Hyperbranched polythioethers, curable high refractive index compositions and articles thereof, and methods of making such compounds and articles

Abstract

Described herein are hyperbranched polythioethers comprising a plurality of terminal functional groups, wherein the terminal functional groups comprise terminal carbon-carbon double bonds or thiol groups, and wherein the hyperbranched polythioethers have a refractive index of at least 1.600 and a number average molecular weight of at least 1000 g / mol and at most 5000 g / mol. In some embodiments, the hyperbranched polythioethers are reacted with a multifunctional compound, wherein the multifunctional compound has complementary terminal functional groups that can react with the hyperbranched polythioethers in a thiol-ene reaction. These curable compositions have a high refractive index of at least 1.660 when cured (when measured at 450 nm) and can be used in optical devices.

Description

Technical Field

[0001] This document discloses hyperbranched polysulfides comprising multiple terminal thiol groups or carbon-carbon double bonds, and methods for their preparation. It also discloses reacting these hyperbranched polysulfides with multifunctional compounds in a thiol-ene reaction to obtain compositions with high refractive indices. Curable compositions and articles for use in, for example, optical devices are 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] It is desirable to identify new compounds with high refractive indices that can be used to prepare curable organic compositions, in some embodiments of which are inkjet printable and used to prepare high refractive index layers.

[0005] In one aspect, a hyperbranched polysulfide is described. The hyperbranched polysulfide comprises a plurality of terminal carbon-carbon double bonds or thiol groups, and wherein the hyperbranched polysulfide has a refractive index of at least 1.600 and a number-average molecular weight of at least 1000 g / mol and at most 5000 g / mol.

[0006] In one aspect, a method for preparing hyperbranched polysulfides is described. The method comprises mixing: at least one unsaturated compound having p vinyl or allyl groups and consisting of C, H, and optionally O and / or Si atoms, wherein each p is an integer greater than or equal to 2; and at least one organothiol having q thiol groups and consisting of C, H, S, and optionally O atoms, wherein each q is an integer greater than or equal to 2.

[0007] In one aspect, a curable composition is described, the curable composition comprising: (i) a hyperbranched polysulfide comprising a plurality of terminal carbon-carbon double bonds or thiol groups, wherein the hyperbranched polysulfide has a refractive index of at least 1.660 and a number-average molecular weight of at least 1000 g / mol and at most 5000 g / mol; and (ii) at least one multifunctional compound, wherein components (i) and (ii) react via a thiol-ene reaction; and The curable compositions are essentially solvent-free.

[0008] 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 primary surface of the substrate, wherein the cured organic layer is derived from (i) a hyperbranched polysulfide; and (ii) at least one multifunctional compound; 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 1.660 (measured at 450 nm).

[0009] 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 polysulfide comprising a plurality of terminal carbon-carbon double bonds or thiol groups, wherein the hyperbranched polysulfide has a refractive index of at least 1.600 and a number-average molecular weight of at least 1000 g / mol and at most 5000 g / mol; and (ii) at least one multifunctional compound wherein components (i) and (ii) react via a thiol-ene reaction; 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 1.660 measured at 450 nm; and An inorganic barrier layer is deposited on a cured organic layer.

[0010] 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

[0011] 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.

[0012] Figure 1 A cross-sectional view of an embodiment of the article of manufacture disclosed herein is shown.

[0013] Figure 2 A cross-sectional view of an embodiment of another article of the present disclosure is shown.

[0014] In the following description of the illustrated embodiments, reference is made to the accompanying drawings, which illustrate various embodiments in which the present disclosure may be practiced. It should be understood that embodiments may be utilized and structural changes may be made without departing from the scope of the present disclosure. The drawings are not necessarily drawn to scale. Similar numbers used in the drawings refer to similar components. 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

[0015] As used in this article, terminology

[0016] "A," "an," and "the / described" are used interchangeably and refer to one or more; and

[0017] "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).

[0018] 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.).

[0019] 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.).

[0020] 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.

[0021] 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.

[0022] This disclosure describes hyperbranched polysulfide compounds comprising multiple terminal functional groups. The terminal functional groups may be carbon-carbon double bonds (e.g., vinyl or allyl groups) or thiol groups.

[0023] The polysulfide compounds disclosed herein are hyperbranched, meaning they are dendritic polymers that are polydisperse.

[0024] In some embodiments, the hyperbranched polysulfide 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 polysulfide according to this disclosure has a molecular weight of up to 5000 g / mol, 4000 g / mol, 3500 g / mol, 3000 g / mol, or even 2500 g / mol.

[0025] The hyperbranched polysulfide disclosed herein contains at least two terminal functional groups, more preferably at least three or even at least four terminal functional groups. Typically, the hyperbranched polysulfide disclosed herein contains no more than 10, 15, or even 20 terminal functional groups. Generally, the hyperbranched polysulfide contains multiple terminal carbon-carbon double bonds (vinyl groups or allyl groups) or terminal thiol groups, but not both.

[0026] The hyperbranched polysulfide disclosed herein has a high refractive index. In one embodiment, when measured as a liquid via a refractometer, the hyperbranched polysulfide has a refractive index of at least 1.600, 1.610, 1.620, 1.640, 1.650, 1.660, or even 1.680.

[0027] The hyperbranched polysulfides according to this disclosure can be prepared via a so-called thiol-olefin click reaction. The thiol-olefin reaction is known in the art and is a reaction in which a thiol group forms a thioether with an olefin. The reaction typically has a high rate and high yield. In some embodiments, at least one unsaturated compound reacts with at least one organothiol in a thiol-olefin type reaction.

[0028] In some embodiments, at least one unsaturated compound independently has p vinyl or p allyl groups and is composed of C, H, and optionally Si and / or O atoms. Each p is an integer greater than or equal to 2 (e.g., 3, 4, 5, 6, 7, or 8).

[0029] In some embodiments, the useful unsaturated compound has 4 to 20 carbon atoms (e.g., 4 to 20, 4 to 18, 4 to 16, 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 O is present, it is preferably present in an ether bond (i.e., COC). 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 O 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, Si, and O atoms. In some embodiments, the useful unsaturated compounds contain aromatic carbon atoms, while in other embodiments they do not contain aromatic carbon atoms.

[0030] In some embodiments, the unsaturated compound used is an organosilane. Exemplary organosilanes contain at least one silicon atom, such as those 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.

[0031] 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).

[0032] 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.

[0033] Exemplary organosilanes 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 polydisiloxanes Methylsiloxane; 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-pentamethylcyclopentanesiloxane; hexavinyldisiloxane; and 1,3,5,7,9,11-hexavinyl-hexamethylcyclohexylsiloxane. 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. Among these tetravinylsilanes, tetraallylsilane; 1,2,4-trivinylcyclohexane; and 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane are preferred in some embodiments.

[0034] Exemplary unsaturated compounds that do not contain Si atoms include trivinylcyclohexane and triallyl isocyanurate.

[0035] To prepare hyperbranched polysulfides, an unsaturated compound is reacted with at least one organothiol. In some embodiments, the organothiol has q thiol groups and is composed of C, H, S, and optionally O and / or N atoms. Each q is independently an integer greater than or equal to 2 (e.g., 3, 4, 5, 6, 7, or 8).

[0036] In some embodiments, the useful organothiol has 4 to 20 carbon atoms (e.g., 4 to 20, 4 to 18, or 4 to 12 carbon atoms), 2 to 10 sulfur atoms (e.g., 2 to 10, 2 to 8, 2 to 6, or 2 to 4 silicon atoms), 0 to 9 oxygen atoms (e.g., 0 to 9, 0 to 6, 0 to 4, 0 to 2, or 0 to 1 oxygen atoms), and 0 to 9 nitrogen atoms (e.g., 0 to 9, 0 to 6, 0 to 4, 0 to 2, or 0 to 1 nitrogen atoms). In some embodiments, the useful organothiol is composed of C, H, and S atoms. In some embodiments, the useful organothiol is composed of C, H, S, and O and / or N atoms.

[0037] In some implementations, the organothiol is independently derived from the formula HS-R 4 -Ar-R 4 -SH indicates that each R 4 It is independently a direct bond or a hydrocarbon group having 1 to 12 carbon atoms (e.g., 1 to 12, 2 to 12 or 4 to 12 carbon atoms), and Ar is an aryl group containing C, H and optionally S and / or N atoms.

[0038] Exemplary organothiols include 1,3-benzenedithiol; 1,3-benzenedimethylthiol; and 2,3-bis-2-mercaptoethylthio-1-propanethiol.

[0039] In some embodiments, the reaction of at least one unsaturated compound and at least one organothiol is initiated by at least one radical initiator. Typically, the initiator is a photoinitiator, meaning that the initiator is activated by light, usually 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.). Photoinitiators are known in the art. Examples of suitable 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 OMNIRAD 819.

[0040] 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 100 parts by weight of the total reactive components (i.e., thiols and carbon-carbon double bonds) in the reaction composition.

[0041] In the reaction of unsaturated compounds with organothiols, one terminal carbon-carbon double bond reacts with one terminal thiol. Therefore, to generate functionalized hyperbranched polysulfides, more moles of one of these functional groups are required. In other words, p (C=C bond groups) + q (thiol groups) is greater than 4 (e.g., greater than 5, 6, 7, 8, or even 9). Thus, using more p C=C bond groups will produce hyperbranched polysulfides with multiple terminal carbon-carbon double bonds. Similarly, using more q thiol groups will produce hyperbranched polysulfides with multiple terminal thiol groups.

[0042] The resulting reaction mixture is exposed to a light source required to initiate the reaction, such as UV light or visible light.

[0043] The resulting hyperbranched polysulfide can have a high refractive index, for example, greater than 1.600. The presence of phenyl groups and / or sulfur can increase the refractive index. Therefore, in some embodiments, the hyperbranched polysulfide contains at least one phenyl group. Such phenyl groups can be introduced by using phenyl-containing reactants, such as phenyl-containing organosilanes. Advantageously, the presence of phenyl groups can also cause an increase in the glass transition temperature (Tg) of the molecule. In some embodiments, the hyperbranched polysulfide contains at least 20 wt%, 25 wt%, 30 wt%, or even 40 wt% sulfur, which can be empirically determined by calculating the ratio of the weight of sulfur atoms to the total weight of atoms in the hyperbranched polysulfide.

[0044] Curable Composition

[0045] In this disclosure, it has been found that curable compositions comprising the hyperbranched polysulfides and multifunctional compounds disclosed herein can produce curable compositions having a high refractive index and, in some embodiments, an increased glass transition temperature (Tg) after curing.

[0046] The curable compositions disclosed herein are substantially solvent-free and contain at least one multifunctional compound. In one embodiment, the multifunctional compound can be reacted with the hyperbranched polysulfide in a thiol-olefin reaction as discussed above. In another embodiment, the hyperbranched polysulfide containing terminal carbon-carbon double bonds can optionally be reacted with the multifunctional compound containing terminal carbon-carbon double bonds in the presence of a free radical initiator to form a cured article.

[0047] In a first embodiment, the multifunctional compounds disclosed herein comprise a plurality of functional groups that can react with hyperbranched polysulfides via a thiol-olefin reaction. For example, if a hyperbranched polysulfide comprising terminal carbon-carbon double bonds is used, the multifunctional compound comprises a plurality of terminal thiol groups. Such multifunctional compounds 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. These multifunctional compounds can have a molecular weight of about 70 to 1000 g / mol in the case of small molecules, and about 1000 to 5000 g / mol in the case of the hyperbranched polysulfides disclosed herein.

[0048] To ensure the cured composition has a high refractive index, it is helpful to select a multifunctional compound with a high refractive index. Generally, aromatic groups can increase the refractive index of the compound. Typically, the refractive index of non-aromatic multifunctional thiols does not exceed 1.620, as determined using a white light refractometer. However, multifunctional compounds containing multiple terminal thiol groups can be either aromatic or non-aromatic thiols.

[0049] Exemplary non-aromatic polyfunctional compounds 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'-thiodiethanethiol; di(mercaptoethyl) sulfide; 2,5-bis(mercaptomethyl)-1,4-dithiane; tetra(ethylene glycol) dithiol; 2,2'-(ethylenedioxy)diethanethiol; pentaerythritol tetra(3-mercaptopropionate); trimethylolpropane tri(3-mercaptopropionate). and .

[0050] In some embodiments, the polyfunctional compound is an aromatic thiol. Aromatic thiols may have 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.

[0051] If hyperbranched polysulfides containing terminal thiol groups are used, the multifunctional compound contains multiple terminal carbon-carbon double bonds.

[0052] Exemplary polyfunctional compounds containing terminal carbon-carbon double bonds include tetravinylsilane, tetraallylsilane, and trivinylcyclohexane.

[0053] In some embodiments, a hyperbranched polysulfide containing multiple terminal carbon-carbon double bond groups is reacted with a hyperbranched polysulfide containing multiple terminal thiols.

[0054] The hyperbranched polysulfide reacts with the aforementioned polyfunctional compound. Typically, sufficient amounts are used to react the hyperbranched polysulfide and the polyfunctional compound to ensure that no residual reactive groups remain in the cured product. The terminal double bond reacts with a thiol. Therefore, ideally, the molar ratio of the terminal double bond in the hyperbranched polymer to the thiol group in the polyfunctional thiol compound should be 1:1. In some embodiments, the molar ratio of the terminal carbon-carbon double bond in the hyperbranched polymer 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.

[0055] 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 below 80°C, 70°C, 60°C, 50°C, 40°C, or even 30°C at ambient pressure (e.g., 760 mm Hg).

[0056] In another embodiment, the first hyperbranched polysulfide containing terminal carbon-carbon double bonds can optionally react with another polyfunctional compound containing terminal carbon-carbon double bonds in the presence of a free radical initiator. Such polyfunctional compounds containing terminal carbon-carbon double bonds include tetravinylsilane, tetraallylsilane, and trivinylcyclohexane as mentioned above, but may also include a second hyperbranched polysulfide containing terminal carbon-carbon double bonds. Such a second hyperbranched polysulfide containing terminal carbon-carbon double bonds may be the same as or different from the first hyperbranched polysulfide containing terminal carbon-carbon double bonds.

[0057] 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.

[0058] In some embodiments, the curable composition comprises at least one free radical initiator as described above for the synthesis of hyperbranched polysulfide compounds.

[0059] 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 100 parts by weight of the total reactive components (i.e., thiols and C=C double bonds) in the curable composition.

[0060] 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.

[0061] 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 an amount of 2% by weight or less. 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 "AGERITED"; 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.

[0062] In some embodiments, the curable composition has a viscosity of 100 centipoise (cP) or less over a temperature range 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.

[0063] 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.

[0064] 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.

[0065] Curable compositions can be exposed to heat 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. Various types of UV light sources are available. Low-intensity lamps (such as black lights) typically provide a range of 0.1 mW / cm². 2 Or 0.5mW / cm 2 (mW / cm²) to 10mW / cm² 2 The intensity (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 values ​​above 10 mW / cm². 2 15mW / cm 2 Or 20mW / cm 2 Up to 450mW / cm 2 Or even higher intensities. In some implementations, high-intensity light sources provide up to 500 mW / cm². 2 600mW / cm 2 700mW / cm 2 800mW / cm 2 900mW / cm 2 Or 1000mW / cm 2 The intensity of 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. Reagents can also be polymerized using higher-intensity light sources available from Fusion UV Systems Inc. The UV exposure time used 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 achieved with exposure times ranging from approximately 30 to 300 seconds; while complete curing using high-intensity light can be achieved with shorter exposure times ranging from approximately 5 to 20 seconds. Partial curing using high-intensity light typically takes place with exposure times ranging from approximately 2 to approximately 5 or 10 seconds.

[0066] Typically, when measured at 450 nm, the cured layer will have a refractive index of at least 1.660, 1.670, or even 1.680. 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.

[0067] 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.

[0068] In some embodiments, the glass transition temperature of the cured composition is at least -20°C, -10°C, 0°C, or even 5°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.

[0069] 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 illustrated substrate 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 or PC. Alternatively, substrate 120 may be a flexible polymeric film, such as a film of PET, PEN, PC, polyimide, PEEK, 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.

[0070] 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.

[0071] 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.

[0072] Figure 2 Devices incorporating the multilayer articles of this disclosure are shown. Figure 2An 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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 5 to 30 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.

[0082] 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.

[0083] 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.

[0084] 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).

[0085] Example

[0086] 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.

[0087]

[0088] Preparation of Hyperbranched Polymer (HBP) Examples

[0089] HBP 1 (allyl-terminated)

[0090] UV irradiation (395nm, 2 minutes, 100% corresponds to 319mW / cm²) 2A mixture of 0.36 g of 13BDT (5.06 mmol thiol) and excess Si(allyl)4 (0.75 g, 15.6 mmol allyl) was stirred in a glass vial containing 0.02 g of TPOL at a distance of 1 cm for 2 minutes. The resulting colorless oil was precipitated in methanol, the upper methanol fraction was removed, and the product was washed three times with acetonitrile to remove excess monomer. The product was obtained as a colorless, viscous liquid.

[0091] HBP 2 (thiol-terminated)

[0092] Under UV irradiation (as described above), a mixture of Si(allyl)4 (0.24 g, 5.06 mmol allyl) and excess 13BDT (1.11 g, 15.6 mmol thiol) was stirred with TPOL (0.02 g) in a glass vial. The resulting colorless oil was precipitated into heptane, the upper heptane fraction was removed, and the product was washed three times with methanol to remove excess monomer. The product was obtained as a colorless, viscous liquid.

[0093] HBP 3 (vinyl-terminated)

[0094] Under UV irradiation (as described above), a mixture of 13BDT (0.36 g, 5.06 mmol thiol) and excess Si(vinyl)4 (0.54 g, 15.6 mmol vinyl) was stirred with TPOL (0.02 g) in a glass vial and separated into a colorless viscous liquid as described above for HBP 1.

[0095] HBP 4 (thiol-terminated)

[0096] Under UV irradiation (as described above), a mixture of Si(vinyl)4 (0.17 g, 5.06 mmol vinyl) and excess 13BDT (1.11 g, 15.6 mmol thiol) was stirred with TPOL (0.02 g) in a glass vial and separated into a colorless viscous liquid as described above for HBP 2.

[0097] HBP 5 (vinyl-terminated)

[0098] Under UV irradiation (as described above), a mixture of 13BDT (0.36 g, 5.06 mmol thiol) and excess TVCH (0.57 g, 10.5 mmol vinyl) was stirred with TPOL (0.02 g) in a glass vial and separated into a colorless, very viscous liquid as described above for HBP 1.

[0099] HBP 6 (thiol-terminated)

[0100] Under UV irradiation (as described above), a mixture of TVCH (0.17 g, 5.06 mmol vinyl) and excess 13BDT (0.75 g, 10.5 mmol thiol) was stirred with TPOL (0.02 g) in a glass vial and separated into a colorless, very viscous liquid as described above for HBP 2.

[0101] HBP 7 (vinyl-terminated)

[0102] Under UV irradiation (as described above), a mixture of 13BDMT (0.43 g, 5.06 mmol thiol) and excess Si(vinyl)4 (0.54 g, 15.6 mmol vinyl) was stirred with TPOL (0.02 g) in a glass vial and separated into a colorless viscous liquid as described above for HBP 1.

[0103] HBP 8 (thiol-terminated)

[0104] Under UV irradiation (as described above), a mixture of Si(vinyl)4 (0.17 g, 5.06 mmol vinyl) and excess 1,3-benzenedimethylthiol (1.32 g, 15.6 mmol thiol) was stirred with TPOL (0.02 g) in a glass vial and separated into a colorless viscous liquid as described above for HBP 2.

[0105] HBP 9 (vinyl-terminated)

[0106] Under UV irradiation (as described above), a mixture of DMPT (0.44 g, 5.06 mmol thiol) and excess Si(vinyl)4 (1.06 g, 30.9 mmol vinyl) was stirred with TPOL (0.02 g) in a glass vial and separated into a colorless viscous liquid as described above for HBP 1.

[0107] Gel permeation chromatography (GPC)

[0108] Solutions of various hyperbranched polymers at approximate concentrations of 1.5 mg / mL were prepared in toluene. The samples were vortexed on an orbital shaker for 12 hours. The sample solutions were filtered through a 0.45 µ PTFE injection filter and then analyzed by GPC. A liquid chromatography instrument (1260 LC, Agilent Technologies, Santa Clara, CA) was used with an Agilent “PLgel MIXED B + C” column at 40 °C, toluene eluent at 1.0 mL / min, an Agilent 1260 evaporative light scattering detector, and a polystyrene standard reference material with a narrow molecular weight distribution obtained under the trade name NIST SRM 705a.

[0109] Nuclear magnetic resonance (NMR) spectroscopy

[0110] Various hyperbranched polymers were analyzed as solutions in deuterated chloroform. NMR spectroscopy was performed using a Bruker AVANCE III 500MHz NMR spectrometer equipped with a CPBBO gradient cryopreservation probe, a Bruker B-ACS 60 autosampler, and Bruker Topspin 3.04 software. Spectra were analyzed using Advanced Chemistry Development software (Toronto, Canada). Analysis of chemical shifts and integrals in the proton spectra confirmed the formation of the target structures. For vinyl and allyl-terminated polymers, the end-group content (in mmol / g) was calculated by comparing the integrals associated with the end groups and the integrals associated with the internal polymer repeating units.

[0111] For the selected hyperbranched polymers synthesized above, the number-average molecular weight (Mn) determined by GPC and the amount of terminal olefins determined by NMR are reported in Table 2.

[0112]

[0113] Refractive index of liquid

[0114] The refractive index was measured using a refractometer (model: 334610, Milton Roy, Houston, TX). The liquid sample was sealed between two prisms, and the refractive index was measured at 589 nm using a sodium lamp at 20 °C. Results for various hyperbranched polymers are shown in Table 3.

[0115] Comparative Example 1 (C1)

[0116] M1 is used, which is one of the highest refractive index acrylates available and is a low-viscosity liquid.

[0117]

[0118] Curing agents

[0119] Examples 1 and 2 (E1-E2)

[0120] Hyperbranched polysulfide (0.5 g) was thoroughly mixed with TPO-L (0.015 g, 3% by weight). The colorless liquid formulation was cast onto a polyethylene terephthalate (PET) film using a Mayer rod (No. 10), and an LED system (CF1000 UV, available from Clearstone, Palo Alto, CA) was used at 395 nm and 100% intensity (corresponding to 319 mW / cm²). 2 UV curing for 5 minutes at a distance of 1 cm from the sample surface produces a transparent hard coating on PET.

[0121] Differential scanning calorimetry (DSC)

[0122] DSC samples for thermal analysis were prepared by weighing the material and loading it into an aluminum DSC sample pan (TA Instruments, New Castle, DE). The samples were analyzed using a TA Instruments Discovery differential scanning calorimeter in standard mode (10 °C / min from -155 °C to approximately 150 °C). After data collection, the thermal transition was analyzed using TA Instruments' general analysis procedures. The glass transition temperature (Tg) was assessed using the step change in the standard heat flux (HF) profile. The midpoint (half-high) temperature of the second thermal transition was reported.

[0123] Refractive index of solids

[0124] The refractive index of the surface coating was determined by measuring samples E1-E2 at 450 nm using a digital prism coupler (model 2010, Metricon Inc., Pennington, NJ).

[0125] Table 4 reports the Tg of both the colorless liquid formulation and the cured transparent hard coating of the identified samples, as well as the refractive index of the cured transparent hard coating.

[0126]

[0127] As shown in Table 4 above, both HBP 1 (allyl-terminated hyperbranched polysulfide) and HBP 7 (vinyl-terminated hyperbranched polysulfide) are self-curing, showing an increase in Tg after curing.

[0128] Comparative Example 2 (C2)

[0129] As described in U.S. Patent 11,584,863 (Schwartz et al.) for Example 4, acrylate formulation C2 is prepared from M1 and M2 in a weight ratio of 95 to 5.

[0130] Examples 3 and 4 (E3-E4)

[0131] The thiol-olefin formulation was prepared from a mixture of thiol (SH)-terminated HBP and an olefin-terminated analog HBP in a 1:1 functional group ratio. TPO-L was added at 3% by weight, and the formulation was thoroughly mixed. The liquid formulation was cast onto a polyethylene terephthalate (PET) film using a Mayer rod (No. 10), and an LED system (CF1000 UV, available from Clearstone, Palo Alto, CA) was used at 395 nm, 100% intensity (corresponding to 319 mW / cm²). 2 UV curing for 2 minutes at a distance of 1 cm from the sample surface produces a transparent hard coating on PET.

[0132] The refractive index of the cured transparent hard coating of various samples was tested using the solid refractive index method described above, and the results are reported in Table 5.

[0133]

[0134] 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 hyperbranched polysulfide comprising a plurality of terminal carbon-carbon double bonds or thiol groups, the hyperbranched polysulfide having a refractive index of at least 1.600 and a number-average molecular weight of at least 1000 g / mol and at most 5000 g / mol.

2. The hyperbranched polysulfide according to claim 1, wherein the hyperbranched polysulfide further comprises phenyl groups.

3. The hyperbranched polysulfide according to any one of the preceding claims, wherein the hyperbranched polysulfide contains at least 20% by weight of sulfur atoms.

4. The hyperbranched polysulfide according to any one of the preceding claims, wherein the hyperbranched polysulfide is a reaction product of at least one unsaturated compound and at least one organothiol, wherein the at least one unsaturated compound independently has p vinyl or allyl groups and is composed of C, H and optionally Si and / or O atoms, wherein each p is an integer greater than or equal to 2; wherein the at least one organothiol has q thiol groups and is composed of C, H, S and optionally O and / or N atoms, wherein each q is an integer greater than or equal to 2, wherein p+q is greater than 4.

5. The hyperbranched polysulfide according to claim 4, wherein the at least one unsaturated compound is independently represented by the following formula: Si(OSiR 2 2CH=CH2) b (R 2 CH=CH2) c (R 1 ) d Each R2 is independently a direct bond or an alkylene group having 1 to 12 carbon atoms, each R1 is independently a hydrocarbon 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, provided that b+c≥2 and b+c+d=4.

6. The hyperbranched polysulfide according to any one of claims 4 to 5, wherein the at least one unsaturated compound is an organosilane selected from the group consisting of: tetravinylsilane; tetraallylsilane; 1,2,4-trivinylcyclohexane; and combinations thereof.

7. The hyperbranched polysulfide according to any one of claims 4 to 6, wherein R 1 and R 3 It contains optionally substituted phenyl groups.

8. The hyperbranched polysulfide according to any one of claims 4 to 7, wherein the at least one organic thiol comprises a divalent aromatic compound and is independently represented by the formula HS-R4-Ar-R4-SH, wherein each R4 is independently a direct bond or an alkylene group having 1 to 12 carbon atoms, and Ar is an arylene group comprising C, H and optionally S or N atoms.

9. The hyperbranched polysulfide according to claim 8, wherein the at least one organic thiol is selected from the group consisting of: 1,3-benzenedithiol; 1,3-benzenedialkylthiol; or combinations thereof.

10. The hyperbranched polysulfide according to any one of claims 4 to 7, wherein the at least one organic thiol comprises 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-dithiane; tetra(ethylene glycol) dithiol; 2,2'-(ethylenedioxy)diethanedithiol; pentaerythritol tetra(3-mercaptopropionate); trimethylolpropane tri(3-mercaptopropionate); ; ;or Their combination.

11. A method for preparing hyperbranched polysulfide, the method comprising mixing: at least one unsaturated compound, said at least one unsaturated compound independently having p vinyl or allyl groups and consisting of C, H and optionally Si and / or O atoms, wherein each p is an integer greater than or equal to 2; and At least one organic thiol, said at least one organic thiol having q thiol groups and consisting of C, H, S and optionally O and / or N atoms, wherein each q is independently an integer greater than or equal to 2.

12. A curable composition, said curable composition comprising: (i) the hyperbranched polysulfide according to any one of claims 1 to 11; and (ii) at least one multifunctional compound, wherein components (i) and (ii) react via a thiol-ene reaction; and The curable composition is substantially solvent-free.

13. The curable composition of claim 12, wherein the terminal functional groups of the hyperbranched polysulfide comprise carbon-carbon double bonds, and the at least one multifunctional compound comprises a plurality of terminal thiol groups.

14. The curable composition according to claim 13, wherein the at least one polyfunctional compound comprising a plurality of terminal thiol groups is an aromatic polythiol.

15. The curable composition according to claim 13, wherein the at least one polyfunctional compound comprising a plurality of terminal thiol groups is 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; 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetra(3-mercaptopropionate), trimethylolpropane tri(3-mercaptopropionate), or combinations thereof.

16. The curable composition of claim 12, wherein the terminal functional groups of the hyperbranched polysulfide comprise thiol groups, and the at least one multifunctional compound comprises a plurality of terminal carbon-carbon double bonds.

17. The curable composition of claim 16, wherein the at least one polyfunctional compound comprising a plurality of terminal carbon-carbon double bonds is a hyperbranched polysulfide, tetravinylsilane, tetraallylsilane, trivinylcyclohexane, and combinations thereof.

18. The curable composition according to any one of claims 12 to 17, wherein the at least one multifunctional compound is a hyperbranched polythiol ether according to any one of claims 1 to 11.

19. The curable composition according to any one of claims 12 to 18, wherein the ratio of thiol groups to terminal carbon-carbon double bonds is from 1:0.8 to 0.8:

1.

20. The curable composition according to any one of claims 12 to 19, wherein the curable composition further comprises a free radical initiator.

21. A curable composition comprising: (i) the hyperbranched polysulfide according to any one of claims 1 to 11, wherein the hyperbranched polysulfide comprises a plurality of terminal carbon-carbon double bonds; (ii) Free radical initiators; and (iii) Optionally, at least one multifunctional compound comprising multiple terminal carbon-carbon double bonds; and The curable composition is substantially solvent-free.

22. The curable composition of claim 21, wherein the multifunctional compound is a hyperbranched polysulfide comprising a plurality of terminal carbon-carbon double bonds according to any one of claims 1 to 11.

23. The curable composition of claim 22, wherein the curable composition comprises at least two hyperbranched polysulfides with different compositions, wherein the at least two hyperbranched polysulfides with different compositions comprise a plurality of terminal carbon-carbon double bonds.

24. The curable composition according to any one of claims 12 to 23, wherein the curable composition, after curing, has a refractive index greater than or equal to 1.660 (measured at 450 nm).

25. The curable composition according to any one of claims 12 to 24, wherein the curable composition further comprises an inhibitor.

26. The curable composition according to any one of claims 12 to 25, wherein the curable composition further comprises a heat stabilizer.

27. The curable composition according to any one of claims 12 to 26, wherein the curable composition further comprises an adhesion promoter.

28. The curable composition according to any one of claims 12 to 27, wherein the curable composition has a viscosity of 100 cp or less in a temperature range of room temperature to 35°C.

29. An article of manufacture comprising: A substrate having a first main surface and a second main surface; A cured organic layer, said cured organic layer being adjacent to at least a portion of the second main surface of the substrate, wherein said cured organic layer is derived from a curable composition according to any one of claims 12 to 28; and An inorganic barrier layer is in contact with the cured organic layer, wherein the cured organic layer has a refractive index greater than or equal to 1.660 (measured at 450 nm).

30. The article of claim 29, wherein the cured organic layer is optically transparent.

31. The article of any one of claims 29 to 30, wherein the cured organic layer has at least 5 The glass transition temperature of C.

32. The article of any one of claims 29 to 31, wherein the cured organic layer has a thickness of 5 micrometers to 30 micrometers and a surface roughness of less than or equal to 5 nanometers.

33. The article of any one of claims 29 to 32, wherein the article of any one further comprises a device disposed on a second main surface of the substrate and adjacent to the cured organic layer.

34. The article of manufacture according to claim 33, wherein the device comprises an OLED (organic light-emitting diode).

35. A method for preparing an article of articles, the method comprising: A substrate having a first main surface and a second main surface is provided; Provide a curable composition according to any one of claims 12 to 28; The curable composition is disposed on at least a portion of the second main surface of the 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 1.660 measured at 450 nm; and An inorganic barrier layer is deposited on the cured organic layer.

36. The method of claim 35, wherein depositing the curable composition on the second primary surface of the substrate to form a curable layer comprises inkjet printing to a thickness of 5 micrometers to 30 micrometers.

37. The method of any one of claims 35 to 36, the method further comprising providing a device; and disposing the device on the second main surface of the substrate prior to disposing the curable composition on the second main surface of the substrate to form a curable layer.

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