Hyperbranched polymers for curable high refractive index compositions, articles thereof, and methods of making such articles

Abstract

Described herein is a curable composition derived from (i) a hyperbranched polymer comprising a plurality of first terminal carbon-carbon double bonds, where the hyperbranched polymer comprises the reaction product of (a) at least one unsaturated compound, a compound consisting of C, H and optionally an Si atom, an O atom, or Si and O atoms and having p second terminal carbon-carbon double bonds wherein each p is independently an integer greater than or equal to 2; (b) at least one organosilane compound consisting of C, H, Si and optionally O atoms and having q Si-H groups wherein each q is independently an integer greater than or equal to 2; and (c) at least one hydrosilylation reaction catalyst, wherein p / q is at least 2.1; and (ii) at least one multifunctional thiol comprising at least 2 thiol groups. These curable compositions when cured have a refractive index of at least 1.610 (when measured at 450 nm).

Description

Technical Field

[0001] This document discloses unsaturated hyperbranched polymers that are reacted in a thiol-olefin reaction to obtain compositions having high refractive indices. Curable compositions and articles thereof for use in, for example, optical devices are also disclosed. Summary of the Invention

[0002] In the display industry, a series of alternating organic and inorganic layers (called thin-film encapsulation, TFE) can be used on top of optical displays such as organic light-emitting devices (OLEDs) or quantum dot displays to protect the display underneath and enhance its performance and lifespan.

[0003] In thin-film encapsulation, the inorganic layer functions to prevent air and moisture from entering the underlying optical components. The organic layer serves a dual function: 1) to planarize the substrate and create a smooth interface for depositing the inorganic layer; and 2) to decouple any defects (pinholes, microcracks) that may occur in the inorganic layer on either side of the organic layer. The organic layer can be considered a buffer layer that is crucial for the successful barrier function of the inorganic layer.

[0004] The aim is to identify curable organic compositions with low viscosity that can be inkjet printed and produce organic layers with high refractive index.

[0005] In one aspect, a curable composition is described, the curable composition comprising: (i) a hyperbranched polymer comprising a plurality of first-terminal carbon-carbon double bonds, wherein the hyperbranched polymer comprises a reaction product of the following components: (a) At least one unsaturated compound consisting of C, H and optionally Si, O, or Si and O atoms and having p second-terminal carbon-carbon double bonds, wherein each p is an integer greater than or equal to 2 independently; (b) at least one organosilanes comprising C, H, Si and optionally O atoms and having q Si-H groups, wherein each q is an independent integer greater than or equal to 2; and (c) at least one hydrosilylation catalyst, wherein the p / q ratio is at least 2.1; and (ii) at least one polyfunctional thiol, the polyfunctional thiol comprising at least two thiol groups; and The curable compositions are essentially solvent-free.

[0006] In another aspect, an article of manufacture is disclosed. The article of manufacture includes a substrate having a first main surface and a second main surface; A cured organic layer, the cured organic layer being adjacent to at least a portion of the second main surface of the substrate, wherein the cured organic layer is derived from (i) a hyperbranched polymer comprising a plurality of first terminal carbon-carbon double bonds, wherein the hyperbranched polymer comprises a reaction product of the following components: (a) At least one unsaturated compound consisting of C, H and optionally Si, O, or Si and O atoms and having p second-terminal carbon-carbon double bonds, wherein each p is an integer greater than or equal to 2 independently; (b) at least one organosilanes comprising C, H, Si and optionally O atoms and having q Si-H groups, wherein each q is an independent integer greater than or equal to 2; and (c) at least one hydrosilylation catalyst, wherein the p / q ratio is at least 2.1; and (ii) at least one polyfunctional thiol, the polyfunctional thiol comprising at least two thiol groups; and An inorganic barrier layer is in contact with a cured organic layer, wherein the cured organic layer has a refractive index of at least 1.610 (measured at 450 nm).

[0007] In another aspect, a method for preparing an article of articles is described. This method includes: A substrate having a first main surface and a second main surface is provided; A curable composition is provided, the curable composition comprising: (i) a hyperbranched polymer comprising a plurality of first-terminal carbon-carbon double bonds, wherein the hyperbranched polymer comprises a reaction product of the following components: (a) At least one unsaturated compound consisting of C, H and optionally Si, O, or Si and O atoms and having p second-terminal carbon-carbon double bonds, wherein each p is an integer greater than or equal to 2 independently; (b) at least one organosilanes comprising C, H, Si and optionally O atoms and having q Si-H groups, wherein each q is an independent integer greater than or equal to 2; and (c) at least one hydrosilylation catalyst, wherein the p / q ratio is at least 2.1; and (ii) at least one polyfunctional thiol, the polyfunctional thiol comprising at least two thiol groups; A curable composition is disposed on at least a portion of the second primary surface of a substrate to form a curable layer; The curable layer is cured to form a cured organic layer, wherein the cured organic layer has a refractive index of at least 1.610 measured at 450 nm; and An inorganic barrier layer is deposited on a cured organic layer.

[0008] The above description is not intended to illustrate every embodiment. Details of one or more embodiments of the invention are also set forth in the following detailed description. Other features, objectives, and advantages will become apparent from this specification and the claims. Attached Figure Description

[0009] 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.

[0010] Figure 1 A cross-sectional view of an embodiment of the article of manufacture disclosed herein is shown.

[0011] Figure 2 A cross-sectional view of an embodiment of another article of the present disclosure is shown.

[0012] 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

[0013] As used in this article, terminology

[0014] “A,” “an,” and “the” are used interchangeably and refer to one or more; and

[0015] "And / or" is used to indicate that one or both of the stated situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0016] Furthermore, in this document, the ranges expressed by the endpoints include all numbers contained within that range (e.g., 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

[0017] Furthermore, in this document, the expression "at least one" includes all numbers that are one or greater than one (e.g., at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).

[0018] The terms “room temperature” and “ambient temperature” are used interchangeably and have their usual meanings, referring to a temperature between 20°C and 25°C.

[0019] As used herein, the term "adjacent" refers to two floors that are adjacent to each other. Adjacent floors may be in direct contact with each other, or there may be an intervening floor. There is no blank space between adjacent floors.

[0020] As used in this article, "containing at least one of A, B, and C" means containing only element A, containing only element B, containing only element C, containing both A and B, containing both A and C, containing both B and C, and combinations containing all three.

[0021] In this disclosure, it has been found that curable compositions comprising unsaturated hyperbranched polymers and polyfunctional thiols can produce curable compositions with high refractive indices and optionally high glass transition temperatures (Tg).

[0022] The curable compositions disclosed herein are substantially solvent-free and contain at least one polyfunctional thiol and a hyperbranched polymer containing a plurality of first-terminal C-C double bonds (or -olefins).

[0023] The hyperbranched polymers according to this disclosure can be prepared by hydrosilylation of carbon-carbon double bonds from unsaturated compounds with Si-H bonds from organosilanes, promoted by at least one hydrosilylation catalyst.

[0024] Useful unsaturated compounds consist of C, H, and optionally Si and / or O atoms, and may independently have p second-terminal carbon-carbon double bond groups. In some embodiments, useful unsaturated compounds have 4 to 50 carbon atoms (e.g., 4 to 50, 4 to 36, 4 to 18, or 4 to 12 carbon atoms), 0 to 10 silicon atoms (e.g., 0 to 10, 1 to 10, 0 to 6, 1 to 6, 2 to 10, 2 to 6, or 2 to 4 silicon atoms), and 0 to 9 oxygen atoms (e.g., 0 to 9, 0 to 6, 0 to 4, 0 to 2, or 0 to 1 oxygen atom). If Si is present, it is preferable not to have a Si-H functional group, as it can induce a self-reaction. If O is present, it is preferably present in an ether bond (i.e., COC). Each p is independently an integer greater than or equal to 2 (e.g., 3, 4, 5, 6, 7, or 8). In some embodiments, the useful unsaturated compound consists of C and H atoms. In some embodiments, the useful unsaturated compound consists of C, H, and Si atoms. In some embodiments, the useful unsaturated compound consists of C, H, and O atoms. In some embodiments, the useful unsaturated compound consists of C, H, Si, and O atoms. In some embodiments, the useful unsaturated compound contains aromatic carbon atoms, while in other embodiments, they do not contain aromatic carbon atoms.

[0025] In some implementations, the useful unsaturated compound contains at least one silicon atom, such as that represented by the following formula: Si(OSiR 2 2CH=CH2) b (R 2 CH=CH2) c (R 1 ) d Each R 2 An alkylene group that is independently a direct bond (i.e., a covalent bond) or has 1 to 12 carbon atoms and optionally contains at least one ether bond. Examples include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-1,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl, hexane-1,6-diyl, octane-1,8-diyl, decane-1,10-diyl, dodecane-1,12-diyl, 1,4-phenylene, and 1,8-biphenylene.

[0026] Each R 1 Independently, it is a hydrocarbon group having 1 to 12 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, phenyl, biphenyl, and alkyl-substituted phenyl), and optionally containing at least one ether bond. In some embodiments, R 1 It contains an optionally substituted phenyl group (e.g., phenyl, biphenyl, tolyl, xylyl, methoxyphenyl).

[0027] b is an integer from 0 to 4 (i.e., 0, 1, 2, 3 or 4), c is an integer from 0 to 4 (i.e., 0, 1, 2, 3 or 4), and d is an integer from 0 to 2 (i.e., 0, 1 or 2), provided that b+c≥2 (in some implementations, b+c≥3) and b+c+d=4.

[0028] Exemplary unsaturated silicon-containing compounds include: 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane; 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane; 1,4-bis(vinyldimethylsilyl)benzene; 1,5-divinyl-3-phenylpentamethyltrisiloxane; 1,3-divinyl-1,1,3,3-tetramethyldisiloxane; 1,4-divinyl-1,1,4,4-tetramethyl-1,4-disilbutane; divinyldimethylsilane; 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane; 1,3-divinyltetra(trimethylsiloxy)disiloxane; 1,5-divinylhexamethyltrisiloxane; bis(divinyl)-terminated Polydimethylsiloxane; 1,3-divinyltetraethoxydisiloxane; 1,3-divinyl-1,3-dimethyl-1,3-dimethoxydisiloxane; trivinylmethoxysilane; 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane; 1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane; 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane; 1,1,3,3-tetravinyldimethyldisiloxane; tetravinylsilane; tetraallylsilane; 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclopentasiloxane; hexavinyldisiloxane; and 1,3,5,7,9,11-hexavinylhexamethylcyclohexylsiloxane. The aforementioned vinyl compounds are available from commercial suppliers such as, for example, Gelest, Inc., Morrisville, and Pennsylvania, and / or can be synthesized by known methods. Tetravinylsilane, tetraallylsilane, and 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane are preferred in some embodiments.

[0029] In some embodiments, the useful unsaturated compound does not contain silicon, but is a hydrocarbon composed of C and H atoms. The hydrocarbon can be aromatic or aliphatic. The hydrocarbon can be cyclic, straight-chain, or branched in nature. The hydrocarbon preferably has at least 3, 4, 6, or even more vinyl or allyl groups. Such exemplary unsaturated compounds include trivinylcyclohexane.

[0030] The useful organosilane compound reacting with the above-mentioned unsaturated compounds may independently have q Si-H groups and consist of C, H, Si, and optionally O atoms. In some embodiments, the useful organosilane compound has 4 to 50 carbon atoms (e.g., 4 to 50, 4 to 36, 4 to 18, or 4 to 12 carbon atoms), 2 to 10 silicon atoms (e.g., 2 to 10, 2 to 6, or 2 to 4 silicon atoms), and 0 to 9 oxygen atoms (e.g., 0 to 9, 0 to 6, 0 to 4, 0 to 2, or 0 to 1 oxygen atom). If O is present, Z is preferably a single oxygen atom or oxygen is present in the ether bond, as shown in the equation below. Each q is independently an integer greater than or equal to 2 (e.g., 3, 4, 5, 6, 7, or 8). In some embodiments, the useful organosilane compound consists of C, H, and Si atoms. In some embodiments, the useful organosilane compounds contain aromatic carbon atoms, while in other embodiments they do not contain aromatic carbon atoms.

[0031] In some implementations, useful organosilane compounds are independently represented by the following formula: Z(SiR 1 2H) a Each Z is an α-valent group independently composed of Si and O, or Z is an α-valent group composed of C, H and optional O.

[0032] Each Z independently has 1 to 12 carbon atoms. For example, Z can be a carbon atom (tetravalent), an oxygen atom (divalent), a methylene group (divalent), an ethyl-1,2-diyl group (divalent), a propionic-1,3-diyl group (divalent), or a CH3CH3(CH2-)3 group (trivalent). In some embodiments, Z is a phenylene group.

[0033] Each R 1 Independently as previously defined above.

[0034] a is an integer from 2 to 8 (i.e., 2, 3, 4, 5, 6, 7 or 8).

[0035] Exemplary organosilane compounds include: 1,1,4,4-tetramethyl-1,4-disilbutane; 1,4-bis(dimethylsilyl)benzene; 1,2-bis(dimethylsilyl)benzene; tris(dimethylsiloxy)phenylsilane; 1,1,3,3-tetramethyldisiloxane; 1,3-disilpropane; bis[(p-dimethylsilyl)phenyl] ether; 1,3,5,7,9-pentamethylcyclopentasiloxane; 1,1,3,3,5,5 - Hexamethyltrisiloxane; 1,3,5,7-tetramethylcyclotetrasiloxane; 1,3-diphenyltetra(dimethylsiloxy)disiloxane; tris(dimethylsiloxy)ethoxysilane; methyltris(dimethylsiloxy)silane; 1,1,1,3,3,5,5-heptamethyltrisiloxane; 1,1,3,3-tetraisopropyldisiloxane; 4,4'-bis(dimethylsilyl)biphenyl; and tetra(dimethylsiloxy)silane. The aforementioned compounds containing Si-H groups are available from commercial suppliers such as, for example, Gallester, and / or can be synthesized by known methods. In some embodiments, 1,1,4,4-tetramethyl-1,4-disilbutane, 1,4-bis(dimethylsilyl)benzene, bis[(p-dimethylsilyl)phenyl] ether, and tetra(dimethylsiloxy)silane are preferred.

[0036] Hydrosilylation (also known as catalytic hydrosilylation) describes the addition of Si-H bonds to unsaturated bonds. When hydrosilylation is used to synthesize hyperbranched polymers according to this disclosure, carbon-carbon double bonds on an unsaturated compound react with Si-H groups on an organosilane compound. The stoichiometry of the reactants is adjusted such that there is at least a 2.1 equivalence excess of carbon-carbon double bonds relative to the Si-H groups; that is, the p / q ratio is at least 2.1. This ensures that the hyperbranched polymer will have side-chain carbon-carbon double bonds and helps to limit unwanted crosslinking of the polymer during its synthesis. In some embodiments, the p / q ratio is at least 2.1, 2.5, 3, 3.1, 3.5, 4, 4.5, or even at least 5.

[0037] Hydrosilylation reactions are typically catalyzed by platinum catalysts and usually involve the application of heat to achieve the reaction. In this reaction known in the art, Si-H undergoes addition to the double bond to form new CH and Si-C bonds.

[0038] Useful hydrosilylation catalysts can include thermal catalysts and / or photocatalysts. Exemplary thermal catalysts include platinum and rhodium complexes, such as H2PtCl6 (Speier catalyst); organometallic platinum complexes, such as coordination complexes of platinum and divinyldisiloxane (Karstedt catalyst); and tris(triphenylphosphine)rhodium(I) chloride (Wilkinson catalyst).

[0039] Useful platinum photocatalysts are disclosed, for example, in U.S. Patent No. 7,192,795 (Boardman et al.) and the references cited therein. Exemplary platinum photocatalysts are selected from the group consisting of: Pt(II) β-diketone complexes (such as those disclosed in U.S. Patent No. 5,145,886 (Oxman et al.), (η5-cyclopentadienyl)tris(σ-aliphatic)platinum complexes (such as those disclosed in U.S. Patent No. 4,916,169 (Boardman et al.) and U.S. Patent No. 4,510,094 (Drahnak), and C 7-20 -Aryl-substituted (η5-cyclopentadienyl)tri(ó-aliphatic)platinum complexes (such as the complexes disclosed in U.S. Patent No. 6,150,546 (Butts)). Hydrosilylation photocatalysts are activated, for example, by exposure to photochemical radiation (typically ultraviolet light) according to known methods.

[0040] The amount of hydrosilylation catalyst can be any effective amount. In some embodiments, the amount of hydrosilylation catalyst is about 0.5 to about 30 parts of platinum per million parts of the total weight of Si-H and carbon-carbon double bond groups, but more or less can also be used.

[0041] To prepare hyperbranched polymers, unsaturated compounds and organosilane compounds are combined with a hydrosilylation catalyst under conditions that allow hydrosilylation to occur. In some cases, mixing alone is sufficient. In others, heating and / or irradiation with ultraviolet light may be helpful.

[0042] In some embodiments, the hyperbranched polymer according to this disclosure has a molecular weight of at least 1000 g / mol, 1500 g / mol, or even 2000 g / mol. In some embodiments, the hyperbranched polymer according to this disclosure has a molecular weight of up to 5000 g / mol, 4000 g / mol, 3500 g / mol, or even 3000 g / mol.

[0043] The hyperbranched polymers disclosed herein contain multiple terminal unsaturated sites, wherein the unsaturated sites are C-C double bonds (-enes). The hyperbranched polymers disclosed herein contain at least two terminal unsaturated sites, more preferably at least three or even at least four terminal unsaturated sites. Typically, the hyperbranched polymers disclosed herein contain no more than 10, 15, or even 20 terminal unsaturated sites.

[0044] The hyperbranched polymer according to this disclosure can be used, for example, to prepare curable compositions. The curable compositions comprise the hyperbranched polymer and a polyfunctional thiol.

[0045] The polyfunctional thiols of this disclosure comprise at least two thiol (i.e., -SH) groups, although they may have more than two thiol groups, such as three, four, or even five thiol groups. The polyfunctional thiols of this disclosure may comprise aromatic or non-aromatic thiols. In some embodiments, the polyfunctional thiols are liquid under ambient conditions, in other words, at room temperature and 1 atmosphere. In some embodiments, the polyfunctional thiols of this disclosure have a melting point onset temperature at ambient pressure (e.g., 760 mm Hg) below 80°C, 70°C, 60°C, 50°C, 40°C, or even 30°C.

[0046] In some embodiments, the polyfunctional thiol is a non-aromatic thiol having a liquid refractive index of at least 1.620, 1.625, 1.630, 1.635, 1.640, 1.650, 1.655, or even 1.660, as measured by a white light refractometer. Typically, the refractive index of non-aromatic polyfunctional thiols does not exceed 1.71 or even 1.70. Exemplary non-aromatic polyfunctional thiols having a refractive index of at least 1.620 include: 2,3-bis-2-mercaptoethylthio-1-propanethiol, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane. Other non-aromatic polyfunctional thiols include: poly(ethylene glycol) dithiol; 1,2,3-trimercaptopropane; 2,3-bis-2-mercaptoethylthio-1-propanethiol; 1,2-ethanedithiol; 2,2'-thiodiethanedithiol; di(mercaptoethyl) sulfide; 2,5-bis(mercaptomethyl)-1,4-disulfide cyclopentane; tetra(ethylene glycol) dithiol; 2,2'-(ethylenedioxy)diethanedithiol; pentaerythritol tetra(3-mercaptopropionate); trimethylolpropane tri(3-mercaptopropionate). as well as .

[0047] Most (if not all) of the latter type of non-aromatic polyfunctional thiols have a liquid refractive index of less than 1.620. However, these non-aromatic polyfunctional thiols, in addition to those with a refractive index of at least 1.620, and / or in addition to aromatic polyfunctional thiols, can be used to improve the solubility of the components in the curable composition. However, care should be taken to minimize the amount of these lower refractive index materials in order to maintain a high refractive index in the finished product.

[0048] In some embodiments, the polyfunctional thiol is an aromatic thiol. Aromatic thiols can have a high refractive index, thereby contributing to the production of cured compositions with a high refractive index. Exemplary aromatic polyfunctional thiols include: 1,3-benzenedithiol; toluene dithiol; 1,3-benzenedimethylthiol; 1,3,4-thiadiazole-2,5-dithiol; (1,2,4)thiadiazole-3,5-dithiol; 1,3,5-trimercaptobenzene; 2-thiazoline-2-thiol; 1,1',4',1”-terphenyl-4-thiol; 5-bromopyridine-2-thiol; biphenyl-4-thiol; 1,7-naphthalenedithiol; and 1,5-naphthalenedithiol.

[0049] In some embodiments, a low molecular weight unsaturated compound comprising at least two or more terminal unsaturated groups is added to the curable composition. Such low molecular weight compounds comprise at least two, three, four, or even five terminal unsaturated groups. The terminal unsaturated groups include carbon-carbon double bonds (i.e., -alkenyl) or carbon-carbon triple bonds (i.e., -ynyl). In some embodiments, these low molecular weight compounds have a molecular weight of less than 800 g / mol, 700 g / mol, 600 g / mol, 500 g / mol, or even 400 g / mol.

[0050] The aforementioned hyperbranched polymer, polyfunctional thiol, and optionally low molecular weight unsaturated compound react in a so-called thiol-ene reaction. Typically, sufficient amounts of the hyperbranched polymer, polyfunctional thiol, and optionally low molecular weight unsaturated compound are used to ensure that no residual reactive groups remain in the cured product. The terminal double bond reacts with one thiol, while the terminal alkyne reacts with two thiols. Therefore, ideally, the molar ratio of the terminal double bond in the hyperbranched polymer to the thiol groups in the polyfunctional thiol compound should be 1:1, and in the case of a triple bond that may be present in the optionally low molecular weight unsaturated compound, the molar ratio of the terminal alkyne bond to the thiol groups should be 1:2. In some embodiments, the molar ratio of the terminal CC double bond in the hyperbranched polymer (and optionally the low molecular weight unsaturated compound) to the thiol (-SH) in the polyfunctional thiol compound is 0.8:1 to 1:0.8 or even 0.9:1 to 1:0.9. If a terminal CC triple bond is present in the curable composition, more thiol will be required.

[0051] When preparing a curable composition, the composition is substantially solvent-free. As used herein, “substantially solvent-free” means a curable composition having less than 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, or even 0.5 wt% of a nonpolymerizable (e.g., organic) solvent. The concentration of the solvent can be determined by known methods, such as gas chromatography (e.g., as described in ASTM D5403-93). It should be noted that whether a curable composition is substantially solvent-free or solvent-free, no solvent is intentionally added to the composition. The term “solvent” as used herein is consistent with the commonly understood technical terminology and covers volatile organic and organic materials that are liquid at room temperature.

[0052] In some embodiments, the curable composition comprises at least one free radical initiator. Typically, the initiator is a photoinitiator, meaning that the initiator is activated by light, typically ultraviolet (UV) light, but other light sources may be used depending on the appropriate selection of the initiator (such as visible light initiators, infrared light initiators, etc.). Thus, the curable composition can generally be cured by UV or visible light, typically UV light. Photoinitiators are known in the art. Examples of suitable free radical photoinitiators include OMNIRAD 4265, OMNIRAD 184, OMNIRAD 651, OMNIRAD 1173, OMNIRAD 819, OMNIRAD TPO, and OMNIRAD TPO-L, which are commercially available from IGM Resins, Charlotte, NC, North Carolina. Particularly suitable photoinitiators include those characterized by high absorbance above 365 nm wavelengths. These photoinitiators include the acylphosphine oxide family of photoinitiators, such as OMNIRAD TPO, OMNIRAD TPO-L, and OMNIRAD819.

[0053] If an initiator is used, it is typically used in amounts of 0.01 to 10 parts by weight, more typically 0.1 to 2.0 parts by weight, relative to the total reactive components (i.e., thiols, alkenes, and ynees) in 100 parts by weight of the curable composition.

[0054] In some embodiments, the curable composition may include additional, optional non-curable components, provided that such components do not impede the curing of the curable composition and do not adversely affect the properties of the cured composition. As needed or desired, the curable composition may also contain polymerization inhibitors, UV absorbers, light stabilizers (e.g., hindered amine light stabilizers (HALS)), adhesion promoters, sensitizers, synergists, antioxidants, catalysts, dispersants, desiccants, surfactants, leveling agents, etc.

[0055] In some embodiments, the curable composition further comprises polymerization inhibitors and / or heat stabilizers. Typically, these polymerization inhibitors and / or heat stabilizers are added to the curable composition in amounts from 1 mM to 1 M. Exemplary inhibitors include BHT (2,6-di-tert-butyl-p-cresol), MEHQ (4-methoxyphenol), and pyrogallol. Exemplary heat stabilizers include 4-methoxyphenol, pyrogallol, or 4-tert-butyl-1,2-dihydroxybenzene. Acidic compounds may also be used as co-stabilizers, including benzoic acid, benzenesulfonic acid, phenylphosphonic acid, and vinylphosphonic acid. Typical concentrations of co-stabilizers in curable compositions range from 1 mM to 1 M. Useful antioxidants include, but are not limited to, amines such as N-N'-di-β-naphthyl-1,4-phenylenediamine, available as "AGERITE D"; phenols such as 2,5-di(tert-amyl)hydroquinone, available as "SANTOVAR A" from Monsanto Chemical Co.; tetra[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, available as "IRGANOX 1010" from Ciba-Geigy Corp.; and 2-2'-methylenebis(4-methyl-6-tert-butylphenol), available as Antioxidant 2246; and dithiocarbamates such as zinc dithiobutylcarbamate.

[0056] In some embodiments, the curable composition has a viscosity of 100 centipoise (cP) or less at temperatures from room temperature to about 60°C. In some embodiments, the curable composition has a viscosity of at least 1 cP, 2 cP, 3 cP, 4 cP, or even 5 cP at room temperature; and at most 100 cP, 80 cP, 60 cP, 50 cP, 40 cP, 30 cP, 25 cP, 20 cP, 15 cP, or even 10 cP. In some embodiments, the curable composition has a viscosity of at least 1 cP, 2 cP, 3 cP, 4 cP, or even 5 cP at 35°C; and at most 100 cP, 80 cP, 60 cP, 50 cP, 40 cP, 30 cP, 25 cP, 20 cP, 15 cP, or even 10 cP. In some embodiments, the curable composition has a viscosity of at least 1 cp, 2 cp, 3 cp, 4 cp, or even 5 cp at 60°C; and at most 30 cp, 25 cp, 20 cp, 15 cp, or even 10 cp, as measured by a viscometer under ambient conditions. For example, viscosity can be measured by taking 17 mL of the curable composition and loading it into a 25 mm diameter double-gap coaxial concentric cylindrical apparatus on a viscometer (BOHLIN VISCO 88, Malvern Instruments Ltd, Malvern, UK). Water heated to 25°C can be recirculated in a thermal jacket on the viscometer's double-gap pool to maintain a constant temperature during testing. For example, the system can be equilibrated for 30 minutes before each measurement. The shear rate can be increased from 100 Hz to 1000 Hz in 100 Hz intervals, and the measurement is repeated three times to determine the average viscosity.

[0057] Curable compositions can be deposited onto surfaces using techniques known in the art, including conventional coating techniques such as bar coating, roller coating, curtain coating, rotary gravure coating, spraying, or dip coating. The curable compositions disclosed herein can be used, in particular, as organic layers in thin-film encapsulated parts. Typically, printing techniques such as inkjet printing are used to deposit these organic layers.

[0058] A variety of substrates are suitable for the articles of manufacture disclosed herein. Suitable substrates include a wide range of flexible and non-flexible substrates. For example, the substrate may be a layer of glass, silicon nitride, silicon oxynitride, or a relatively thick polymeric material such as PMMA (polymethyl methacrylate) or PC (polycarbonate). Alternatively, the substrate may be a flexible polymeric film, such as a film of PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), polyimide, PEEK (polyetheretherketone), etc. In some embodiments, the substrate includes a thermosensitive substrate. A variety of thermosensitive substrates are suitable, such as OLED panels.

[0059] Curable compositions can be exposed to thermal or light radiation to initiate a reaction between thiols and the carbon-carbon double bonds of hyperbranched polymers, thereby producing a cured composition. Curable compositions can be exposed to ultraviolet (UV)A radiation with a maximum value in the range of 280 nm to 425 nm. UV light sources can be of various types. Low-intensity light, such as black lights, typically provides intensities ranging from 0.1 mW / cm² or 0.5 mW / cm² (milliwatts per square centimeter) to 10 mW / cm² (measured according to procedures approved by the National Institute of Standards and Technology, such as, for example, using a UVIMAP UM365 LS radiometer manufactured by Electronic Instrumentation & Technology, Inc., Sterling, VA). High-intensity light sources typically provide intensities greater than 10 mW / cm², 15 mW / cm², or 20 mW / cm², ranging up to 450 mW / cm² or greater. In some implementations, the high-intensity light source provides intensities up to 500 mW / cm², 600 mW / cm², 700 mW / cm², 800 mW / cm², 900 mW / cm², or 1000 mW / cm². The UV light used to polymerize these monomer components can be provided by a variety of light sources, such as light-emitting diodes (LEDs), black lights, medium-pressure mercury lamps, or combinations thereof. The reagents can also be polymerized using even higher-intensity light sources available from Fusion UV Systems Inc. The UV exposure time for polymerization and curing can vary depending on the intensity of the light source used. For example, complete curing using low-intensity light can be completed with an exposure time ranging from approximately 30 to 300 seconds; while complete curing using a high-intensity light source can be completed with a shorter exposure time ranging from approximately 5 to 20 seconds. Partial curing using a high-intensity light source can typically be completed with an exposure time ranging from approximately 2 to approximately 5 or 10 seconds.

[0060] Typically, the cured layer will have a refractive index of at least 1.600, 1.610, 1.620, 1.630, 1.640, 1.650, 1.660, 1.670, or even 1.680 (when measured at 450 nm). High-refractive-index nanoparticles, such as polymer particles, metal particles, or metal oxide particles having a refractive index of at least 1.6, are commonly used to increase the refractive index of the cured layer. However, advantageously, the cured composition of this disclosure has a high refractive index without the use of nanoparticles.

[0061] In some embodiments, the cured composition has a glass transition temperature of at least -20°C, -10°C, 10°C, 20°C, 30°C, 40°C, 45°C, 50°C, or even 54°C, and at most 120°C, 110°C, 100°C, 90°C, or even 80°C. The terms "Tg" and "glass transition temperature" are used interchangeably. If measured, the Tg value at the midpoint (or half-height) is determined by differential scanning calorimetry (DSC) using a second heating at a scan rate of 10°C / min. In some embodiments, the Tg of the cured composition is higher (e.g., at least 5°C, 10°C, 20°C, or even 30°C higher) than that of the same sample, wherein the hyperbranched polymer is replaced by Si(vinyl)4.

[0062] Ideally, the cured composition is optically transparent. Unless otherwise specified, "optically transparent" means that the layer, film, or article has high transmittance and exhibits low haze over at least a portion of the visible spectrum (about 400 nm to about 700 nm). Typically, using techniques such as ASTM D1003-21, an optically transparent layer, film, or article has a visible light transmittance value of at least 85%, or even 90%, typically at least 95%, and a haze value of 5% or less, typically 2% or less.

[0063] This document also discloses articles. A wide variety of articles can be prepared using the above-described curable composition. The articles can be relatively simple, such as... Figure 1 The substrate shown has a layer of cured composition disposed thereon, wherein article 100 includes a substrate 120 and a cured organic layer 110 disposed on the substrate. Substrate 120 includes a wide variety of flexible and non-flexible substrates. For example, substrate 120 may be a layer of glass, silicon nitride, silicon oxynitride, or a relatively thick polymeric material such as PMMA (polymethyl methacrylate) or PC (polycarbonate). Alternatively, substrate 120 may be a flexible polymeric film, such as a film of PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), polyimide, PEEK (polyetheretherketone), etc. The cured organic layer 110 is a cured layer derived from the curable composition described herein. In some embodiments, the cured organic layer has a thickness of 1 micrometer to 50 micrometers, and in some embodiments, 5 micrometers to 30 micrometers.

[0064] In other embodiments, the article is more complex, such as a multilayer article comprising a substrate and an inorganic barrier layer, wherein a cured organic layer is interposed therebetween, wherein the cured layer serves as a decoupling layer. The substrate may optionally have an inorganic coating present on its surface, such that the cured organic layer may contact the substrate surface or the optional inorganic coating.

[0065] In some embodiments, the article includes a substrate having a first main surface and a second main surface, and a cured organic layer having a first main surface and a second main surface, wherein the first main surface of the cured organic layer is adjacent to at least a portion of the second main surface of the substrate.

[0066] Figure 2 Devices incorporating the multilayer articles of this disclosure are shown. Figure 2 An article 200 including a substrate 230 is shown, and a device 240 is disposed on the substrate 230. An inorganic barrier layer 250 is in contact with the device 240, and a cured organic layer 210 is in contact with the inorganic barrier layer 250. Figure 2 It also includes an optional inorganic layer 260 that contacts the cured organic layer 210. An optional layer 270 contacts the optional inorganic layer 260 and also contacts the substrate 280. Additionally, optional alternating pairs of cured organic layers (210) and inorganic layers (260) may exist between the optional layers 260 and 270. For clarity, these optional layers are not shown, but a stack of layers in the order 250 / 210 / 260 / 210 / 260 or 250 / 210 / 260 / 210 / 260 / 210 / 260, etc., can be readily imagined.

[0067] The curable compositions disclosed herein can be cured and used as organic layers in thin-film encapsulated parts. These organic layers should be deposited onto a surface in a precise and consistent manner, which is typically accomplished using printing techniques. In printing techniques, the curable composition, which forms a polymer upon curing, is printed onto a substrate surface to form a layer. A wide variety of printing techniques can be used, with inkjet printing being particularly desirable due to its excellent precision. Because curable compositions can be printable, they may also be referred to herein 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 that they have suitable viscosity and other properties required 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. In this disclosure, printable curable compositions, which can be considered "inks," are described, and these curable compositions have several characteristics that make them suitable for forming layers within multilayer optical devices. As described above, the curable compositions of this disclosure are substantially solvent-free, which is advantageous because drying the coating to remove solvent not only reduces the layer thickness but also adversely affects surface smoothness and may introduce defects into the coating. In many applications of optical devices, it is desirable for coatings to be precise, meaning they do not lose thickness or smoothness during drying. Therefore, the curable compositions of this disclosure are preferably “100% solids,” meaning they do not contain volatile solvents and all substances deposited on the surface remain on the surface, with no volatile substances lost from the coating.

[0068] The thickness of the cured composition is limited by the application. For thin-film encapsulated products, the cured organic layer typically has a thickness of 1 micrometer to 50 micrometers, and in some embodiments 5 micrometers to 30 micrometers. Additionally, in many embodiments, the cured organic layer has a surface roughness of less than or equal to 10 nanometers, and in some embodiments less than or equal to 5 nanometers.

[0069] An example of an optical device utilizing thin-film layers is an OLED (Organic Light-Emitting Diode) device. Specifically, OLEDs are susceptible to degradation due to the permeation of certain liquids and gases, such as water vapor and oxygen. To reduce permeability to these liquids and gases, a barrier coating is applied to the OLED device. Typically, these barrier coatings are not used alone, but rather in a barrier stack comprising multiple pairs of layers. A pair of layers is a two-layer structure comprising a barrier layer (i.e., an inorganic layer) and a decoupling layer (i.e., an organic layer). The decoupling layer provides a planarized and / or smooth surface for depositing the inorganic barrier layer.

[0070] The inorganic barrier layer 250, in contact with the cured organic layer 210, can be made of a variety of materials, including metals, metal oxides, metal nitrides, metal oxide nitrides, metal carbides, metal boron oxides, and combinations thereof. A wide range of metals are suitable for metal oxides, metal nitrides, and metal oxide nitrides; specifically, suitable metals include Al, Zr, Si, Zn, Sn, and Ti. A particularly suitable inorganic barrier layer material is silicon nitride.

[0071] There is no specific limitation on the thickness of the inorganic barrier layer 250, which is typically between 20 nanometers and 1 micrometer (1000 nanometers). More typically, the thickness is between 20 nanometers and 100 nanometers.

[0072] The optional inorganic barrier layer 260 has a similar thickness to the inorganic barrier layer 250 and may contain the same inorganic material, or it may be a different inorganic material.

[0073] One embodiment of device 200 is a touch sensing device. In this device, substrate 230 is a thin-film transistor, device 240 is an OLED device, optional layer 270 is an optically transparent adhesive layer, and substrate 280 is a touch sensor.

[0074] In some embodiments, a curable composition is applied to the surface of a substrate and then cured to form a cured organic layer. In some embodiments, an inorganic barrier layer is disposed on the exposed surface of the cured organic layer.

[0075] In some embodiments, the curable composition can be printed and then cured to form a layer. In some embodiments, the cured composition has a thickness of 1 micrometer to 16 micrometers and a surface roughness of less than or equal to 5 nanometers. In many embodiments, setting the curable composition on a second primary surface of a substrate to form a curable layer includes printing, particularly inkjet printing. As mentioned above, inkjet printing has several desirable characteristics that make it particularly suitable for preparing curable layers, including the ability to deposit precise patterns on complex substrates and form a uniform coating with a low surface roughness of less than 10 nanometers, and in some embodiments less than or equal to 5 nanometers.

[0076] In some embodiments, the article also includes a device disposed on a second main surface of the substrate and adjacent to the cured organic layer.

[0077] In some embodiments, the substrate includes an inorganic coating present on a second primary surface, such that the first primary surface of the cured organic layer is in contact with the inorganic coating.

[0078] The above-described structure can also be used as a component of more complex articles. In some embodiments, the article further includes a device disposed on a second main surface of the substrate and adjacent to the first main surface of the cured organic layer. In some embodiments, an inorganic coating is disposed on the device and the second main surface of the substrate, such that the first main surface of the cured organic layer is in contact with the inorganic coating. In some specific embodiments, the device includes an OLED (organic light-emitting diode).

[0079] Example

[0080] Unless otherwise specified, all parts, percentages, ratios, etc., in the examples and the remainder of the description are by weight, and all reagents used in the examples are derived from or purchased from common chemical suppliers, such as, for example, Millipore-Sigma Company, Saint Louis, Missouri, or Gelest, Morristown, Pennsylvania, or can be synthesized by conventional methods.

[0081]

[0082] Preparation of hyperbranched polymers (HBP1 ​​and HBP2)

[0083] HBP1 is prepared as described in HYPERBRANCHED POLYMER, METHOD OF MAKING, AND CURABLE COMPOSITIONINCLUDING THE SAME (patent application WO / 2022 / 058810, published March 24, 2022) for polymer 1, having 6.14 mmol / g vinyl groups, Mn 2500, average vinyl functionality 15, and a core derived from tetravinylsilane and 1,4-bis(dimethylsilyl)benzene.

[0084] HBP2 (5.62 mmol / g vinyl, Mn 2100, average vinyl functionality 12) was prepared from 1,2,4-trivinylcyclohexane and 1,4-bisdimethylsilylbenzene by the same method.

[0085] Refractive index

[0086] The refractive index of the cured film on a PET substrate was measured at 450 nm at 20 °C using a digital prism coupler (model 2010, Metricon Inc., Pennington, NJ).

[0087] Differential scanning calorimetry (DSC)

[0088] DSC samples for thermal analysis were prepared by weighing the material and loading it into an aluminum DSC sample tray from TA Instruments (New Castle, Delaware). The samples were analyzed using a TA Instruments Discovery Differential Scanning Calorimeter (DSC - SN DSC1-0091, New Castle, DE) in standard mode (10 °C / min from -155 °C to approximately 150 °C). After data collection, the thermal transitions were analyzed using TA's universal analytical procedures. The glass transition temperature was assessed using a step change in the standard heat flux (HF) curve. The midpoint (half-high) temperature of the second thermal transition was reported.

[0089] Average functionality

[0090] The average functionality of the resulting cured polymer is theoretically determined by multiplying the percentage of functional groups present by the product of the number of functional groups present (i.e., SH and C=C). For example, in sample C1, the average functionality is (0.67 × 2) + (0.33 × 4) = 2.66.

[0091] Examples 1 to 7 (E1-E7) and Comparative Examples 1 to 10 (C1-C10)

[0092] The thiol olefin formulation was prepared from a mixture of liquid thiol with a hyperbranched polymer and optionally a low molecular weight olefin, in a mass ratio such that the molar ratio of thiol groups to carbon-carbon double bonds was 1:1. TPO-L was added at 3% by weight, and the formulation was thoroughly mixed. The liquid formulation was cast onto a polyethylene terephthalate (PET) substrate using a Mayer rod (No. 10) and cured using a UV LED curing system (Clearstone Technologies Inc., Hopkins, MN, 395 nm, 100% intensity corresponding to 319 mW / cm²). 2 UV curing was performed at a distance of 1 cm from the sample surface for 2 minutes to obtain a transparent hard coating. The glass transition temperature and refractive index of the sample were tested, and the average functionality was determined. The results are reported in Table 2.

[0093]

[0094] Foreseeable modifications and alterations to the invention will be apparent to those skilled in the art without departing from its scope and spirit. The invention should not be limited to the embodiments shown in this application for illustrative purposes. In the event of any conflict or contradiction between the disclosure in this written specification and any document incorporated herein by reference, the written specification shall prevail.

Claims

1. A curable composition comprising: (i) a hyperbranched polymer comprising a plurality of first terminal carbon-carbon double bonds, wherein the hyperbranched polymer comprises the reaction product of: (a) at least one unsaturated compound consisting of C, H, and optionally Si, O atoms, or Si and O atoms and having p second terminal carbon-carbon double bonds, wherein each p is independently an integer greater than or equal to 2; (b) at least one organosilane compound consisting of C, H, Si, and optionally O atoms and having q Si-H groups, wherein each q is independently an integer greater than or equal to 2; and (c) at least one hydrosilylation reaction catalyst, wherein p / q is at least 2.1; and (ii) at least one multifunctional mercaptan comprising at least 2 mercaptan groups; and wherein the curable composition is substantially free of solvent.

2. The curable composition of claim 1, wherein p / q is at least 3.

3. The curable composition of any one of the preceding claims, wherein the at least one organosilane compound in component (b) is independently represented by the formula: Z(SiR 1 2H) a wherein Z is an a-valent group consisting of C, H, and optionally O, wherein Z has 1 to 12 carbon atoms, each R 1 independently a hydrocarbyl group having 1 to 12 carbon atoms, and a is an integer from 2 to 8.

4. The curable composition of claim 3, wherein Z comprises a phenylene group.

5. The curable composition of any one of the preceding claims, wherein the at least one unsaturated compound in component (a) is independently represented by the formula: Si(OSiR 2 2CH=CH2) b (R 2 CH=CH2) c (R 3 ) d wherein each R 2 independently a direct bond or an alkylene group having 1 to 12 carbon atoms, each R 3 independently a hydrocarbyl group having 1 to 12 carbon atoms, b is an integer from 0 to 4, c is an integer from 0 to 4, and d is an integer from 0 to 2, with the proviso that b + c > 2 and b + c + d = 4.

6. The curable composition of claim 5, wherein at least one first compound in component (a) is selected from the group consisting of tetra-vinyl silane or tetra-allyl silane.

7. The curable composition of any one of claims 1 to 4, wherein at least one first compound in component (a) is a hydrocarbon having at least 3 vinyl or allyl groups, optionally, component (a) is tri-vinyl cyclohexane.

8. The curable composition of any one of the preceding claims, wherein the hyperbranched polymer has a molecular weight of at least 1000 g / mol and up to 5000 g / mol.

9. The curable composition of any one of the preceding claims, wherein the curable composition further comprises a low molecular weight compound comprising at least 2 or more terminal unsaturated groups, wherein the terminal unsaturated groups are selected from -alkenyl or -alkynyl groups.

10. The curable composition of claim 9, wherein the low molecular weight compound has a molecular weight of less than 800 g / mol.

11. The curable composition of any one of the preceding claims, wherein the ratio of mercaptan groups to the first terminal carbon-carbon double bonds is 1 : 0.8 to 0.8:

1.

12. The curable composition of any one of the preceding claims, wherein the multifunctional mercaptan is an aromatic mercaptan.

13. The curable composition of any of the preceding claims, wherein the multifunctional mercaptan is 4-mercaptomethyl- 1,8-dimercapto-3,6-dithiaoctane; 5,7-dimercaptomethyl- 1, 11 -dimercapto-3,6,9- tri thi a undecane; 4,8-dimercaptomethyl- 1, 11 -dimercapto-3,6,9-trithiaundecane; 4,7- dimercaptomethyl- 1, 11 -dimercapto-3,6,9-trithiaundecane, pentaerythritol tetra(3- mercapto propionate), trimethylolpropane tri(3-mercaptopropionate or mixtures thereof.

14. The curable composition of any of the preceding claims, wherein the curable composition further comprises a free radical initiator.

15. The curable composition of any of the preceding claims, wherein the curable composition has a refractive index (measured at 450 nm) of greater than 1.

610.

16. The curable composition of any of the preceding claims, wherein the Tg of the curable composition is higher than the Tg of a comparative example wherein the hyperbranched polymer is replaced by Si(vinyl)4.

17. The curable composition of any of the preceding claims, wherein the curable composition further comprises an inhibitor.

18. The curable composition of any of the preceding claims, wherein the curable composition further comprises a thermal stabilizer.

19. The curable composition of any of the preceding claims, wherein the curable composition further comprises an adhesion promoter.

20. The curable composition of any of the preceding claims, wherein the curable composition has a viscosity of 100 cp or less at a temperature of room temperature to 35°C.

21. An article comprising: a substrate having a first major surface and a second major surface; a cured organic layer adjacent to at least a portion of the second major surface of the substrate, wherein the cured organic layer is derived from (i) a hyperbranched polymer comprising a plurality of first terminal carbon-carbon double bonds, wherein the hyperbranched polymer comprises the reaction product of: (a) at least one unsaturated compound consisting of C, H, and optionally Si, O atoms, or Si and O atoms and having p second terminal carbon-carbon double bonds, wherein each p is independently an integer greater than or equal to 2; (b) at least one organosilane compound consisting of C, H, Si, and optionally O atoms and having q Si-H groups, wherein each q is independently an integer greater than or equal to 2; and (c) at least one hydrosilylation reaction catalyst, wherein p / q is at least 2.1 ; and (ii) at least one multifunctional mercaptan comprising at least 2 mercaptan groups; and an inorganic barrier layer in contact with the cured organic layer, wherein the cured organic layer has a refractive index (measured at 450 nm) of at least 1.

610.

22. The article of claim 21, wherein the cured organic layer is optically transparent.

23. The article of any one of claims 21-22, wherein the cured organic layer has a glass transition temperature of at least 10 C.

24. The article of any one of claims 21 to 23, wherein the cured organic layer has a thickness of 1 micrometer to 16 micrometers and a surface roughness of less than or equal to 5 nanometers.

25. The article of any one of claims 21 to 24, wherein the article further comprises a device disposed on the second major surface of the substrate and adjacent to the cured organic layer.

26. The article of claim 25, wherein the device comprises an OLED (organic light emitting diode).

27. A method of making an article, the method comprising: providing a substrate having a first major surface and a second major surface; providing a curable composition according to any one of claims 1 to 25; disposing the curable composition on at least a portion of the second major surface of the substrate to form a curable layer; curing the curable layer to form a cured organic layer, wherein the cured organic layer has a refractive index of at least 1.610 measured at 450 nm; and depositing an inorganic barrier layer on the cured organic layer.

28. The method of claim 27, wherein disposing the curable composition on the second major surface of the substrate to form a curable layer comprises inkjet printing to a thickness of 1 micrometer to 16 micrometers.

29. The method of any one of claims 27 to 28, further comprising providing a device; and disposing the device on the second major surface of the substrate prior to disposing the curable composition on the second major surface of the substrate to form a curable layer.

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