Metal-polymer hybrid materials with high refractive index

Abstract

Disclosed are coatable compositions comprising a metal-(meth)acrylate hybrid material that, upon curing, forms a metal-polymer hybrid layer having a relatively high refractive index. The curable metal-(meth)acrylate hybrid composition comprises a photoinitiator, a polyoxometalate, and one of a hydroxyl-functional (meth)acrylate or a mixture of a hydroxyl-functional (meth)acrylate and an aromatic (meth)acrylate. The printable, solvent-free composition forms, upon coating, an optically transparent and metal-polymer hybrid layer having a refractive index of at least 1.52.

Description

Technical Field

[0001] This document discloses a coatable composition containing a metal-(meth)acrylate hybrid material and an article containing a relatively high refractive index layer, wherein the metal-(meth)acrylate hybrid material forms a metal-polymer hybrid layer with a relatively high refractive index upon curing. Background Technology

[0002] Optical devices are becoming increasingly complex and include more and more functional layers. As light passes through these layers, it can be altered in a wide variety of ways. For example, light can be reflected, refracted, or absorbed. In many cases, layers included in optical devices adversely affect optical properties for non-optical reasons. For instance, if the included support layer is not optically transparent, the absorption of light by the non-optical support layer can adversely affect the overall transmittance of the device.

[0003] A common challenge in multilayer optics is the refraction of light at the interface when layers with different refractive indices are adjacent to each other. In some devices, this refraction is desirable, but in others it is undesirable. Efforts have been made to minimize or eliminate this refraction at the interface between two layers to minimize the difference in refractive indices between the two layers forming the interface. However, with the use of a wider range of materials within optics, refractive index matching can become increasingly difficult. Organic polymer films and coatings commonly used in optics have a limited range of refractive indices. As higher refractive index materials are increasingly used in optical devices, it becomes increasingly difficult to prepare organic polymer compositions with suitable refractive indices while maintaining the desired characteristics of organic polymers, such as ease of processing and flexibility. Summary of the Invention

[0004] This document discloses a coatable composition comprising a metal-(meth)acrylate hybrid material that, upon curing, forms a metal-polymer hybrid layer with a relatively high refractive index. In some embodiments, the curable metal-(meth)acrylate hybrid composition comprises at least one aromatic (meth)acrylate, at least one hydroxyl-functionalized (meth)acrylate, a polyoxometalate, and a photoinitiator. The composition is solvent-free, printable at temperatures below 50°C, and, upon coating and curing, forms an optically transparent metal-polymer hybrid layer with a refractive index of at least 1.52.

[0005] In other embodiments, the curable metal-(meth)acrylate hybrid composition comprises at least one (meth)acrylate, a polyoxometalate, and a photoinitiator, wherein the (meth)acrylate comprises at least one hydroxyl group. The composition is solvent-free, printable at temperatures below 50°C, and forms an optically transparent metal-polymer hybrid layer with a refractive index of at least 1.52 after coating and curing.

[0006] This document also discloses articles of manufacture. In some embodiments, the articles of manufacture include: a substrate having a first primary surface and a second primary surface; and a metal-polymer hybrid layer adjacent to at least a portion of the second primary surface of the substrate. The metal-polymer hybrid layer comprises a layer prepared from a coatable and curable composition, wherein the coatable and curable composition comprises the aforementioned composition. In some embodiments, the coatable and curable composition comprises at least one (meth)acrylate, a polyoxometalate, and a photoinitiator, wherein the at least one (meth)acrylate comprises a (meth)acrylate having a hydroxyl group, or a mixture of (meth)acrylates containing at least one aromatic (meth)acrylate and at least one hydroxyl-functionalized (meth)acrylate. The layer has a thickness of 50 nanometers to 16 micrometers, is optically transparent, and has a refractive index of at least 1.52. Attached Figure Description

[0007] This application can be more fully understood by referring to the following detailed description of various embodiments of this disclosure in conjunction with the accompanying drawings.

[0008] Figure 1 This is a cross-sectional view of the optical article disclosed herein.

[0009] In the following description of the illustrated embodiments, reference is made to the accompanying drawings, in which various embodiments in which this disclosure may be practiced are shown by way of example. It should be understood that embodiments may be utilized and structural changes may be made without departing from the scope of this disclosure. The drawings are not necessarily drawn to scale. Similar numbers used in the drawings refer to similar parts. However, it should be understood that the use of numbers to refer to parts in a given drawing is not intended to limit parts labeled with the same numbers in another drawing. Detailed Implementation

[0010] The increasing complexity of optical devices makes it increasingly difficult to meet the requirements for the materials used in them. Specifically, organic polymer materials are widely used in optical devices, but the requirements for these polymer materials are becoming increasingly stringent.

[0011] For example, thin organic polymer films are desirable for a wide range of applications in optical devices, such as adhesives, protective layers, and spacers. As products become more complex, the physical requirements for these layers increase. For instance, as optical devices become smaller and typically include more layers, the need for thinner layers is growing. Simultaneously, the thinner layers also require greater precision. For example, to function as effective spacers, thin spacers (1 micrometer thick) need to be flat and free of gaps and pores to provide proper spacer functionality. This necessitates the deposition of organic layers in a precise and consistent manner.

[0012] Furthermore, these layers must not only provide their physical functions (adhesion, protection, spacing, etc.) but also the required optical properties. Among these properties, refractive index is becoming increasingly important. When light passes through the layers of a multilayer article, it encounters the interfaces between the layers. If the refractive indices of the layers are different, then the light can be refracted. Therefore, to minimize this refraction, matching the refractive indices of the layers within a multilayer article is desirable.

[0013] Because multiple layers within optical devices have a higher refractive index than typical organic polymer layers, considerable effort has been devoted to developing organic polymer layers with higher refractive indices. However, these organic polymer layers typically have drawbacks.

[0014] Various techniques for preparing polymer layers with high refractive indices using organic polymer layers have been described. Typically, these methods involve using high-refractive-index monomers, high-refractive-index additives, or a combination of these methods. Each of these methods has its advantages and disadvantages. Generally, high-refractive-index monomers suitable for preparing high-refractive-index polymers (such as aromatic monomers) are expensive and often have high viscosity, making it difficult to prepare coatable compositions with these monomers. Furthermore, using high-refractive-index additives such as metal oxide nanoparticles can increase viscosity, making it difficult to prepare coatable compositions, and can also reduce the flexibility of the layer and increase its brittleness, making it less suitable for use as a thin optical layer.

[0015] Techniques for fabricating polymer layers with high refractive indices include organometallic polymer materials, such as those described in U.S. Patent Publication 2015 / 0349295 (Boesch et al.). Boesch describes a device utilizing paired layers as a barrier coating, wherein the paired layers comprise a first layer (decoupling layer) of an organic-inorganic hybrid material and a second layer of an inorganic barrier layer. The organic-inorganic hybrid decoupling layer comprises an organic matrix having an organometallic polymer or inorganic nanoparticles, such that the inorganic material has an increased refractive index to better match the refractive index of the inorganic barrier layer.

[0016] The organometallic polymers used in Boesch's layers contain metal atoms that are bonded to or react with the organic polymer to form the organometallic polymer. Some of these polymers are prepared from monomers such as (meth)acrylate monomers having metal atoms bonded to them. An exemplary embodiment of Boesch's work uses monomer blends containing acrylate monomers chemically bonded to Zr atoms. This monomer blend is spin-coated, heated, and cured under ultraviolet light. Boesch's curable compositions typically have high viscosity.

[0017] This disclosure describes coatable compositions that are curable metal-(meth)acrylate hybrid compositions. These compositions are hybrids of POM (polyoxometalate) and (meth)acrylate. POM materials have a high refractive index, but as solid materials, their usefulness in curable compositions suffers from the same disadvantages as the aforementioned inorganic metal oxide particles. In the curable compositions of the present invention, POM is part of a metal-(meth)acrylate hybrid, meaning that the POM material is linked to and thus solubilized by the (meth)acrylate, making the POM-(meth)acrylate hybrid composition a fluid material. Therefore, unlike compositions containing particles such as metal oxide nanoparticles, the hybrid compositions of the present invention are fluids that can be coated and printed. In this way, many common problems associated with the use of nanoparticles in optical materials are avoided: agglomeration leading to increased haze and reduced transmittance; the need for surface treatment of nanoparticles to optimize compatibility with the surrounding polymer matrix; increased viscosity / hardness / brittleness; increased processing difficulty; and reduced flexibility.

[0018] POM-(meth)acrylate hybrid compositions not only overcome the aforementioned common problems, but also surprisingly demonstrate that even small amounts of hydroxyl-functionalized (meth)acrylates can solubilize other insoluble POM materials. Additional (meth)acrylate monomers, including aromatic (meth)acrylate monomers, can be added to further modify the properties of the composition; these additional (meth)acrylate monomers also tend to have higher refractive indices.

[0019] In some embodiments, the composition has two components: POM; and a hydroxy-functionalized (meth)acrylate. The hydroxy-functionalized (meth)acrylate may be an alkyl hydroxy-functionalized (meth)acrylate or it may also contain one or more aromatic groups. In other embodiments, the composition has three components: POM; a hydroxy-functionalized (meth)acrylate; and an aromatic (meth)acrylate. The composition also includes a photoinitiator for curing. The cured composition is optically transparent and has a refractive index of at least 1.52. The curable composition can be coated and cured to form a layer in an optical article.

[0020] Unless otherwise specified, all figures used in the specification and claims to express structural dimensions, quantities, and physical properties should in all cases be understood to be modified by the term "about". Therefore, unless stated to the contrary, the numerical parameters listed in the foregoing specification and appended claims are approximations, which may vary according to the desired properties sought by a person skilled in the art using the teachings disclosed herein. Numerical ranges expressed in terms of endpoints include all numbers contained within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5) and any range within that range.

[0021] Unless otherwise expressly stated, as used in this specification and the appended claims, the singular forms “a,” “an,” and “described” cover embodiments having multiple referents. For example, the reference to “a layer” covers embodiments having one layer, two layers, or more layers. Unless otherwise expressly stated, as used in this specification and the appended claims, the term “or” is generally used in a meaning that includes “and / or.”

[0022] The term "(meth)acrylate" refers to the monomeric acrylate or methacrylate of an alcohol. Acrylates and methacrylate monomers or oligomers are collectively referred to herein as "(meth)acrylate". Materials described as "(meth)acrylate functional" are materials containing one or more (meth)acrylate groups.

[0023] The terms "room temperature" and "ambient temperature" are used interchangeably, referring to temperatures in the range of 20°C to 25°C.

[0024] As used herein, the term "adjacent" in the context of two floors means that the two floors are adjacent to each other and there is no intervening opening space between them. They may be in direct contact with each other (e.g., stacked together) or there may be an intervening floor.

[0025] The term "polymer" as used in this article is consistent with its common chemical usage. A polymer is composed of many repeating subunits and is a material obtained by a polymerization reaction.

[0026] The term "alkyl" refers to a monovalent group that is an alkane group, where the alkane is a saturated hydrocarbon. Alkyl groups can be straight-chain, branched, cyclic, or combinations thereof, and typically have 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 ester.

[0027] The term "aryl" refers to a monovalent group that is aromatic and carbon-cyclic or has heteroatom ring substitutions. An aryl group may have one to five rings attached to or fused with an aromatic ring. Other ring structures may be aromatic, non-aromatic, or combinations thereof. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, anthryl, naphthyl, acenaphthenic, anthraquinone, phenanthryl, anthracenyl, pyrene, peryl, and fluorenyl. In some embodiments, the aromatic ring may contain one or more heteroatom ring substituents, such as nitrogen, oxygen, or sulfur. Examples of carbon-cyclic aromatic rings with heteroatom ring substitutions include pyridine, furan, and thiophene.

[0028] The term "alkanediol" refers to a divalent group that is a group of an alkane. Alkanediols can be straight-chain, branched, cyclic, or a combination thereof. Alkanediols typically have 1 to 20 carbon atoms. In some embodiments, alkanediols contain 1 to 18, 1 to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. The group center of the alkanediol can be on the same carbon atom (i.e., an alkylidene group) or on different carbon atoms.

[0029] The term "aromatic group" refers to a divalent group that is aromatic and carbon-cyclic or has heterocyclic rings substituted with heteroatoms. This group has one to five rings, either linked, fused, or a combination thereof. Other rings may be aromatic, non-aromatic, or a combination thereof. In some embodiments, the aromatic group has up to five rings, up to four rings, up to three rings, up to two rings, or one aromatic ring. For example, the aromatic group may be a phenylene group.

[0030] The term "heteroalkylene" refers to a divalent group comprising at least two alkylene groups linked by a thio, oxygen, or -NR- group, where R is an alkyl group. Heteroalkylene groups can be straight-chain, branched, cyclic, substituted with alkyl groups, or combinations thereof. Some heteroalkylene groups are polyoxyalkylenes, where the heteroatom is oxygen, such as, for example, -CH2CH2(OCH2CH2). n OCH2CH2-.

[0031] The term "aranediol" refers to the formula –R a -Ar a - a divalent group, wherein R a It is an alkylene group, and Ar a It is an arylene (i.e., an alkylene group bonded to an arylene).

[0032] The term "heteroarylene" refers to a divalent group that contains a heteroatom such as sulfur, oxygen, nitrogen, or a halogen such as fluorine, chlorine, bromine, or iodine.

[0033] Unless otherwise specified, the terms "optically transparent" and "visible light transmittance" are used interchangeably and refer to articles, films, or adhesives having high transmittance over at least a portion of the visible light spectrum (about 400 nm to about 700 nm). Typically, optically transparent articles have at least 90% visible light transmittance and less than 10% haze.

[0034] Unless otherwise specified, "optically transparent" means an adhesive or article that has high transmittance and exhibits low haze (typically less than about 5%, or even less than about 2%) over at least a portion of the visible light spectrum (about 400 nm to about 700 nm). In some embodiments, the optically transparent article exhibits haze of less than 1% or even 0.5% at a thickness of 50 micrometers. Typically, the optically transparent article has at least 95%, and typically higher, such as 97%, 98%, or even 99% or higher, of visible light transmittance.

[0035] This document discloses curable metal-(meth)acrylate hybrid compositions. These metal-(meth)acrylate hybrid compositions are coatable fluids. Typically, the curable compositions of this disclosure are “100% solids,” meaning they do not contain volatile solvents and all substances deposited on a surface remain on that surface, with no volatile substances lost from the coating. The terms “coatable composition” and “ink” are used interchangeably in this disclosure. In some embodiments, polyoxometalates (POMs) are neutralized with an alkali such as sodium hydroxide. In these embodiments, a small amount of water is typically added to solubilize the alkali.

[0036] The curable compositions disclosed herein can be used as inks, meaning they can be printed without solvents at temperatures ranging from room temperature to 50°C, or even from room temperature to 35°C, using, for example, inkjet printing technology. Typically, printable curable compositions have a viscosity of 30 centipoise or less at these temperatures.

[0037] Curable compositions are “substantially solvent-free” or “solvent-free.” As used herein, “substantially solvent-free” means that the curable ink composition contains less than 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, and 0.5 wt% of a nonpolymerizable (e.g., organic) solvent. The solvent concentration can be determined by known methods, such as gas chromatography (as described in ASTM D5403). The term “solvent-free” means, as the name suggests, that there is no solvent in the composition. It should be noted that whether a curable composition is substantially solvent-free or solvent-free, no solvent is intentionally added.

[0038] Curable compositions are printable and can therefore be described as inks. Curable compositions are not necessarily used as inks; that is, they are not necessarily printed and then cured. Curable compositions can be delivered to a substrate surface in a wide variety of ways, but they are printable. Specifically, the printable compositions of this disclosure are generally inkjet printable, meaning they have suitable viscosity and other properties for inkjet printing. The term "inkjet printable" is not a process description or limitation, but a material description, meaning that the curable composition can be inkjet printed, not that the composition must have been inkjet printed. This is similar to the expression "thermally melt processable," meaning that the composition can be thermally melt processable, but not that the composition has been thermally melt processable.

[0039] The curable composition comprises at least one polyoxometalate (POM) and a hydroxyl-functionalized (meth)acrylate as reactive components. The curable composition also comprises at least one photoinitiator to achieve curing of the curable composition. A wide range of formulations are disclosed herein. In some embodiments, the curable composition is referred to as a 2-component composition, meaning that it comprises POM and at least one hydroxyl-functionalized (meth)acrylate. In other embodiments, the curable composition is referred to as a 3-component composition, meaning that it comprises POM, at least one hydroxyl-functionalized (meth)acrylate, and at least one aromatic (meth)acrylate. A wide variety of hydroxyl-functionalized (meth)acrylates and aromatic (meth)acrylates are suitable, as described in more detail below.

[0040] The curable compositions disclosed herein contain polyoxometalate (POM) as a high refractive index additive. POM is a highly polar inorganic protic acid substance that is solid and generally incompatible and immiscible with high refractive index aromatic organic (meth)acrylates. It has been found that combinations of POM with hydroxyl-functionalized (meth)acrylates solubilize POM and provide fluid compositions. It has been further found that POM can be solubilized not only in its acidic form but also when neutralized with sodium hydroxide.

[0041] A wide range of polyoxometalates are suitable for preparing the coatable compositions of this disclosure. Polyoxometalates (abbreviated as POM) are polyatomic ions, typically anions, consisting of three or more transition metal oxyanions linked together by shared oxygen atoms to form a closed three-dimensional framework. Two broad categories have been recognized: homopolyoxometalates consisting of only one type of metal and oxide, and heteropolyoxometalates consisting of one metal, oxide, and main group oxygen-containing anions (phosphate, silicate, etc.).

[0042] Typically, the polyoxometalates disclosed herein include polyoxometalates of tungsten, molybdenum, vanadium, tantalum, or niobium. Particularly suitable polyoxometalates are tungsten or molybdenum polyoxometalates. A particularly suitable polyoxometalate includes silicotungstic acid.

[0043] As described above, the curable composition further comprises at least one hydroxyl-functionalized (meth)acrylate. Embodiments of curable compositions comprising POM, at least one hydroxyl-functionalized (meth)acrylate, and a photoinitiator are referred to herein as 2-component compositions.

[0044] A wide range of hydroxyl-functionalized (meth)acrylates are suitable. In some embodiments, the two-component composition comprises a single hydroxyl-functionalized (meth)acrylate, while in other embodiments, the hydroxyl-functionalized (meth)acrylate comprises a mixture of hydroxyl-functionalized (meth)acrylates.

[0045] Suitable hydroxy-functional (meth)acrylates include alkyl hydroxy-functional (meth)acrylates and hydroxy-functional (meth)acrylates having hydroxy-functional aromatic groups or groups containing aromatic and hydroxy groups.

[0046] Hydroxyl-functionalized (meth)acrylates include (meth)acrylates of general formula 2:

[0047] H2C = CHR 1 -(CO)-OR 3

[0048] Formula 2

[0049] Where R 1 It is a hydrogen atom or a methyl group; and R 3 It is a hydroxyl functional part that contains an alkyl subunit, a heteroalkyl subunit, an aryl subunit, a heteroaryl subunit, or a combination of groups.

[0050] In some embodiments, the hydroxy-functionalized (meth)acrylate of Formula 2 is a hydroxy-functionalized (meth)acrylate alkyl. An example of a hydroxy-functionalized (meth)acrylate alkyl is one in which R... 3 It contains -(CH2) a Those with -CH2OH groups, where a is an integer of 1 or greater. Examples include hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), hydroxybutyl acrylate, and polypropylene glycol (meth)acrylate.

[0051] In other embodiments, the hydroxy-functionalized (meth)acrylate comprises one or more hydroxyl groups and at least one aromatic group. Examples of hydroxy-functionalized (meth)acrylates having at least one aromatic group include (meth)acrylates of general formula 3:

[0052] H2C = CHR 1 -(CO)-O-Ar OH

[0053] Formula 3

[0054] Where R 1 It is a hydrogen atom or a methyl group; and Ar OH It is a hydroxyl-functionalized aromatic group or a group containing both an aromatic group and a hydroxyl group. In some embodiments, Ar OH Groups containing: -(CH2) a -(CH(OH))-(CH2) b -O-Ph group, wherein a is an integer of 1 or greater; b is an integer of 1 or greater; and Ph is a phenyl group or a substituted phenyl group.

[0055] As described above, embodiments of the 2-component curable composition may include a single hydroxyl-functional (meth)acrylate or a combination thereof that may include hydroxyl-functional (meth)acrylates. Adding an aromatic hydroxyl-functional (meth)acrylate can help increase the refractive index of the cured composition. Some particularly suitable 2-component curable compositions contain POM and an aromatic hydroxyl-functional (meth)acrylate.

[0056] This document also discloses a curable metal-(meth)acrylate three-component hybrid composition. The curable metal-(meth)acrylate hybrid composition comprises at least one aromatic (meth)acrylate, at least one hydroxyl-functionalized (meth)acrylate, a polyoxometalate, and a photoinitiator. Similar to the two-component curable compositions described above, the three-component composition is solvent-free, printable at temperatures below 50°C, and forms an optically transparent layer with a refractive index of at least 1.52 upon coating.

[0057] The POM component and the hydroxyl-functionalized (meth)acrylate component have been described above. The 3-component composition also contains at least one aromatic (meth)acrylate. A wide range of aromatic (meth)acrylates is suitable. At least one aromatic (meth)acrylate includes aromatic (meth)acrylates of general formula 1:

[0058] H2C = CHR 1 -(CO)-O-Ar

[0059] Formula 1

[0060] Where R 1 Ar is a hydrogen atom or a methyl group; and Ar is an aromatic group comprising a phenyl group, a substituted phenyl group, an arylene group, or a heteroarylene group. In some embodiments, Ar comprises an arylene or heteroarylene group containing: –(CH2) n -(C6R 2 4)-Z-(C6R 2 5) arylene or heteroarylene groups; where n is an integer of 1 or greater; each R 2Independently, it is a hydrogen atom or an alkyl group; Z is a single bond or an oxygen or sulfur atom. In other embodiments, Ar is a -(CH2-CH2)-T-(C6R) group. 2 4)-Z-(C6R 2 5) heteroarylene groups, wherein T is an oxygen or sulfur atom; each R 2 It can be a hydrogen atom or an alkyl group independently; and Z can be a single bond or an oxygen or sulfur atom.

[0061] The curable composition also contains at least one photoinitiator, meaning that the initiator is activated by light (typically ultraviolet (UV) light). Photoinitiators are well known to those skilled in the art of (meth)acrylate polymerization. Examples of suitable free radical photoinitiators include DAROCURE 4265, IRGACURE 184, IRGACURE 651, IRGACURE 1173, IRGACURE 819, LUCIRINTPO, and LUCIRIN TPO-L, which are commercially available from BASF, Charlotte, NC, North Carolina.

[0062] Generally speaking, the photoinitiator is used in amounts of 0.01 to 1 part by weight, more typically 0.1 to 0.5 parts by weight, relative to 100 parts by weight of total reactive components.

[0063] Curable compositions may contain additional reactive or non-reactive components, but such components are not essential and may impair the final properties of the resulting (meth)acrylate-based polymer. As mentioned above, curable ink compositions are substantially solvent-free or solvent-free.

[0064] This document also discloses articles, particularly multilayer articles. In some embodiments, the article includes: a substrate having a first main surface and a second main surface; and a cured metal-polymer hybrid layer adjacent to at least a portion of the second main surface. The cured metal-polymer hybrid layer comprises a layer prepared from a coatable and curable composition, wherein the coatable and curable composition comprises the aforementioned 2-component or 3-component curable composition. In some embodiments, the coatable and curable composition comprises at least one (meth)acrylate, a polyoxometalate, and a photoinitiator, wherein the at least one (meth)acrylate comprises a (meth)acrylate having a hydroxyl group, or a mixture of (meth)acrylates containing at least one aromatic (meth)acrylate and at least one hydroxyl-functionalized (meth)acrylate. The cured layer has a thickness of 50 nanometers to 16 micrometers, is optically transparent, and has a refractive index of at least 1.52.

[0065] In some embodiments, the article of manufacture further includes a device disposed on a second main surface of the substrate and adjacent to the metal-polymer hybrid layer. A wide variety of devices are suitable. In some embodiments, the device is an OLED (organic light-emitting diode), a quantum dot light-emitting diode, a micro-light-emitting diode, or a quantum nanorod electronic device.

[0066] Figure 1 Exemplary embodiments of the articles of manufacture disclosed herein are shown in the figure. Figure 1 An exemplary electronic device 100 is shown, comprising optical electronic components in the form of an OLED display. The OLED display 130 is hosted on an array of thin-film transistors (TFTs) 120 on an OLED mother glass substrate 110. A thin-film encapsulation (TFE) layer 140 comprises a cured composition according to the composition disclosed herein. Layer 140 is disposed on and encapsulates the OLED display 130. A touch sensor assembly (e.g., an on-cell touch assembly (OCTA)) 150 is disposed on the cured composition 140.

[0067] Example

[0068] These embodiments are for illustrative purposes only and are not intended to limit the scope of the appended claims. Unless otherwise specified, all parts, percentages, ratios, etc., in the embodiments and the remainder of the specification are by weight. The following abbreviations are used: mm = millimeter; nm = nanometer; mL = milliliter; g = gram; mg = milligram; s = second; min = minute; hr = hour; cps = centipoise. The terms "% by weight", "% by weight", and "wt%" are used interchangeably.

[0069] Table A: Material Description

[0070]

[0071]

[0072] Preparation of formulation

[0073] The formulation was prepared by mixing the components in a sealed glass vial at room temperature with a magnetic stir bar for 2 hours. The pH was measured using pH test strips (Ricca Chemical Company pH test strip 0-14, product number 8880-1).

[0074] Refractive index measurement

[0075] The refractive index was measured using a Milton Roy Company refractometer (model: 334610). The liquid sample was sealed between two prisms, and the refractive index was measured at 23°C using a sodium lamp at a 589 nm line.

[0076] Viscosity measurement

[0077] Rheological measurements were performed on an ARES G2 strain-controlled rheometer using a concave concentric cylindrical geometry (25 mm diameter and 32 mm length bob; 27 mm diameter cup) according to ASTM D7867-13 Test Method A. Measurements were collected at 25°C and 50°C under a nitrogen atmosphere. Measurements were taken over 10 s. -1 It was obtained at a shear rate of [value missing].

[0078] UV curing agents

[0079] The liquid formulation was UV-cured as follows: 1 wt% (based on polymer solids) of PI photoinitiator was added, coated onto a glass slide, and passed through a Light Hammer (LHC10 Mark 2) UV processor (Fusion UV Systems Inc., Gaithersburg, MD) using a "D-bulb," with the conveyor belt running three times at 50 feet per minute (15 meters per minute). Upon curing, a transparent solid coating was obtained.

[0080] Examples and Comparative Examples

[0081] As described in Table 1, the liquid formulations of the examples were prepared using POM (labeled E) or without POM (labeled C for comparison).

[0082] Table 1. Based on aromatic (meth)acrylates (PBA, OPPEA, BPMA, PTPBA) and hydroxy-(meth)acrylates Refractive index and viscosity of formulations containing (HEMA and HPPA) and POM (TAH, unless otherwise stated) .

[0083]

[0084] Examples with neutralized POM

[0085] As described in Table 2, the liquid formulations of the examples were prepared using neutralized POM (labeled E) or without neutralized POM (labeled C for comparison).

[0086] Table 2. Refractive index and pH of the formulation in which POM was neutralized with sodium hydroxide (6.7 mol excess relative to TAH). .

[0087]

Claims

1. A curable metal-(meth)acrylate hybrid composition comprising: At least one aromatic (meth)acrylate, said at least one aromatic (meth)acrylate comprising an aromatic (meth)acrylate of general formula 1: H2C=CHR 1 -(CO)-O-Ar Formula 1 Where R 1 It is a hydrogen atom or a methyl group; and Ar is an aromatic group containing a phenyl group, a substituted phenyl group, an arylene group, or a heteroarylene group; At least one hydroxyl-functionalized (meth)acrylate, said hydroxyl-functionalized (meth)acrylate comprising a (meth)acrylate of general formula 2: H2C=CHR 1 -(CO)-OR 3 Formula 2 Where R 1 It is a hydrogen atom or a methyl group; and R 3 It is a hydroxyl functional part that contains an alkyl subunit group, a heteroalkyl subunit group, an arylalkyl subunit group, or a combination of groups; Polyoxometalate, wherein the polyoxometalate is an anion of tungsten, molybdenum, vanadium, tantalum, or niobium; and A photoinitiator; wherein the composition is solvent-free, printable at temperatures below 50°C, and forms an optically transparent layer with a refractive index of at least 1.52 upon coating.

2. The curable metal-(meth)acrylate hybrid composition according to claim 1, wherein the polyoxometalate comprises a tungsten or molybdenum polyoxometalate.

3. The curable metal-(meth)acrylate hybrid composition according to claim 1, wherein the polyoxometalate comprises silicotungstic acid.

4. The curable metal-(meth)acrylate hybrid composition according to claim 1, wherein Ar comprises an aromatic or heteroaromatic group, said aromatic or heteroaromatic group comprising: Contains -(CH2) n -(C6R 2 4)-Z-(C6R 2 5) arylene or heteroarylene groups, Where n is an integer of 1 or greater; Each R 2 It can be independently a hydrogen atom or an alkyl group; Z is a single bond or an oxygen or sulfur atom; or Contains -(CH2-CH2)-T-(C6R) 2 4)-Z-(C6R 2 5) heteroarylene groups, Where T represents an oxygen or sulfur atom; Each R 2 Independently a hydrogen atom or an alkyl group; and Z represents a single bond or an oxygen or sulfur atom.

5. The curable metal-(meth)acrylate hybrid composition according to claim 1, wherein the hydroxyl functional portion comprises: Contains -(CH2) a -CH2OH group, Where a is an integer of 1 or greater; Contains -(CH2) a -(CH(OH))-(CH2) b -O-Ph group, Where a is an integer of 1 or greater; b is an integer of 1 or greater; and Ph represents a phenyl group or a substituted phenyl group.

6. A curable metal-(meth)acrylate hybrid composition comprising: At least one (meth)acrylate, wherein the (meth)acrylate comprises at least one hydroxyl group, and the (meth)acrylate comprising at least one hydroxyl group comprises an aromatic (meth)acrylate of general formula 3: H2C=CHR 1 -(CO)-O-Ar OH Formula 3 Where R 1 It is a hydrogen atom or a methyl group; and Ar OH It is a hydroxyl-functionalized aromatic group or a group containing both an aromatic group and a hydroxyl group; Polyoxometalate, wherein the polyoxometalate is an anion of tungsten, molybdenum, vanadium, tantalum, or niobium; and A photoinitiator; wherein the composition is solvent-free, printable at temperatures below 50°C, and forms an optically transparent layer with a refractive index of at least 1.52 upon coating.

7. The curable metal-(meth)acrylate hybrid composition according to claim 6, wherein the polyoxometalate comprises a tungsten or molybdenum polyoxometalate.

8. The curable metal-(meth)acrylate hybrid composition according to claim 6, wherein the polyoxometalate comprises silicotungstic acid.

9. The curable metal-(meth)acrylate hybrid composition according to claim 6, wherein the (meth)acrylate containing at least one hydroxyl group comprises a hydroxyl-functionalized alkyl (meth)acrylate.

10. The curable metal-(meth)acrylate hybrid composition according to claim 6, wherein the Ar OH Groups include: Contains -(CH2) a -(CH(OH))-(CH2) b -O-Ph group, Where a is an integer of 1 or greater; b is an integer of 1 or greater; and Ph represents a phenyl group or a substituted phenyl group.

11. An article comprising: A substrate having a first main surface and a second main surface; A metal-polymer hybrid layer, said metal-polymer hybrid layer being adjacent to at least a portion of the second main surface of said substrate, said metal-polymer hybrid layer comprising a layer prepared from a coatable and curable composition, said coatable and curable composition comprising: At least one (meth)acrylate, said at least one (meth)acrylate comprising: Hydroxyl-functional alkyl (meth)acrylates or (meth)acrylates of general formula 3 containing aromatic and hydroxyl groups: H2C=CHR 1 -(CO)-O-Ar OH Formula 3 Where R 1 It is a hydrogen atom or a methyl group; and Ar OH It contains -(CH2) a -(CH(OH))-(CH2) b -O-Ph group, Where a is an integer of 1 or greater; b is an integer of 1 or greater; and Ph is a phenyl group or a substituted phenyl group; or It contains the following mixture: At least one aromatic (meth)acrylate of general formula 1: H2C=CHR 1 -(CO)-O-Ar Formula 1 Where R 1 It is a hydrogen atom or a methyl group; and Ar is an aromatic group comprising a phenyl group, a substituted phenyl group, an arylene group, or a heteroarylene group, wherein the arylene or heteroarylene group comprises: Contains -(CH2) n -(C6R 2 4)-Z-(C6R 2 5) arylene or heteroarylene groups, Where n is an integer of 1 or greater; Each R 2 It can be independently a hydrogen atom or an alkyl group; Z is a single bond or an oxygen or sulfur atom; or Contains -(CH2-CH2)-T-(C6R) 2 4)-Z-(C6R 2 5) heteroarylene groups, Where T represents an oxygen or sulfur atom; Each R 2 Independently a hydrogen atom or an alkyl group; and Z is a single bond or an oxygen or sulfur atom; and Hydroxyl-functionalized (meth)acrylates of general formula 2: H2C=CHR 1 -(CO)-OR 3 Formula 2 Where R 1 It is a hydrogen atom or a methyl group; and R 3 The hydroxyl functional group contains: Contains -(CH2) a -CH2OH group, Where a is an integer of 1 or greater; Contains -(CH2) a -(CH(OH))-(CH2) b -O-Ph group, Where a is an integer of 1 or greater; b is an integer of 1 or greater; and Ph represents a phenyl group or a substituted phenyl group; Polyoxometalate, wherein the polyoxometalate is an anion of tungsten, molybdenum, vanadium, tantalum, or niobium; and A photoinitiator; wherein the layer has a thickness of 50 nanometers to 16 micrometers, the layer is optically transparent, and has a refractive index of at least 1.

52.

12. The article of claim 11, wherein the article of claim 11 further comprises a device disposed on the second main surface of the substrate and adjacent to the metal-polymer hybrid layer.

13. The article of claim 12, wherein the device comprises an OLED (organic light-emitting diode), a quantum dot light-emitting diode, a micro light-emitting diode, or a quantum nanorod electronic device.

Images