0027] As used herein, the term “siloxane or siloxane-based” refers to a polymer containing units having dialkyl or diaryl siloxane (-SiR2O-) repeating units. Siloxane-based polymers may be segmented copolymers or polysiloxane polymers. The terms silicon and siloxane are used interchangeably.

[0028] As used herein, the term “hydrocarbon group” refers to any monovalent group containing mainly or solely carbon and hydrogen atoms. Alkyl and allyl groups are examples of hydrocarbon groups.

[0029] The term "alkyl" refers to a monovalent group that is a radical of an alkane, which is a saturated hydrocarbon. The alkyl group may be linear, branched, cyclic, or a combination thereof, and typically has 1 to 20 carbon atoms. In some embodiments, the alkyl group contains 1 to 18, 1 to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, and ethylhexyl.

[0030] The term "aryl" refers to a monovalent group that is aromatic and carbocyclic. The aryl may have one to five rings connected to or fused to an aromatic ring. Other ring structures may be aromatic, non-aromatic, or a combination thereof. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, anthryl, naphthyl, acenaphthyl, anthraquinonyl, phenanthryl, anthracenyl, pyrenyl, perylenyl, and fluorenyl.

[0031] The term "alkylene" refers to a divalent group that is a radical of an alkane. An alkylene can be straight-chain, branched, cyclic, or a combination thereof. An alkylene often has 1 to 20 carbon atoms. In some embodiments, an alkylene contains 1 to 18, 1 to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. The radical center of an alkylene may be on the same carbon atom (i.e., alkylidene) or on different carbon atoms.

[0032] The term "heteroalkylene" refers to a divalent group comprising at least two alkylene groups connected by thio, oxy, or -NR- (where R is alkyl). Heteroalkylenes may be linear, branched, cyclic, substituted with alkyl groups, or a combination thereof. Some heteroalkylenes are polyoxyalkylenes in which the heterovalence oxygen is, for example,

[0033] -CH2CH2(OCH2CH2) n OCH2CH2-is.

[0034] The terms "heteroaromatic" or "heteroaryl" are used interchangeably and refer to an aromatic ring containing at least one heteroatom within a ring structure as used herein.

[0035] The term "arylene" refers to a carbocyclic and aromatic divalent group. This group has one to five rings that are linked, fused, or a combination thereof. The other rings may be aromatic, non-aromatic, or a combination thereof. In some embodiments, the arylene group has up to 5 rings, up to 4 rings, up to 3 rings, up to 2 rings, or 1 aromatic ring. For example, the arylene group may be phenylene.

[0036] The term "heteroarylene" refers to a divalent group that is carbocyclic and aromatic and contains a heteroatom such as sulfur, oxygen, nitrogen, or a halogen, e.g., fluorine, chlorine, bromine, or iodine.

[0037] The term "aralkylene" has the chemical formula -R a -Ar a -'s 2 refers to the element, where, R a is an alkylene, and Ar a is an arylene (i.e., an alkylene is bonded to the arylene).

[0038] Unless otherwise indicated, “optically transparent” refers to a layer, film, or article having high light transmittance over at least part of the visible light spectrum (about 400 nm to about 700 nm). Typically, an optically transparent layer, film, or article has a light transmittance of 90% or more.

[0039] Unless otherwise indicated, “optically transparent” refers to a layer, film, or article having high light transmittance over at least part of the visible light spectrum (about 400 nm to about 700 nm) and exhibiting low turbidity. Typically, the optically transparent layer, film, or article has a visible light transmittance value of 90% or more, often 95% or more, and a turbidity value of 5% or less, often 2% or less.

[0040] A coatable metal-hybrid composition is disclosed herein, which spontaneously self-assembles upon coating to form a cross-linked matrix. In some embodiments, the metal-polymer hybrid composition comprises a polyoxometallate and a siloxane-based polyamine. The coatable composition forms a layer upon coating in which the amino groups of the polyoxometallate and the siloxane-based polyamine form cross-links through acid-base interactions. The layer is optically transparent and has a refractive index of 1.42 or higher.

[0041] Polyoxometallates are acid-functional compounds, and siloxane-based polyamines are clearly basic-functional compounds. When these two components are mixed, they form acid-base interactions, which, for the purposes of the present invention, include crosslinking. The acid-base interactions existing between the polymer components can be described as Brønsted acid-base type interactions. Brønsted acid-base interactions involve a proton (H + It involves the transfer of ions. In Brønsted acid-base interactions, the acidic component contains a transferable, ionizable terminal hydrogen atom, and the basic component contains an electron pair capable of accepting a proton ion. Brønsted acid-base reactions form interactions that are effectively ionic and are often described as ionic bonds.

[0042] A wide range of polyoxometalates is suitable for preparing the coatingable composition of the present invention. Polyoxometalates (abbreviated as POM) are polyatomic ions, usually anions, consisting of three or more transition metal oxyanions connected together by shared oxygen atoms to form a closed three-dimensional framework. Two broad series are recognized: isopolymetalates composed of only one type of metal and oxide, and heteropolymetalates composed of one metal, an oxide, and a main group oxyanion (phosphate, silicate, etc.).

[0043] Typically, the polyoxometallate of the present invention comprises a polyoxometallate of tungsten, molybdenum, vanadium, tantalum, or niobium. One particularly suitable polyoxometallate comprises tungstosilicic acid.

[0044] The coatingable composition also comprises a siloxane-based polyamine. In many embodiments, the siloxane-based polyamine comprises at least two amino groups, the amino groups being pendant groups, terminal groups, or a combination thereof.

[0045] A wide range of siloxane-based polyamines are suitable. Numerous amino-terminated polydimethylsiloxane materials are available for purchase. In some embodiments, these materials have the general structure shown in Chemical Formula I below:

[0046] [Chemical Formula I]

[0047] HR 1 NA-Si(CH3)2-O-[-Si(CH3)2-O-] n -Si (CH3)2-A-NHR 1

[0048] Here, R 1 is a hydrogen atom or an alkyl or aryl group, A is an alkylene linker, typically a propylene group, and n is an integer greater than 1. R 1 In this embodiment where the hydrogen atom is present, the amine is a primary amine, and R 1 In this embodiment, the amine is a secondary amine. Among the commercially available amino-terminated polydimethylsiloxane materials are various aminopropyl-terminated polydimethylsiloxanes under the trade names DMS-A11, DMS-A12, DMS-A15, DMS-A21, DMS-A31, DMS-A32, and DMS-A35 from Gelest, Morrisville, Pennsylvania, USA.

[0049] In another embodiment, the siloxane-based polyamine can be described as a (aminopropylmethylsiloxane)-dimethylsiloxane copolymer having the general structure shown in Formula II below:

[0050] [Chemical Formula II]

[0051] (CH3)3Si-O-[-Si(CH3)2-O-] m -[-Si(CH3)(CH2CH2CH2-NHR 1 )-O-] p -Si (CH3)3

[0052] Here, R 1 is a hydrogen atom or an alkyl or aryl group, m is an integer greater than or equal to 1, and p is an integer greater than or equal to 2. Among commercially available (aminopropylmethylsiloxane)-dimethylsiloxane copolymer materials are various (aminopropylmethylsiloxane)-dimethylsiloxane copolymers with the trade names AMS-132, AMS-152, AMS-191, AMS-1203, AMS-162, and AMS-163 from Gelest, Morrisville, Pennsylvania, USA.

[0053] The coatable composition of the present invention comprises at least one polyoxometallate compound and at least one siloxane-based polyamine, and may also comprise various other additional components if desired. One component that may be present is a solvent. The solvent is a fluid that serves as a carrier medium for the polyoxometallate and the siloxane-based polyamine and is compatible with these components. The solvent does not react with any component and does not permanently interact with them so as not to adversely affect the crosslinking interactions formed by the polyoxometallate and the siloxane-based polyamine. The solvent may interact with the polyoxometallate and / or the siloxane-based polyamine to prevent these components from interacting to form physical crosslinks until the solvent is removed. Since the solvent does not become part of the layer formed by the coatable composition, the solvent is removed after the coating is formed by contacting the coatable composition with a surface. The solvent may be removed by allowing it to evaporate, or evaporation may be accelerated by exposure to heat, for example, by placing the coating in an oven. The solvent in the present invention is distinguished from the fluid described below in that the solvent is merely a temporary component of the composition and is removed when the layer is formed, whereas the fluid described below is a permanent component of the composition and remains in the layer when the layer is formed.

[0054] Examples of suitable solvents include ethers, e.g., diethyl ether and tetrahydrofuran; esters, e.g., ethyl acetate; ketones, e.g., acetone and MEK (methyl ethyl ketone); alcohols, e.g., methanol, ethanol, and isopropanol; halogenated solvents, e.g., CHCl3 or CH2Cl2; aromatic solvents, e.g., benzene, toluene, and xylene; or mixtures thereof.

[0055] In some embodiments, the coatable composition further comprises a fluid. As previously mentioned, the solvent is merely a temporary component of the composition and is removed when the layer is formed, whereas the fluid described below is a permanent component of the composition and remains within the layer when the layer is formed; in this respect, the fluid in the present invention is distinguished from the solvent. A layer comprising a physically cross-linked matrix of a polyoxometallate and a siloxane-based polyamine and a fluid is referred to as a gel in the present invention. The layer of the gel composition is also optically transparent and has a refractive index of 1.42 or higher.

[0056] A wide range of fluids are suitable for the gel composition of the present invention. PDMS (polydimethylsiloxane) and polyalkylarylsiloxane fluids are particularly suitable fluids. Examples of suitable PDMS fluids include decamethylcyclopentasiloxane, available for purchase as 42412 from Alfa Aesar, Tewkesbury, Massachusetts, USA. Examples of suitable polyalkylarylsiloxane fluids include polyphenylmethylsiloxane, available for purchase as PMS-H03 from Gelest, Morrisville, Pennsylvania, USA.

[0057] Similar to the aforementioned coatingable composition, the gel composition may also include one or more solvents. The solvent may be removed when coating the coatingable composition to form a gel layer.

[0058] In some embodiments, the coatingable composition may be a solution. A solution is well understood in the art as a composition containing a solid component dissolved in a fluid medium. Since polyoxometalates and siloxane-based polyamines spontaneously form crosslinks through acid-base interactions, dissolving and dispersing these components in a solution can help prevent such crosslinks from forming until desired. The coatingable composition solution of the present invention comprises polyoxometalates and siloxane-based polyamines and further comprises at least one solvent. Suitable solvents are described above. In some embodiments, the coatingable composition solution also further comprises a fluid as described above. Particularly suitable fluids are PDMS and polyphenylmethylsiloxane fluids.

[0059] Metal-polymer hybrid compositions comprising a polyoxometallate and a siloxane-based monoamine are also disclosed herein. Similar to the compositions described above, the composition comprising a polyoxometallate and a siloxane-based monoamine is a coatable composition that forms a layer in which the amino groups of the polyoxometallate and the siloxane-based monoamine form acid-base interactions upon coating, and the layer is optically transparent and has a refractive index of 1.42 or higher. Since the siloxane-based amine is monofunctional, the layer comprising the layer is not a cross-linked composition and may remain in a liquid state in some embodiments.

[0060] As with the compositions described above, a wide range of polyoxometallates are suitable for preparing a coatingable composition. Typically, the polyoxometallates of the present invention comprise polyoxometallates of tungsten, molybdenum, vanadium, tantalum, or niobium. One particularly suitable polyoxometallate comprises tungstosilicic acid.

[0061] The coating composition also includes siloxane-based monoamines. A wide range of siloxane-based monoamines are suitable. Numerous mono-amino-functional polydimethylsiloxane materials are commercially available. In some embodiments, these materials have the general structure shown in Formula III below:

[0062] [Chemical Formula III]

[0063] R 1 HN-A-Si(CH3)2-O-[-Si(CH3)2-O-] q -Si (CH3)2-R 2

[0064] Here, A is an alkylene linker, typically a propylene group; q is an integer greater than 1; and R 1 is hydrogen or an alkyl or aryl group; R 2 is an alkyl group having 1 to 10 carbon atoms. R 1 In this embodiment where the hydrogen atom is present, the amine is a primary amine, and R 1 In this embodiment where the alkyl or aryl group is present, the amine is a secondary amine. Among commercially available mono-amino-functional polydimethylsiloxane materials is the formula III of the trade name MCR-A11 from Gelest, Morrisville, Pennsylvania, USA (wherein A is a propylene group, and R 1 There is an asymmetric aminopropyl-terminated polydimethylsiloxane described as a butyl group.

[0065] As with the aforementioned coatingable composition, the coatingable composition of polyoxometallate and siloxane-based monoamine may further comprise a solvent. Suitable solvents are discussed above. In some embodiments, the coatingable composition of polyoxometallate and siloxane-based monoamine is a solution, wherein the coatingable composition further comprises at least one solvent.

[0066] In some embodiments, the coating composition further comprises a siloxane-based polyamine. The siloxane-based polyamine is described in detail above.

[0067] Articles are also disclosed. In some embodiments, the article comprises a substrate having a first main surface and a second main surface, and a metal-polymer hybrid layer adjacent to at least a portion of the second main surface of the substrate. The metal-polymer hybrid layer comprises a layer prepared from a coatable composition, the coatable composition comprising a polyoxometallate and at least one siloxane-based polyamine. The siloxane-based polyamine is described in detail above. The layer has a thickness of 50 nanometers to 16 micrometers, is optically transparent, and has a refractive index of 1.42 or higher. In some embodiments, the article further comprises an inorganic barrier layer in contact with the metal-polymer hybrid layer.

[0068] A wide range of flexible and non-flexible substrates are suitable. For example, the substrate may be glass or a relatively thick layer of polymer material, such as PMMA (polymethyl methacrylate) or PC (polycarbonate). Alternatively, the substrate may be a flexible polymer film, such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), polyimide, PEEK (polyether ether ketone), etc.

[0069] The inorganic barrier layer in contact with the metal-polymer hybrid layer can be made from various materials including metals, metal oxides, metal nitrides, metal oxynitrides, metal carbides, metal oxyborides, and combinations thereof. A wide range of metals are suitable for use in metal oxides, metal nitrides, and metal oxynitrides, and particularly suitable metals include Al, Zr, Si, Zn, Sn, and Ti.

[0070] The refractive index of the inorganic barrier layer is not particularly limited, but is generally greater than 1.60, and in many embodiments, the refractive index of the inorganic barrier layer is greater than 1.70. One particularly suitable inorganic barrier layer material is silicon nitride.

[0071] An inorganic barrier layer can be deposited on a metal-polymer hybrid layer in various ways. Generally, any suitable deposition method may be used. Examples of suitable methods include vacuum processes, such as sputtering, chemical vapor deposition, metal-organic chemical vapor deposition, plasma-enhanced chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma-enhanced chemical vapor deposition, and combinations thereof.

[0072] In many embodiments, the substrate has an inorganic layer disposed on a second main surface. In these embodiments, the metal-polymer hybrid layer contacts the inorganic layer instead of contacting the substrate itself directly. The inorganic layer is similar to the aforementioned inorganic barrier layer and may actually be a barrier layer. The composition and properties of the inorganic layer are the same as those of the inorganic barrier layer. The inorganic layer and the inorganic barrier layer on the substrate may have the same material composition or may be different.

[0073] A coatable composition suitable for forming articles of the present invention is described in detail above. The coatable composition comprises a polyoxometalate and a siloxane-based polyamine. The coatable composition may further comprise a solvent, a fluid, or a combination thereof. The coatable composition is disposed on a substrate surface to form a metal-polymer hybrid layer. In some embodiments, the metal-polymer hybrid layer is a gel layer, wherein the layer further comprises a fluid. Examples of suitable fluids are described above, and PDMS or polyphenylmethylsiloxane fluids are particularly suitable.

[0074] In some embodiments, the article further comprises a device disposed on a second main surface of the substrate and adjacent to a metal-polymer hybrid layer. A wide range of devices is suitable. In some embodiments, the device comprises an OLED (organic light-emitting diode).

[0075] FIG. 1 illustrates an article (100) comprising a substrate (110) adjacent to a metal-polymer hybrid layer (120), and an inorganic barrier layer (130) in contact with the metal-polymer hybrid layer (120). FIG. 1 also comprises an optional inorganic layer (140) which is in contact with the substrate (110) and in contact with the metal-polymer hybrid layer (120). Each of these elements is described above.

[0076] FIG. 2 illustrates a device comprising a multilayer article of the present invention. FIG. 2 illustrates a device (200) comprising a substrate (210), wherein a device (250) is disposed on the substrate (210). As in FIG. 1, a metal-polymer hybrid layer (220) is adjacent to the substrate and the device (250), and an inorganic barrier layer (230) is in contact with the metal-polymer hybrid layer (220). FIG. 2 also includes an optional inorganic layer (240), which is in contact with the substrate (210) and the device (250) and is in contact with the metal-polymer hybrid layer (220). The optional layer (260) may be a single layer or multiple layers, may include both an organic layer and an inorganic layer, and may include an adhesive layer, an optical layer, etc. Layer (210) (substrate), layer (220) (metal-polymer hybrid layer), layer (230) (inorganic barrier layer), and layer (240) (optional inorganic layer) are the same as those described for FIG. 1.

[0077] The device (250) may include various devices, particularly optical devices where the use of an inorganic barrier layer is useful. Among the particularly suitable devices are OLED devices. OLED devices are well known in the art.

[0078] A method for manufacturing an article is also disclosed. In some embodiments, the method comprises the steps of providing a substrate having a first main surface and a second main surface, providing a coatable composition, and disposing of the coatable composition on at least a portion of the second main surface of the substrate to form a metal-polymer hybrid layer. The coatable composition comprises a polyoxometallate and at least one siloxane-based polyamine. The amino groups of the polyoxometallate and the siloxane-based monoamine form acid-base interactions upon the formation of the metal-polymer hybrid layer. The layer has a thickness of 50 nanometers to 16 micrometers, is optically transparent, and has a refractive index of 1.42 or higher.

[0079] The coating composition is described in detail above. As previously stated, the coating composition may further comprise a solvent, a fluid, or a combination thereof. In some embodiments, the metal-polymer hybrid layer comprises a gel layer, wherein the layer further comprises a fluid. Examples of suitable fluids are described above, and PDMS or polyphenylmethylsiloxane fluids are particularly suitable.

[0080] Generally, when a solvent is used in the coating composition, the present method further includes a drying step. In some embodiments, drying includes the application of heat, for example, by an oven.

[0081] The present invention includes the following embodiments.

[0082] Among the embodiments, there is a coatingable composition. Embodiment 1 is a metal-polymer hybrid composition comprising a polyoxometallate and a siloxane-based polyamine, wherein the composition is a coatingable composition in which, upon coating, the amino groups of the polyoxometallate and the siloxane-based polyamine form a crosslink through acid-base interactions to form a layer, and the layer is optically transparent and has a refractive index of 1.42 or higher.

[0083] Embodiment 2 is a composition of Embodiment 1 in which the siloxane-based polyamine comprises at least two amino groups, wherein the amino groups are pendant groups, terminal groups, or a combination thereof.

[0084] Embodiment 3 is a composition of Embodiment 1 or Embodiment 2, wherein the polyoxometallate comprises a polyoxometallate of tungsten, molybdenum, vanadium, tantalum, or niobium.

[0085] Embodiment 4 is a composition of Embodiment 1 or Embodiment 2 in which the polyoxometallate comprises tungsosilicate.

[0086] Embodiment 5 is a composition of any of Embodiments 1 to 4, comprising a gel composition in which the layer further comprises a fluid.

[0087] Embodiment 6 is the composition of Embodiment 5, wherein the fluid comprises PDMS (polydimethylsiloxane) fluid or polyphenylmethylsiloxane fluid.

[0088] Embodiment 7 is a composition of any of Embodiments 1 to 6, wherein the composition is a solution comprising at least one additional solvent.

[0089] Embodiment 8 is a composition of Embodiment 7 in which the solution further comprises a fluid.

[0090] Embodiment 9 is the composition of Embodiment 8, wherein the fluid comprises PDMS (polydimethylsiloxane) fluid or polyphenylmethylsiloxane fluid.

[0091] Embodiment 10 is a metal-polymer hybrid composition comprising a polyoxometallate and a siloxane-based monoamine, wherein the composition is a coatable composition in which, upon coating, the amino groups of the polyoxometallate and the siloxane-based monoamine form an acid-base interaction to form a layer, and the layer is optically transparent and has a refractive index of 1.42 or higher.

[0092] Embodiment 11 is a composition of Embodiment 10 in which the polyoxometallate comprises a polyoxometallate of tungsten, molybdenum, vanadium, tantalum, or niobium.

[0093] Embodiment 12 is the composition of Embodiment 10, in which the polyoxometallate comprises tungsosilicate.

[0094] Embodiment 13 is a composition of any of Embodiments 10 to 12, wherein the composition is a solution comprising at least one additional solvent.

[0095] Embodiment 14 is a composition of any of Embodiments 10 to 13, wherein the composition further comprises a siloxane-based polyamine.

[0096] An article is also disclosed. Embodiment 15 is an article comprising: a substrate having a first main surface and a second main surface; a metal-polymer hybrid layer adjacent to at least a portion of the second main surface of the substrate—the metal-polymer hybrid layer comprises a layer made from a coatable composition, wherein the coatable composition comprises a polyoxometallate; and at least one siloxane-based polyamine; wherein the layer has a thickness of 50 nanometers to 16 micrometers, is optically transparent, and has a refractive index of 1.42 or higher—; and an inorganic barrier layer in contact with the metal-polymer hybrid layer.

[0097] Embodiment 16 is an article of Embodiment 15, wherein the metal-polymer hybrid layer is in contact with the inorganic coating layer, and the substrate comprises an inorganic coating layer present on a second main surface.

[0098] Embodiment 17 is an article of Embodiment 15 or Embodiment 16, wherein the metal-polymer hybrid layer comprises a gel layer further comprising a fluid.

[0099] Embodiment 18 is an article of any of embodiments 15 to 17, wherein the coatingable composition further comprises at least one solvent.

[0100] Embodiment 19 is an article of any of embodiments 15 to 18, wherein the article is disposed on a second main surface of a substrate and further comprises a device adjacent to a metal-polymer hybrid layer.

[0101] Embodiment 20 is an article of Embodiment 19 in which the device includes an OLED (organic light-emitting diode).

[0102] A method for manufacturing an article is also disclosed. Embodiment 21 is a method for manufacturing an article, comprising the steps of: providing a substrate having a first main surface and a second main surface; providing a coatable composition comprising a polyoxometallate and at least one siloxane-based polyamine; and disposing of the coatable composition on at least a portion of the second main surface of the substrate to form a layer; wherein the layer has a thickness of 50 nanometers to 16 micrometers, the amide groups of the polyoxometallate and the siloxane-based polyamine form acid-base interactions, and the layer is optically transparent and has a refractive index of 1.42 or higher.

[0103] Embodiment 22 is the method of Embodiment 21, wherein the metal-polymer hybrid layer comprises a gel layer that further comprises a fluid.

[0104] Embodiment 23 is the method of Embodiment 22, wherein the fluid comprises PDMS (polydimethylsiloxane) or polyphenylmethylsiloxane fluid.

[0105] Embodiment 24 is a method of any of embodiments 21 to 23, wherein the coatingable composition further comprises at least one solvent.

[0106] Embodiment 25 is a method of any of embodiments 21 to 24, which further comprises a step of drying a layer.

[0107] Examples

[0108] A metal-polymer hybrid composition was prepared. The refractive index of the dried composition was measured. These examples are for illustrative purposes only and are not intended to limit the scope of the appended claims. Unless otherwise noted, all parts, percentages, ratios, etc. in the examples and the remainder of this specification are by weight. The following abbreviations are used herein: g = gram; °C = temperature; mol = mole; mol% = mole percentage; Mw = weight-average molecular weight; wt% = weight percentage; nm = nanometer.

[0109] ingredient

[0110]

[0111] Exemplary manufacturing method

[0112] (M1) Preparation of an amine-functionalized polysiloxane formulation supporting 12-tungsilicate (TAH), refer to the formulation in Table 1.

[0113] 12-tungsilicate hydrate (0.50 g) and tetrahydrofuran (1.00 g) were loaded into a small vial. Amine-functionalized polysiloxane (1.00 g) was added to this solution. A small stirring rod was added, and the solution was magnetically stirred at ambient temperature for 16 hours. During this period, the formulation transitioned from a high-viscosity liquid to a non-flowing gel at room temperature. The sample was deposited onto the surface of a glass slide and dried on a hot plate at 100°C for several hours.

[0114] (M1) Preparation of amine-functionalized polysiloxane formulations supporting 12-tungsilicate (TAH) and additional polysiloxane, refer to the formulations in Table 2.

[0115] 12-tungsilicate hydrate (0.50 g) and tetrahydrofuran (1.00 g) were loaded into a small vial. Amine-functionalized polysiloxane (1.00 g) and an equal amount of decamethylcyclopentasiloxane (1.00 g) were added to this solution. A small stirring rod was added, and the solution was magnetically stirred at ambient temperature for 16 hours. During this period, the formulation transitioned from a high-viscosity liquid to a non-flowing gel at room temperature. The sample was deposited onto the surface of a glass slide and dried on a hot plate at 100°C for several hours.

[0116] Determination of test methods / characteristics

[0117] For amino(NH2)-functionalized polysiloxanes, the substitution type, amine content, and molecular weight were obtained from the source (Gelest Silanes & Silicones Handbook, Gelest 5000-A, ISBN 978-0-578-12235-9). For monofunctional and difunctional polysiloxanes, the amino content is stated in weight%, whereas for polyfunctional polysiloxanes, the amino content is stated in mol%.

[0118] For the clear formulation, the refractive index was measured using a Milton Roy Company refractometer (model number: 334610). The sample was sealed between two prisms, and the refractive index was monitored until it no longer changed. The refractive index was measured at 23°C at the 589 nm line of a sodium lamp.

[0119] Examples

[0120] Exemplary two-component and three-component formulations as described in Tables 1 and 2 were prepared.

[0121] [Table 1]

[0122]

[0123] [Table 2]

[0124]

[0125] [Table 3]

[0126]

[0127] [Table 4]

[0128]

[0129] Adding 33 to 50 wt% of TAH to a low molecular weight amine polysiloxane (Mw < 5000) provides a transparent material with an increased refractive index (E2, E3, E4, E5), whereas adding 33 wt% of TAH to a higher molecular weight amine polysiloxane (5000 or more) provides an opaque material (CE5, CE6, E8).

[0130] Since monofunctional polysiloxanes cannot form a cross-linked network with polyfunctional TAH, adding TAH to a monofunctional amine polysiloxane liquid provides a liquid with an increased refractive index (E1).

[0131] Since difunctional or polyfunctional amine polysiloxanes can form a cross-linked network with polyfunctional TAH, adding TAH to a difunctional amine polysiloxane liquid (E2, E3, E4, E5, CE5, CE6) or to a polyfunctional amino polysiloxane liquid (E6, E7, E8, E9) provides a gel. When the MW of the polysiloxane is less than 5000, the gel is transparent (E2, E3, E4, E5).

[0132] A softer, swollen version of the above gel can be prepared by introducing an inert polysiloxane fluid (E10 to E17), for example, decamethylcyclopentasiloxane ("D5") (E10 to E13), or a higher refractive index fluid, for example, polyphenylmethylsiloxane (E14 to E17), into the formulation. These gels (E5 to E7) maintain an increased refractive index compared to their polysiloxane components (CE2, CE7, CE8, CE9).

Claims

Claim 1 A metal-polymer hybrid composition comprising a polyoxometallate; and a siloxane-based polyamine, wherein the siloxane-based polyamine is represented by Formula I or Formula II: [Formula I]HR 1 NA-Si(CH3)2-O-[-Si(CH3)2-O-] n -Si (CH3)2-A-NHR 1 Here, R 1 is a hydrogen atom or an alkyl or aryl group, A is an alkylene linking group having 1 to 3 carbon atoms, and n is an integer greater than 1; [Chemical Formula II](CH3)3Si-O-[-Si(CH3)2-O-] m -[-Si(CH3)(CH2CH2CH2-NHR 1 )-O-] p -Si (CH3)3 where, R 1 ... is a hydrogen atom or an alkyl or aryl group, m is an integer of 1 or more, and p is an integer of 2 or more; the metal-polymer hybrid composition is a coatingable composition that forms a layer in which the amino groups of a polyoxometallate and a siloxane-based polyamine form crosslinks through acid-base interactions upon coating, the layer is optically transparent and has a refractive index of 1.42 or higher, and the layer comprises a gel composition further comprising a fluid, wherein the fluid comprises a PDMS (polydimethylsiloxane) fluid or a polyphenylmethylsiloxane fluid. Claim 2 The metal-polymer hybrid composition according to claim 1, wherein the polyoxometallate comprises a polyoxometallate of tungsten, molybdenum, vanadium, tantalum, or niobium. Claim 3 A metal-polymer hybrid composition comprising a polyoxometallate; and a siloxane-based monoamine, wherein the siloxane-based monoamine is represented by Formula III: [Formula III]R 1 HN-A-Si(CH3)2-O-[-Si(CH3)2-O-] q -Si (CH3)2-R 2 Here, R 1 is hydrogen or an alkyl or aryl group; R 2 is an alkyl group having 1 to 10 carbon atoms; A is an alkylene linking group having 1 to 3 carbon atoms; and q is an integer greater than 1; the metal-polymer hybrid composition is a coatable composition in which, upon coating, the amino groups of the polyoxometallate and the siloxane-based monoamine form an acid-base interaction, the layer is optically transparent and has a refractive index of 1.42 or higher, and the layer comprises a gel composition further comprising a fluid, wherein the fluid comprises a PDMS (polydimethylsiloxane) fluid or a polyphenylmethylsiloxane fluid. Claim 4 In paragraph 3, the siloxane-based polyamine is further included, wherein the siloxane-based polyamine is represented by Formula I or Formula II: [Formula I]HR 1 NA-Si(CH3)2-O-[-Si(CH3)2-O-] n -Si (CH3)2-A-NHR 1 Here, R 1 is a hydrogen atom or an alkyl or aryl group, A is an alkylene linking group having 1 to 3 carbon atoms, and n is an integer greater than 1; [Chemical Formula II](CH3)3Si-O-[-Si(CH3)2-O-] m -[-Si(CH3)(CH2CH2CH2-NHR 1 )-O-] p -Si (CH3)3 where, R 1 A metal-polymer hybrid composition in which is a hydrogen atom or an alkyl or aryl group, m is an integer of 1 or more, and p is an integer of 2 or more. Claim 5 A substrate having a first main surface and a second main surface; a metal-polymer hybrid layer adjacent to at least a portion of the second main surface of the substrate; and an inorganic barrier layer in contact with the metal-polymer hybrid layer, wherein the metal-polymer hybrid layer comprises a layer prepared from a coatable composition, the coatable composition comprises a polyoxometallate; and at least one siloxane-based polyamine; wherein the siloxane-based polyamine is represented by Formula I or Formula II: [Formula I]HR 1 NA-Si(CH3)2-O-[-Si(CH3)2-O-] n -Si (CH3)2-A-NHR 1 Here, R 1 is a hydrogen atom or an alkyl or aryl group, A is an alkylene linking group having 1 to 3 carbon atoms, and n is an integer greater than 1; [Chemical Formula II](CH3)3Si-O-[-Si(CH3)2-O-] m -[-Si(CH3)(CH2CH2CH2-NHR 1 )-O-] p -Si (CH3)3 where, R 1 ...is a hydrogen atom or an alkyl or aryl group, m is an integer of 1 or more, and p is an integer of 2 or more; the layer has a thickness of 50 nanometers to 16 micrometers, is optically transparent, and has a refractive index of 1.42 or higher, and the layer comprises a gel composition further comprising a fluid, wherein the fluid comprises a PDMS (polydimethylsiloxane) fluid or a polyphenylmethylsiloxane fluid. Claim 6 A method for manufacturing an article comprises the steps of: providing a substrate having a first main surface and a second main surface; providing a coatable composition comprising a polyoxometallate and at least one siloxane-based polyamine; and disposing of the coatable composition on at least a portion of the second main surface of the substrate to form a layer; wherein the siloxane-based polyamine is represented by Formula I or Formula II: [Formula I]HR 1 NA-Si(CH3)2-O-[-Si(CH3)2-O-] n -Si (CH3)2-A-NHR 1 Here, R 1 is a hydrogen atom or an alkyl or aryl group, A is an alkylene linking group having 1 to 3 carbon atoms, and n is an integer greater than 1; [Chemical Formula II](CH3)3Si-O-[-Si(CH3)2-O-] m -[-Si(CH3)(CH2CH2CH2-NHR 1 )-O-] p -Si (CH3)3 where, R 1 A hydrogen atom or an alkyl or aryl group, where m is an integer greater than or equal to 1 and p is an integer greater than or equal to 2; the layer has a thickness of 50 nanometers to 16 micrometers, the amide groups of the polyoxometallate and the siloxane-based polyamine form a polymer matrix through acid-base interactions, and the layer is optically transparent and has a refractive index of 1.42 or higher, method. Claim 7 delete Claim 8 delete Claim 9 delete Claim 10 delete Claim 11 delete Claim 12 delete Claim 13 delete Claim 14 delete Claim 15 delete Claim 16 delete Claim 17 delete Claim 18 delete Claim 19 delete Claim 20 delete

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