Composition

Abstract

The present invention relates to compositions containing mono- or polycycloolefin-like compounds.

Description

[Technical Field]

[0001] The present invention relates to compositions containing mono- or polycycloolefin-like compounds. The present invention further relates to methods for producing films, films, devices, and uses of the compounds. [Background technology]

[0002] Electronic devices, especially organic electronic devices, are becoming thinner every year and are generally encapsulated in an optically transparent insulating material.

[0003] US Pat. No. 9,944,818 discloses a two-component bulk polymerizable composition that can be tailored to a desired refractive index and is suitable as a filler and protective coating material.

[0004] US Pat. No. 1,123,0624 discloses polycycloolefin monomers and catalysts activated by compounds capable of generating photoacid as 3D printing materials. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] 1. U.S. Patent No. 9,944,818 [Patent Document 2] 2. U.S. Patent No. 1,123,0624 Summary of the Invention

[0006] However, the present inventors have newly discovered that there still exist one or more important problems that require improvement, such as the following: Higher transparency of the composition and / or the resulting film at visible light wavelengths, lower haze values ​​of the resulting film, lower dielectric constants of the composition and the resulting film, for example, a dielectric constant of less than 3 and low loss of less than 0.001 at high frequencies such as above 50 GHz, lower dielectric constants of the composition and the resulting film, improved touch sensitivity of the resulting film, high refractive index, good mechanical properties of the resulting film against mechanical stress such as folding and bending, good cure rate of the composition, and good thermal properties.

[0007] The inventors aimed to solve one or more of the problems set forth above.

[0008] The inventors have surprisingly found that one or more of the above mentioned technical problems can be solved by the features defined in the claims.

[0009] That is, a) Formula (I): [ka] [In the formula, m is an integer of 0, 1, or 2; R1, R2, R3 and R4 are the same or different and are selected from the group consisting of hydrogen, halogen, methyl, ethyl, straight or branched chain (C3-C 16 ) alkyl, perfluoro(C1-C 12 ) alkyl, hydroxy (C1-C 16 ) Alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) Bicycloalkyl, (C7-C 14 ) tricycloalkyl, (C6-C 10 ) Aryl, (C6-C 10 ) aryl(C1-C6) alkyl, perfluoro(C6-C 10 ) Aryl, Perfluoro(C6-C 10 ) aryl(C1-C6) alkyl, tri(C1-C6) alkoxysilyl, and a compound of formula (A): -Z 1 -aryl (A) (In the formula, Z 1 is a bond, or (CR5R6) a , O(CR5R6) a , (CR5R6) a O, (CR5R6) a -O-(CR5R6) b , (CR5R6) a -O-(SiR5R6) b , (CR5R6) a -(CO)O-(CR5R6) b , (CR5R6) a -O(CO)-(CR5R6) b , (CR5R6) a -(CO)-(CR5R6) b wherein a and b are integers which may be the same or different and each independently represent an integer of 1 to 12; R5 and R6 are the same or different and are each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C3-C6) alkyl, hydroxy, methoxy, ethoxy, linear or branched (C3-C6) alkyloxy, acetoxy, (C2-C6) acyl, hydroxymethyl, hydroxyethyl, linear or branched hydroxy (C3-C6) alkyl, phenyl, and phenoxy; wherein aryl is each independently selected from the group consisting of phenyl or phenyl substituted with one or more groups selected from the group consisting of methyl, ethyl, straight or branched chain (C3-C6) alkyl, hydroxy, methoxy, ethoxy, straight or branched chain (C3-C6) alkyloxy, acetoxy, (C2-C6) acyl, hydroxymethyl, hydroxyethyl, straight or branched chain hydroxy(C3-C6) alkyl, phenyl, and phenoxy; b) organoruthenium compounds, preferably of formula (II): [ka] [In the formula, c and d are integers from 0 to 5; Z is oxygen or sulfur; R7 is hydrogen, (C1 to C 20 ) Alkyl, (C2-C 20 ) alkenyl, (C2-C 20 ) alkynyl and (C6-C 10 ) aryl; R8, R9, R 10 and R 11 are the same or different and are hydrogen, halogen, (C1 to C 16 ) alkyl, (C1-C 16 ) alkoxy, (C1-C 16 ) perfluoroalkyl, (C3-C7) cycloalkyl, (C2-C 16 ) alkenyl, (C6-C 14 ) Aryl, (C6-C 14 ) Perfluoroaryl, (C3-C 12 ) heterocyclyl, -OR 16 , -NO2, -COOH, -COOR 16 , -CONR 16 R 17 , -SO2NR 16 R 17 , -SO2R 16 , -CHO, -COR 16 each independently selected from the group consisting of: R 16 and R 17 are the same or different and are (C1-C6) alkyl, (C1-C6) perfluoroalkyl, (C6-C 14 ) Aryl, (C6-C 14 ) perfluoroaryl; or R8, R9, R 10 and R 11 two or more of, taken together with the carbon atoms to which they are attached, form a substituted or unsubstituted fused (C4-C8) carbocyclic ring or a substituted or unsubstituted fused aromatic ring; Each R 12 , R 13 and R 14 may be the same or different and independently represent hydrogen, halogen, (C1 to C 16 ) alkyl, (C1-C 16 ) alkoxy, (C1-C16 ) perfluoroalkyl, (C3-C7) cycloalkyl, (C2-C 16 ) alkenyl, (C6-C 14 ) Aryl, (C6-C 14 ) Perfluoroaryl, (C3-C 12 ) heterocyclyl, -OR 16 , -NO2, -COOH, -COOR 16 , -CONR 16 R 17 , -SO2NR 16 R 17 , -SO2R 16 , -CHO, -COR 16 and R 16 and R 17 are the same or different and are (C1-C6) alkyl, (C1-C6) perfluoroalkyl, (C6-C 14 ) Aryl, (C6-C 14 ) perfluoroaryl; R 15 is (C1~C 16 ) alkyl, (C1-C 16 ) Perfluoroalkyl, (C3-C 16 ) cycloalkyl, (C6-C 14 ) Aryl, (C6-C 14 ) Perfluoroaryl and (C3-C 12 ) heterocyclyl; Ar1 and Ar2 are the same or different and are each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthyl, and each of the substituents is independently selected from the group consisting of methyl, ethyl, and straight-chain or branched (C3-C6) alkyl; c) a photosensitizer, preferably a photosensitizer configured to convert the organoruthenium compound to an active form, preferably a photosensitizer of formula (III): [ka] [In the formula, Y is a halogen; R30 and R 31 are the same or different and independently represent hydrogen, methyl, ethyl, straight or branched chain (C3-C 12 ) Alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) Bicycloalkyl, (C7-C 14 ) tricycloalkyl, (C6-C 10 ) Aryl, (C6-C 10 )aryl(C1-C3)alkyl, (C1-C 12 )Alkoxy, (C3-C 12 ) cycloalkoxy, (C6-C 12 ) bicycloalkoxy, (C7-C 14 ) Tricycloalkoxy, (C6-C 10 )aryloxy(C1-C3)alkyl and (C6-C 10 a photosensitizer represented by the formula (I) selected from the group consisting of aryloxy, d) Formula (IV): [ka] [In the formula, p is an integer 0, 1 or 2; R e1 , R e2 , R e3 and R e4 are each independently hydrogen, halogen, methyl, ethyl, straight chain (C1-C 16 ) Alkyl or branched chain (C3-C 16 ) alkyl, perfluoro(C1-C 12 ) alkyl, hydroxy (C1-C 16 ) Alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) Bicycloalkyl, (C7-C 14 ) tricycloalkyl, (C6-C 10 ) Aryl, (C6-C 10 ) aryl(C1-C6) alkyl, perfluoro(C6-C 10 ) Aryl, Perfluoro(C6-C 10) aryl(C1-C6) alkyl, tri(C1-C6) alkoxysilyl, vinyl group, acrylate group, methacrylate group and allyl group, linear (C1-C) alkyl having a vinyl group, acrylate group, methacrylate group or allyl group as a terminal group 16 ) Alkyl or branched chain (C3-C 16 ) alkyl; R e1 , R e2 , R e3 and R e4 At least one of the above is a vinyl group, an acrylate group, a methacrylate group, an allyl group, or a linear (C1-C) copolymer having a vinyl group, an acrylate group, a methacrylate group, or an allyl group as a terminal group. 16 ) Alkyl or branched chain (C3-C 16 ) alkyl. DETAILED DESCRIPTION OF THE INVENTION

[0010] Terms used in this document have the following meanings: As used herein, the articles "a," "an," and "the" include plural referents unless otherwise expressly and unambiguously limited to one referent.

[0011] All numerical values, values ​​and / or expressions referring to quantities of ingredients, reaction conditions, and the like used in this specification and the appended claims are subject to various uncertainties of measurement encountered in obtaining such values ​​and, therefore, should be understood to be modified in all instances by the term "about" unless otherwise indicated.

[0012] When a range of numerical values ​​is disclosed herein, such range is continuous and includes both the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Furthermore, when a range refers to integers, every integer between the minimum and maximum values ​​of such range is included. Furthermore, when multiple ranges are provided to describe a feature or characteristic, such ranges are combinable. That is, unless otherwise indicated, all ranges disclosed herein should be understood to encompass every subrange subsumed therein.

[0013] For example, if a range of "1 to 10" is specified, it should be considered to include all subranges from a minimum of 1 to a maximum of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0014] As used herein, "hydrocarbyl" refers to a group containing carbon and hydrogen atoms, non-limiting examples being alkyl, cycloalkyl, aryl, aralkyl, alkaryl, and alkenyl. The term "halohydrocarbyl" refers to a hydrocarbyl group in which at least one hydrogen has been replaced with a halogen. The term perhalocarbyl refers to a hydrocarbyl group in which all hydrogens have been replaced with halogens.

[0015] As used herein, the term "alkyl" means a saturated, straight or branched chain hydrocarbon substituent having the specified number of carbon atoms. Particular alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like. Derived expressions such as "alkoxy," "thioalkyl," "alkoxyalkyl," "hydroxyalkyl," "alkylcarbonyl," "alkoxycarbonylalkyl," "alkoxycarbonyl," "diphenylalkyl," "phenylalkyl," "phenylcarboxyalkyl," and "phenoxyalkyl" should be construed accordingly.

[0016] As used herein, the term "cycloalkyl" includes all known cyclic groups. Representative examples of "cycloalkyl" include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Derived expressions such as "cycloalkoxy," "cycloalkylalkyl," "cycloalkylaryl," "cycloalkylcarbonyl," and the like, should be construed accordingly.

[0017] As used herein, the term "perhaloalkyl" refers to an alkyl group as defined above, wherein all hydrogen atoms in the alkyl group have been replaced with halogen atoms selected from fluorine, chlorine, bromine, or iodine. Illustrative examples include trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl, pentabromoethyl, pentaiodoethyl, and linear or branched heptafluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl, nonachlorobutyl, undecafluoropentyl, undecachloropentyl, tridecafluorohexyl, tridecachlorohexyl, and the like. The derivative expression "perhaloalkoxy" should be construed accordingly. Furthermore, it should be noted that certain alkyl groups described herein, such as "alkyl," may be partially fluorinated, i.e., only a portion of the hydrogen atoms in the alkyl group may be replaced with fluorine atoms, and should be construed accordingly.

[0018] As used herein, the term "acyl" has the same meaning as "alkanoyl," which may also be structurally represented as "R-CO-," where R is "alkyl" as defined herein having the specified number of carbon atoms. Furthermore, "alkylcarbonyl" has the same meaning as "acyl" as defined herein. Specifically, "(C1-C4)acyl" means formyl, acetyl or ethanoyl, propanoyl, n-butanoyl, etc. Derived expressions such as "acyloxy" and "acyloxyalkyl" should be construed accordingly.

[0019] As used herein, the term "aryl" refers to substituted or unsubstituted phenyl or naphthyl. Specific examples of substituted phenyl or naphthyl include o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, and the like. "Substituted phenyl" or "substituted naphthyl" also includes any of the substituents that may be further defined herein or known in the art.

[0020] As used herein, the term "arylalkyl" means an aryl, as defined herein, further attached to an alkyl, as defined herein. Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like.

[0021] As used herein, the term "alkenyl" means an acyclic straight or branched hydrocarbon chain having the specified number of carbon atoms and containing at least one carbon-carbon double bond, and includes ethenyl, and straight or branched propenyl, butenyl, pentenyl, hexenyl, and the like. Derived expressions "arylalkenyl" and 5- or 6-membered "heteroarylalkenyl" should be construed accordingly. Illustrative examples of such derived expressions include furan-2-ethenyl, phenylethenyl, 4-methoxyphenylethenyl, and the like.

[0022] As used herein, the term "heteroaryl" includes all of the known heteroatom containing aromatic groups. Representative 5-membered heteroaryl groups include furanyl, thienyl, or thiophenyl, pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl, and the like.

[0023] Representative 6-membered heteroaryl groups include groups such as pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, etc. Representative examples of bicyclic heteroaryl groups include groups such as benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, cinnolyl, benzimidazolyl, indazolyl, pyridofuranyl, pyridothienyl, etc.

[0024] "Halogen" or "halo" means chloro, fluoro, bromo, or iodo.

[0025] In a broad sense, the term "substituted" is intended to include all permissible substituents of organic compounds. In certain specific embodiments disclosed herein, the term "substituted" means substituted with one or more substituents independently selected from the group consisting of (C-C) alkyl, (C-C) alkenyl, (C-C) perfluoroalkyl, phenyl, hydroxy, -COH, ester, amido, (C-C) alkoxy, (C-C) thioalkyl, and (C-C) perfluoroalkoxy. However, any other suitable substituents known to those of ordinary skill in the art can be used in these embodiments.

[0026] It should be noted that in the text, schemes, examples and tables herein, atoms with unsatisfied valences are assumed to have the appropriate number of hydrogen atoms to satisfy such valences.

[0027] The term "latent organotransition metal catalyst" refers to an organotransition metal compound that exhibits little or no catalytic activity at a particular temperature (usually at ambient atmospheric conditions) and that initiates such activity with either heat or light, or both. Generally, the catalytic activity of the catalyst can remain latent for extended periods of time, such as 5 days or more, especially when stored in the dark at or below room temperature. Higher temperatures and / or light may enhance catalytic activity.

[0028] The term "actinic radiation" or "photolytic conditions" means subjecting the compositions of the present invention to suitable "electromagnetic radiation," which may be emitted from a laser, a digital processing (DLP) projector, a lamp, a light emitting diode (LED), a mercury arc lamp, fiber optics, or a liquid crystal display (LCD), or the like.

[0029] The terms "dielectric" and "insulating" should be understood to be used interchangeably herein. Thus, a reference to an insulating material or insulating layer includes a dielectric material or layer, and vice versa. Furthermore, as used herein, the term "organic electronic device" should be understood to include the term "organic semiconductor device," as well as certain specific implementations of such devices used, for example, in the electronics, automotive, or other industries.

[0030] As used herein, the dielectric constant (Dk) of a material is the ratio of the charge stored in an insulating material placed between two metal plates to the charge that can be stored when the insulating material is replaced by a vacuum or air. It is also called the electrical permittivity or simply the dielectric constant. It is also sometimes called the relative permittivity, since it is measured relative to the permittivity of free space.

[0031] As used herein, "low loss" refers to the dissipation factor (Df), which is a measure of the rate of energy loss of a vibration mode (mechanical, electrical, electromechanical) in a dissipative system. It is the inverse of the quality factor and represents the "quality" or durability of the vibration.

[0032] The term "derivative" means that a polymer repeat unit is polymerized (formed) from a polycyclic norbornene-type monomer, for example, according to formula (I), (V), or (VI), and the resulting polymer is subjected to ring-opening metathesis polymerization (ROMP), e.g., the 2,3 double bond of the norbornene-type monomer is ring-opened and polymerized as shown below: [ka] Thus, according to the practice of the present invention: a) Formula (I): [ka] [In the formula, m is an integer of 0, 1, or 2; R1, R2, R3 and R4 are the same or different and are selected from the group consisting of hydrogen, halogen, methyl, ethyl, straight or branched chain (C3-C 16 ) alkyl, perfluoro(C1-C 12 ) alkyl, hydroxy (C1-C 16 ) Alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) Bicycloalkyl, (C7-C 14 ) tricycloalkyl, (C6-C 10 ) Aryl, (C6-C 10 ) aryl(C1-C6) alkyl, perfluoro(C6-C 10 ) Aryl, Perfluoro(C6-C 10 ) aryl(C1-C6) alkyl, tri(C1-C6) alkoxysilyl, and a compound of formula (A): -Z-aryl(A) (In the formula, Z is a bond or (CR5R6) a , O(CR5R6) a , (CR5R6) a O, (CR5R6) a -O-(CR5R6) b , (CR5R6) a -O-(SiR5R6) b , (CR5R6) a -(CO)O-(CR5R6)b , (CR5R6) a -O(CO)-(CR5R6) b , (CR5R6) a -(CO)-(CR5R6) b wherein a and b are integers which may be the same or different and each independently represent an integer of 1 to 12; R5 and R6 are the same or different and are each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C3-C6) alkyl, hydroxy, methoxy, ethoxy, linear or branched (C3-C6) alkyloxy, acetoxy, (C2-C6) acyl, hydroxymethyl, hydroxyethyl, linear or branched hydroxy (C3-C6) alkyl, phenyl, and phenoxy; wherein aryl is each independently selected from the group consisting of phenyl or phenyl substituted with one or more groups selected from the group consisting of methyl, ethyl, straight or branched chain (C3-C6) alkyl, hydroxy, methoxy, ethoxy, straight or branched chain (C3-C6) alkyloxy, acetoxy, (C2-C6) acyl, hydroxymethyl, hydroxyethyl, straight or branched chain hydroxy(C3-C6) alkyl, phenyl, and phenoxy; b) organoruthenium compounds, preferably of formula (II): [ka] [In the formula, c and d are integers from 0 to 5; Z is oxygen or sulfur; R7 is hydrogen, (C1 to C 20 ) Alkyl, (C2-C 20 ) alkenyl, (C2-C 20 ) alkynyl and (C6-C 10 ) aryl; R8, R9, R 10 and R 11 are the same or different and are hydrogen, halogen, (C1 to C 16 ) alkyl, (C1-C 16 ) alkoxy, (C1-C16 ) perfluoroalkyl, (C3-C7) cycloalkyl, (C2-C 16 ) alkenyl, (C6-C 14 ) Aryl, (C6-C 14 ) Perfluoroaryl, (C3-C 12 ) heterocyclyl, -OR 16 , -NO2, -COOH, -COOR 16 , -CONR 16 R 17 , -SO2NR 16 R 17 , -SO2R 16 , -CHO, -COR 16 R 16 and R 17 are the same or different and are (C1-C6) alkyl, (C1-C6) perfluoroalkyl, (C6-C 14 ) Aryl, (C6-C 14 ) perfluoroaryl; or R8, R9, R 10 and R 11 two or more of, taken together with the carbon atoms to which they are attached, form a substituted or unsubstituted fused (C4-C8) carbocyclic ring or a substituted or unsubstituted fused aromatic ring; Each R 12 , R 13 and R 14 may be the same or different and independently represent hydrogen, halogen, (C1 to C 16 ) alkyl, (C1-C 16 ) alkoxy, (C1-C 16 ) perfluoroalkyl, (C3-C7) cycloalkyl, (C2-C 16 ) alkenyl, (C6-C 14 ) Aryl, (C6-C 14 ) Perfluoroaryl, (C3-C 12 ) heterocyclyl, -OR 16 , -NO2, -COOH, -COOR 16 , -CONR 16 R 17 , -SO2NR 16 R17 , -SO2R 16 , -CHO, -COR 16 and R 16 and R 17 are the same or different and are (C1-C6) alkyl, (C1-C6) perfluoroalkyl, (C6-C 14 ) Aryl, (C6-C 14 ) perfluoroaryl; R 15 is (C1~C 16 ) alkyl, (C1-C 16 ) Perfluoroalkyl, (C3-C 16 ) cycloalkyl, (C6-C 14 ) Aryl, (C6-C 14 ) Perfluoroaryl and (C3-C 12 ) heterocyclyl; Ar1 and Ar2 are the same or different and are each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthyl, and each of the substituents is independently selected from the group consisting of methyl, ethyl, and straight-chain or branched (C3-C6) alkyl; c) a photosensitizer, preferably a photosensitizer configured to convert the organoruthenium compound to an active form, preferably a photosensitizer of formula (III): [ka] [In the formula, Y is a halogen; R 30 and R 31 are the same or different and independently represent hydrogen, methyl, ethyl, straight or branched chain (C3-C 12 ) Alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) Bicycloalkyl, (C7-C 14 ) tricycloalkyl, (C6-C 10 ) Aryl, (C6-C 10 )aryl(C1-C3)alkyl, (C1-C12 )Alkoxy, (C3-C 12 ) cycloalkoxy, (C6-C 12 ) bicycloalkoxy, (C7-C 14 ) Tricycloalkoxy, (C6-C 10 )aryloxy(C1-C3)alkyl and (C6-C 10 a photosensitizer represented by the formula (I) selected from the group consisting of aryloxy, d) Formula (IV): [ka] [In the formula, p is an integer 0, 1 or 2; R e1 , R e2 , R e3 and R e4 are each independently hydrogen, halogen, methyl, ethyl, straight chain (C1-C 16 ) Alkyl or branched chain (C3-C 16 ) alkyl, perfluoro(C1-C 12 ) alkyl, hydroxy (C1-C 16 ) Alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) Bicycloalkyl, (C7-C 14 ) tricycloalkyl, (C6-C 10 ) Aryl, (C6-C 10 ) aryl(C1-C6) alkyl, perfluoro(C6-C 10 ) Aryl, Perfluoro(C6-C 10 ) aryl(C1-C6) alkyl, tri(C1-C6) alkoxysilyl, vinyl group, acrylate group, methacrylate group and allyl group, linear (C1-C) alkyl having a vinyl group, acrylate group, methacrylate group or allyl group as a terminal group 16 ) Alkyl or branched chain (C3-C 16 ) alkyl; R e1 , R e2 , R e3 and R e4At least one of the above is a vinyl group, an acrylate group, a methacrylate group, an allyl group, or a linear (C1-C) copolymer having a vinyl group, an acrylate group, a methacrylate group, or an allyl group as a terminal group. 16 ) Alkyl or branched chain (C3-C 16 ) alkyl].

[0033] composition Preferably, the compositions of the present invention are stable over a temperature range of from room temperature to 80° C., and are therefore believed to provide excellent shelf-life stability. As used herein, "stable" means that the compositions of the present invention remain clear without increasing in viscosity when stored at temperatures ranging from room temperature to 80° C., particularly when stored in the dark and away from light, for example, in an amber or brown container. Thus, in some embodiments, the compositions of the present invention do not exhibit a change in viscosity when stored at temperatures below 80° C. for more than 30 days.

[0034] Thus, in some embodiments, the compositions of the present invention exhibit less than a 5 percent increase in viscosity when stored for more than 40 days at temperatures below 80° C. In some other embodiments, the compositions of the present invention exhibit less than a 10 percent change in viscosity when stored for 60 to 90 days at temperatures below 80° C.

[0035] In some other embodiments, the compositions of the present invention exhibit less than a 20 percent change in viscosity when stored for 120 to 180 days at temperatures below 80° C. In some other embodiments, the compositions of the present invention exhibit less than a 2 percent change in viscosity when stored at ambient temperatures, e.g., about 20° C. to 25° C., for extended periods of time, which can range from about 120 to 300 days or more.

[0036] That is, the viscosity of the composition remains essentially unchanged when stored under ambient conditions, but the composition undergoes bulk polymerization upon exposure to suitable actinic radiation, as evidenced by UV-DSC measurements disclosed earlier herein, which showed that the heat of polymerization remained unchanged even after the composition was stored for extended periods of time.

[0037] The monomers used in the compositions of the present invention are per se known in the literature, that is to say, can be prepared by any of the methods known in the art for producing such monomers or similar types of monomers.

[0038] Furthermore, the monomers described herein readily undergo bulk polymerization without the use of solvents, i.e., neat, when polymerized under bulk ring-opening metathesis polymerization (ROMP) conditions using certain transition metal catalysts, such as organoruthenium and organosmium compounds. See, e.g., R.H. Grubbs et al., Handbook of Metathesis, Ed.: Wiley-VCH, Weinheim, Germany, 2003; R.H. Grubbs et al., Acc. Chem. Res. 2001, 34, 18-29; R.H. Grubbs et al., Angew. Chem. Int. Ed., 2006, 45, 3760-3765. See also U.S. Pat. No. 6,838,489, the relevant portions of which are incorporated herein by reference. As used herein, the term "bulk polymerization" has its generally accepted meaning in the art, i.e., a polymerization reaction generally conducted substantially in the absence of a solvent.

[0039] However, in some cases, a small amount of solvent may be present in the reaction medium. For example, such a small amount of solvent may be used to dissolve or carry the latent catalyst and / or activator into the reaction medium. A solvent may also be used to reduce the viscosity of the monomer. The amount of solvent that can be used in the reaction medium may range from 0 to 5 weight percent based on the total weight of the monomers used. Any suitable solvent that dissolves the catalyst, activator, and / or monomer may be used in the present invention. Examples of such solvents include alkanes, cycloalkanes, toluene, THF, dichloromethane, dichloroethane, etc.

[0040] Advantageously, it has now been found that one or more monomers themselves can be used to dissolve the latent catalyst and activator, eliminating the need for a solvent. Furthermore, one monomer itself functions as a solvent for the other monomer, eliminating the need for an additional solvent. For example, if a first monomer of formula (I) is solid at room temperature, a second monomer of formula (I) that is liquid at room temperature can be used as a solvent for the first monomer of formula (I) that is solid, and vice versa. Therefore, in such a situation, two or more monomers can be used in the composition of the present invention.

[0041] Generally, the compositions of the present invention exhibit low viscosity at room temperature, which can be 100 centipoise or less. In some embodiments, the viscosity of the compositions of the present invention at room temperature is less than 80 centipoise. In some other embodiments, the viscosity of the compositions of the present invention at room temperature is in the range of about 10 to 100 centipoise. In yet some other embodiments, the viscosity of the compositions of the present invention at room temperature is less than 70 cP, less than 60 cP, less than 40 cP, or less than 20 cP. In some other embodiments, the viscosity may be less than 10 cP, and can vary from 3 cP to 9 cP at room temperature.

[0042] Therefore, the compositions of the present invention can also contain other highly refractive polymeric materials and / or nanoparticles that provide such intended benefits. Examples of such polymers include, but are not limited to, poly(methylstyrene), poly(vinyl-toluene), copolymers of methylstyrene and vinyl-toluene, etc. Examples of such nanoparticles include, but are not limited to, organic or inorganic nanoparticles ranging in size from 1 to 100 nm, including materials such as crosslinked poly(styrene), crosslinked poly(methacrylate), metal oxides (e.g., zinc oxide, magnesium oxide, titanium oxide), silicon, silicon oxide, silicon nitride, and luminescent materials (e.g., III-V semiconductor nanoparticles such as indium phosphide).

[0043] Compounds of formula (I): In some embodiments of the present invention, the refractive index of the monomer of Formula (I) is 1.5 or greater. In some other embodiments, the refractive index of the monomer of Formula (I) is in the range of about 1.5 to 1.6. In yet some other embodiments, the refractive index of the monomer of Formula (I) is 1.55 or greater, 1.6 or greater, or 1.65 or greater. In some other embodiments, it may be 1.7 or greater. Preferably, it is 2.0 or less.

[0044] The monomer of formula (I) is also believed to function as a high refractive index material, imparting a high refractive index to the resulting polymer film by bulk polymerization at a temperature and / or conditions different from those when the composition is applied to the desired substrate.

[0045] When the compositions of the present invention contain two or more monomers, they can be present in any desired amount that provides the intended benefit, including, for example, either refractive index modification or viscosity modification, or both.

[0046] Generally, compositions according to the present invention include one or more of the monomers of formula (I) described above, and optionally additional monomers of formula (I) that are different from one another, and as will be seen below, various composition embodiments are selected to provide such embodiments with properties that are appropriate and desirable for the application for which such embodiments are intended, and thus such embodiments can be tailored to various specific applications.

[0047] For example, as already mentioned above, by appropriately combining the characteristic monomers of formula (I), it is possible to tailor compositions with desired refractive index, viscosity, and optical transmission properties. Additionally, as further described herein, it may be desirable to include other polymeric or monomeric materials, such as inorganic nanoparticles, that are compatible with providing the desired optical properties depending on the end use application.

[0048] Thus, in a preferred embodiment of the present invention, the monomer of formula (I) is: [ka] 5-(4-phenylbutyl)bicyclo[2.2.1]hept-2-ene; [ka] 5-(3-phenylpropyl)bicyclo[2.2.1]hept-2-ene; [ka] 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB); [ka] 5-(benzyloxy)bicyclo[2.2.1]hept-2-ene; [ka] 5-(2-([1,1'-biphenyl]-4-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene; [ka] 5-(2-([1,1'-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtO-2-PhPh); [ka] 5-butylbicyclo[2.2.1]hept-2-ene (BuNB); [ka] 5-Hexylbicyclo[2.2.1]hept-2-ene (HexylNB); [ka] 5-octylbicyclo[2.2.1]hept-2-ene (OctNB); [ka] 5-decylbicyclo[2.2.1]hept-2-ene (DecNB); [ka] 5-Ethylidenebicyclo[2.2.1]hept-2-ene; [ka] 2-Ethylidene-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene; [ka] 3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene (one of the trimers of cyclopentadiene, also known as TCPD1, CPD3); [ka] 5-norbornenylmethyleugenyl acetate (EuAcNB); [ka] 5-norbornenylmethyleugenol (EuOHNB); [ka] NB(MeOH)2; [ka] PhAcNB; [ka] Tetracyclododecene (TD); [ka] 5-(phenoxymethyl)bicyclo[2.2.1]hept-2-ene (NBMeOPh); [ka] 5-(([1,1'-biphenyl]-2-yloxy)methyl)bicyclo[2.2.1]hept-2-ene (NBMeOPhPh); [ka] 2-phenyl-tetracyclododecene (PhTD); [ka] 2-benzyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene; [ka] 2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD); [ka] 2-Butyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (ButylTD); [ka] 2-Hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (HexylTD); [ka] 2-Octyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (OctylTD); [ka] 2-Decyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (DecylTD); [ka] 2-Cyclohexyl-tetracyclododecene (CyclohexylTD); [ka] 2-Cyclohexylmethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene; [ka] 2-Cyclohexylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene; [ka] (1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalen-2-yl)methyl acetate (TDMeOAc); and [ka] tetracyclododecadiene (TDD).

[0049] As mentioned above, preferably the monomer of formula (I) has a refractive index of at least 1.5. The composition is in the form of a clear liquid at room temperature.

[0050] Organoruthenium Compounds As described above, the compositions of the present invention contain at least one organoruthenium compound, preferably a compound represented by Formula (II), which, when subjected to suitable actinic radiation, undergoes bulk polymerization as described herein under ROMP conditions. Generally, such organoruthenium compounds, preferably compounds represented by Formula (II), are "latent" and only activate under specific conditions. As used herein, the term "latent" refers to the extended inactivity of the organoruthenium catalyst employed in the compositions of the present invention when the compositions are stored at ambient temperatures up to 80°C. Thus, in some embodiments, the organoruthenium catalyst remains latent for periods greater than 30 days when stored at temperatures below 80°C. In some other embodiments, the organoruthenium catalyst remains latent for periods of 40 to 90 days when stored at temperatures below 50°C.

[0051] Generally, any latent organoruthenium compound, preferably represented by formula (II), that effects ring-opening metathesis polymerization of monomers of formula (I), (V), or (VI) can be used in the compositions of the present invention. Interestingly, it has been found that organoruthenium compounds of formula (II) are highly stable at temperatures from about 25°C (i.e., ambient conditions) to about 80°C and can be stored, either alone or in the presence of one or more monomers of formula (I), (V), or (VI), for several days, even 3 to 6 months, or even longer. That is, organoruthenium compounds of formula (II) are preferably stable at or near room temperature up to 80°C and further function as latent catalysts that can be easily activated, only when necessary, by a variety of conditions, including, but not limited to, heat, acid, light, and chemical activation. Chemical activation may involve the use of a thermal or photoacid generator.

[0052] Some of the latent catalysts known in the literature are not stable under the conditions specified herein, and most of them do not exhibit the required shelf life stability as described herein. For example, Grubbs, et al., Organometallics, 2011, 30(24): 6713-6717; Sutar et al., Angew. al.,J.Mater.Chem.C.2015,3,693-702;Grubbs,et al.,J.Am.Chem.Soc.,2009,131,203802039;Zak,et al.,Eur.J.Inorg.Chem.,2014,1131-1136;Gawin,et al.,ACS Please refer to Catal.2017,7,5443-5449. Further examples of such catalysts can also be found in U.S. Patent No. 9,328,132, the relevant portions of which are incorporated herein by reference. Accordingly, compositions comprising organoruthenium compounds of formula (II) offer heretofore unattainable advantages in a variety of applications, such as those described herein.

[0053] According to the present invention, such organoruthenium compounds can be any publicly available one. Organoruthenium compounds such as those described in U.S. Pat. No. 1,123,0624 can also be used. Preferably, the organoruthenium compounds are of formula (II), wherein: Z is oxygen; R7 is hydrogen; R8, R9, R 10 and R 11 are the same or different and are each independently selected from the group consisting of hydrogen, methyl, ethyl, and —NO2; R 12 , R 13 and R 14 are the same or different and are each independently selected from the group consisting of hydrogen, methyl, ethyl, and —NO2; R 15is selected from the group consisting of methyl, ethyl, and cyclohexyl; Ar1 and Ar2 are the same or different and are each independently selected from the group consisting of phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di(isopropyl)phenyl, and 2,4,6-trimethylphenyl.

[0054] Thus, some exemplary latent catalysts within the scope of the organoruthenium compounds of formula (II) are: [ka] [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxide-κO}[2-(oxide-κO)benzylidene-κC]ruthenium(II) (Ru-I); [ka] [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]{2-[(E)-({2-[isopropylthio-κS]phenyl}imino-κN)methyl]phenoxide-κO}[2-(oxide-κO)benzylidene-κC]ruthenium(II) (Ru-2); [ka] [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]{2-[(E)-({2-[cyclohexylthio-κS]phenyl}imino-κN)methyl]phenoxide-κO}[2-(oxide-κO)benzylidene-κC]ruthenium(II) (Ru-3); and [ka] [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxide-κO}[2-(oxide-κO)benzylidene-κC]ruthenium(II) (Ru-4).

[0055] Interestingly, it has now been found that organoruthenium compounds of formula (II), when subjected to appropriate photolytic conditions, can be activated by certain known photoactive compounds (photosensitizers) to thereby promote the bulk polymerization of one or more monomers of formula (I) or (V) or (VI) included in the compositions of the present invention under ROMP conditions as described herein.

[0056] The total amount of the organoruthenium compounds is in the range of 0.001 to 1% by weight, preferably 0.005 to 0.5% by weight, more preferably 0.01 to 0.1% by weight, and even more preferably 0.02 to 0.05% by weight, based on the total amount of the compounds of formula (I).

[0057] Photosensitizers According to the present invention, the composition contains a photosensitizer, preferably a photosensitizer configured to activate the organoruthenium compound, preferably a photosensitizer represented by formula (III).

[0058] As the photosensitizer, known photoactive compounds such as substituted xanthone derivatives can be used. Preferably, the photosensitizer is represented by the structural formula (III): [ka] [In the formula, Y is a halogen; R 30 and R 31 are the same or different and independently represent hydrogen, methyl, ethyl, straight or branched chain (C3-C 12 ) Alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12) Bicycloalkyl, (C7-C 14 ) tricycloalkyl, (C6-C 10 ) Aryl, (C6-C 10 )aryl(C1-C3)alkyl, (C1-C 12 )Alkoxy, (C3-C 12 ) cycloalkoxy, (C6-C 12 ) bicycloalkoxy, (C7-C 14 ) Tricycloalkoxy, (C6-C 10 )aryloxy(C1-C3)alkyl and (C6-C 10 ) aryloxy].

[0059] In some embodiments, the compound of formula (III) has the following: Y is chlorine or bromine; R 30 and R 31 are the same or different and are independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, phenyl, cyclohexyl, methoxy, ethoxy, n-propoxy and phenoxy.

[0060] Representative examples of compounds of formula (VII) are: [ka] 1-chloro-4-methoxy-9H-thioxanthen-9-one; [ka] 1-chloro-4-ethoxy-9H-thioxanthen-9-one; [ka] 1-chloro-4-propoxy-9H-thioxanthen-9-one (commercially available from Lambson under the name CPTX); [ka] 1-chloro-2-propoxy-9H-thioxanthen-9-one; [ka] 1-chloro-2-ethoxy-9H-thioxanthen-9-one; [ka] 1-chloro-2-methoxy-9H-thioxanthen-9-one; [ka] 1-chloro-4-methyl-9H-thioxanthen-9-one; [ka] 1-chloro-4-ethyl-9H-thioxanthen-9-one; [ka] 1-Bromo-4-propoxy-9H-thioxanthen-9-one; and [ka] 1-chloro-4-phenoxy-9H-thioxanthen-9-one,

[0061] By using a suitable combination of organoruthenium compounds in combination with one or more photosensitizers (photosensitizers), it is believed that when the composition is subjected to suitable actinic radiation, generally at wavelengths of about 240 nm to 410 nm, bulk polymerization of the monomers can be induced, and the composition will undergo bulk ring-opening metathesis polymerization (ROMP) to form a transparent film or object. For this purpose, a combination of an organoruthenium compound of formula (II) and a photosensitizer of formula (III) is particularly suitable.

[0062] Preferably, the total amount of the photosensitizer (preferably represented by formula (III)) is in the range of 0.01 to 5% by weight, more preferably 0.05 to 1% by weight, and even more preferably 0.08 to 0.5% by weight, based on the total amount of the compound of formula (I).

[0063] In some embodiments, the compositions of the present invention undergo bulk polymerization upon exposure to suitable UV radiation to form a substantially transparent film. The monomers undergo bulk polymerization to form a film that is substantially transparent to visible light, i.e., a large portion of visible light is transmitted through the film. In some embodiments, such films formed from the compositions of the present invention exhibit a visible light transmittance of 90 percent or more. In some other embodiments, such films formed from the compositions of the present invention exhibit a visible light transmittance of 95 percent or more.

[0064] Thus, in some embodiments, the compositions of the present invention can be bulk polymerized to form a solid object, such as a transparent film, in less than 5 seconds after exposure to suitable actinic radiation. In some other embodiments, the compositions of the present invention can be bulk polymerized to form a solid object, such as a transparent film, in less than 10 seconds after exposure to suitable actinic radiation. In yet some other embodiments, the compositions of the present invention can be bulk polymerized to form a solid object, such as a transparent film, in 1-10 seconds, 2-9 seconds, 3-8 seconds, 4-7 seconds, etc. after exposure to suitable actinic radiation.

[0065] In yet another embodiment, the compositions of the present invention undergo bulk polymerization to form a substantially transparent film or object when exposed to suitable UV radiation at temperatures between 80°C and 100°C.

[0066] In some embodiments, the photosensitizer, preferably represented by Formula (III), can be activated by a specific wavelength of electromagnetic radiation, which can range from approximately 240 nm to 400 nm. Accordingly, any compound active at this electromagnetic radiation can be used in the compositions of the present invention. In some embodiments, the wavelength of radiation for activating the photosensitizer, preferably represented by Formula (III), is 260 nm. In some other embodiments, the wavelength of radiation for activating the photosensitizer is 310 nm. In yet some other embodiments, the wavelength of radiation for activating the photosensitizer is 395 nm.

[0067] However, any other known photosensitizer capable of activating the latent organoruthenium compounds used herein can be used in the compositions of the present invention, and all such compounds are part of the present invention.

[0068] Compound of formula (IV) According to the present invention, the composition comprises a compound of formula (IV): [ka] [In the formula, p is an integer 0, 1 or 2; R e1 , R e2 , R e3 and R e4 are each independently hydrogen, halogen, methyl, ethyl, straight chain (C1-C 16 ) Alkyl or branched chain (C3-C 16 ) alkyl, perfluoro(C1-C 12 ) alkyl, hydroxy (C1-C 16 ) Alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) Bicycloalkyl, (C7-C 14 ) tricycloalkyl, (C6-C 10 ) Aryl, (C6-C 10 ) aryl(C1-C6) alkyl, perfluoro(C6-C 10 ) Aryl, Perfluoro(C6-C10 ) aryl(C1-C6) alkyl, tri(C1-C6) alkoxysilyl, vinyl group, acrylate group, methacrylate group and allyl group, linear (C1-C) alkyl having a vinyl group, acrylate group, methacrylate group or allyl group as a terminal group 16 ) Alkyl or branched chain (C3-C 16 ) alkyl; R e1 , R e2 , R e3 and R e4 At least one of the above is a vinyl group, an acrylate group, a methacrylate group, an allyl group, or a linear (C1-C) copolymer having a vinyl group, an acrylate group, a methacrylate group, or an allyl group as a terminal group. 16 ) Alkyl or branched chain (C3-C 16 ) alkyl].

[0069] It is believed that a compound of formula (IV) having at least one polymerizable group selected from a vinyl group, an acrylate group, a methacrylate group, an allyl group, or a combination thereof may reduce the haze value of the compound and the resulting film (layer).

[0070] According to the present invention, as the compound of formula (IV), any publicly available compound falling within the scope of formula (IV) can be used.

[0071] In a preferred embodiment of the present invention, from the viewpoint of reducing the haze value of the film (layer), the monomer of formula (IV) is [ka] [ka] [ka] [ka] [ka] is selected from the group consisting of:

[0072] Most preferably, the composition contains at least vinylnorbornene as the monomer of formula (IV).

[0073] In a preferred embodiment of the present invention, the total amount of the compounds of formula (IV) is in the range of 0.1 to 100% by weight based on the total amount of the compounds of formula (I). From the viewpoint of achieving a good lower haze value of the film (layer) and / or realizing good optical and mechanical properties of the film, it is more preferably in the range of 1 to 50% by weight. It is more preferably 5 to 30% by weight, and even more preferably 8 to 20% by weight.

[0074] Additional monomers (V), (VI) According to the present invention, the composition of the present invention may optionally contain additional monomers. In some embodiments, the composition of the present invention may further contain one or more monomers selected from the monomer of formula (V) and / or the monomer of formula (VI).

[0075] The monomer of formula (V) is [ka] [In the formula, o is an integer from 0 to 2; D is SiR 21 R 22 R 23 , or -(CH2) c -O-SiR 21 R 22 R 23 (E);-(CH2) c -SiR 21 R 22 R 23 (F); and -(SiR 21 R 22 ) c -O-SiR 21 R 22 R 23 (G) c is an integer of 1 to 10, and one or more of CH2 is (C1 to C 10 ) alkyl, (C1-C 10 ) perfluoroalkyl, or (C6-C 14 ) optionally substituted with aryl; R 18 , R 19 and R 20 are the same or different and are independently selected from hydrogen, halogen and hydrocarbyl, where hydrocarbyl is methyl, ethyl, straight or branched chain (C3 to C 12 ) Alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) Bicycloalkyl, (C7-C 14 ) tricycloalkyl, (C6-C 10 ) Aryl, (C6-C 10 )aryl(C1-C3)alkyl, (C1-C 12 )Alkoxy, (C3-C 12 ) cycloalkoxy, (C6-C 12 ) bicycloalkoxy, (C7-C 14 ) Tricycloalkoxy, (C6-C 10 )aryloxy(C1-C3)alkyl or (C6-C 10 ) aryloxy; R 21 , R 22 and R 23 are each independently methyl, ethyl, straight or branched chain (C3-C9) alkyl, substituted or unsubstituted (C6-C 14 )aryl, methoxy, ethoxy, straight or branched chain (C3-C9)alkoxy, or substituted or unsubstituted (C6-C 14 )aryloxy].

[0076] In this aspect of the invention, it has been discovered that monomers of formula (V) offer additional advantages. Namely, depending on the nature of the monomer, monomers of formula (V) can impart a high or low refractive index, a low or high dielectric constant to the composition, and thus can be tailored as needed. Furthermore, monomers of formula (V) can generally be used as "adhesion modifiers" to improve adhesive properties. Finally, monomers of formula (V) can exhibit, among other advantages, low viscosity and good solubility for latent catalysts and / or activators.

[0077] In some embodiments, the compositions of the present invention contain first and second monomers of formula (I) that are different from one another, one of which has a refractive index of at least 1.5 and a viscosity of less than 100 centipoise, and the first monomer is completely miscible with the second monomer to form a clear solution. However, as noted, any one or more monomers of formula (V) can also be used in this embodiment of the present invention.

[0078] The monomer of formula (VI) is [ka] [In the formula, R 24 and R 25 are the same or different and are each independently selected from the group consisting of hydrogen, methyl, ethyl, straight or branched chain (C3-C6) alkyl, methoxy, ethoxy, straight or branched chain (C3-C6) alkyloxy, acetoxy, (C2-C6) acyl, phenyl, and phenoxy; or R 24 is R 25 and together with the carbon atoms to which they are attached form a (C5-C7) carbocyclic ring optionally containing one or more double bonds; R 26 is hydrogen, halogen, methyl, ethyl, straight or branched chain (C3-C 16 ) Alkyl, (C6-C 10 ) Aryl, (C6-C 10) aryl (C1-C6) alkyl, hydroxy, methoxy, ethoxy, straight or branched chain (C3-C 16 )Alkoxy, (C6-C 10 ) Aryloxy, (C6-C 10 )aryl(C1-C6)alkoxy, -O(CO)R 27 and -O(CO)OR 27 and R 27 is methyl, ethyl, straight or branched chain (C3-C 16 ) Alkyl, (C6-C 10 ) aryl and (C6-C 10 )aryl(C1-C6)alkyl].

[0079] Similarly, any of the monomers within the scope of the formula (V) monomers can be used in the compositions of the present invention. Representative examples of the formula (V) monomers include: [ka] (Bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane (NBCH2OSiMePh2); [ka] (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(ethyl)diphenylsilane; [ka] (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(ethyl)(methyl)(phenyl)silane; [ka] (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)dimethyl(phenyl)silane; [ka] Bicyclo[2.2.1]hept-5-en-2-yltrimethoxysilane (TMSNB); [ka] Bicyclo[2.2.1]hept-5-en-2-yltriethoxysilane (NBSi(OC2H5)3); [ka] Bicyclo[2.2.1]hept-5-en-2-yl(tert-butoxy)dimethoxysilane; and [ka] (2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)trimethoxysilane.

[0080] Representative examples of monomers of formula (VI) include: [ka] Dicyclopentadiene (DCPD); [ka] 4,4a,4b,5,8,8a,9,9a-octahydro-1H-1,4:5,8-dimethanofluorene (a trimer of cyclopentadiene, TCPD2); [ka] 1-Methoxy-dicyclopentadiene; [ka] 1-(n-butoxy)-dicyclopentadiene; [ka] 1-(n-octyloxy)-dicyclopentadiene; [ka] 3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-yl acetate; [ka] 3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-yl benzoate; [ka] 3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-yl 2-phenylacetate; and [ka] 3a,4,7,7a-tetrahydro-1H-4,7-methanoinden-1-yl 3-phenylpropanoate.

[0081] ultraviolet (UV) blockers The incorporation of certain ultraviolet (UV) blocking agents is believed to surprisingly impart additional stability to the compositions of the present invention, particularly when used in UV-exposed environments such as, for example, within a 3D printer vat or within the encapsulation of an optical device (e.g., OLED). More importantly, it has been discovered that the incorporation of two or more such UV blocking compounds further provides a synergistic effect, allowing the compositions of the present invention to cure at similar or faster rates when compared to compositions that do not use such two or more UV blocking compounds. Surprisingly, the incorporation of these two or more UV blocking agents does not reduce the bulk polymerization activity of the compositions of the present invention when exposed to appropriate actinic radiation, thus providing a synergistic, beneficial effect.

[0082] It should be further noted that the compositions of the present invention, when exposed to appropriate actinic radiation, undergo bulk polymerization at a rate similar to that of compositions not containing either of the two UV blocking agents. Similarly, the compositions of the present invention exhibit similar polymerization rates when compared to compositions containing only one of the UV blocking agents. Thus, there is no noticeable decrease in the polymerization rate activity of the compositions of the present invention when exposed to appropriate actinic radiation. Furthermore, films formed from the compositions of the present invention exhibit substantially the same transmittance, with the compositions of the present invention demonstrating better than 90% transmittance at wavelengths between 370 nm and 800 nm.

[0083] Thus, the compositions of the present invention comprise a compound of formula (VIII): [ka] [In the formula, n is an integer from 0 to 4; Each R 32 is hydrogen, methyl, ethyl, straight or branched chain (C3-C 12 ) Alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) Bicycloalkyl, (C7-C 14 ) tricycloalkyl, (C6-C 10 ) Aryl, (C6-C 10 )aryl(C1-C3)alkyl, (C1-C 12 )Alkoxy, (C3-C 12 ) cycloalkoxy, (C6-C 12 ) bicycloalkoxy, (C7-C 14 ) Tricycloalkoxy, (C6-C 10 )aryloxy(C1-C3)alkyl and (C6-C 10 ) aryloxy].

[0084] Furthermore, the composition of the present invention comprises a compound of formula (IX): [ka] [In the formula, R 33is methyl, ethyl, straight or branched chain (C3-C 12 ) alkyl and (C3-C 12 ) cycloalkyl].

[0085] R 34 and R 35 may be the same or different, and (C1 to C 10 ) Alkyl, (C6-C 18 ) Aryl, (C6-C 12 ) aryl(C1-C5) alkyl, and (C1-C5) alkyl(C6-C 12 )aryl. In some embodiments, R 34 and R 35 is independently selected from the group consisting of (C4-C8) alkyl, phenyl, and phenyl(C1-C3) alkyl. 34 and R 35 is independently selected from the group consisting of (C5-C8) alkyl, and phenyl(C1-C3) alkyl.

[0086] R 34 and R 35 The alkyl portion of R may be straight or branched, and at each occurrence, all or some of such branched alkyl portions are independently selected. 34 and R 35 One or more of the methylenes of the alkyl portion of R can be replaced with -CO-, -O-, or -COO-. That is, the -CH2- portion of the alkyl is replaced with one of -CO-, -O-, or -COO-. In some embodiments, R 34 and / or R 35 One or more of the hydrogens on the methylene moiety of is replaced with -COO-.

[0087] Surprisingly, the inclusion of the compound of formula (VIII) and the compound of formula (IX) not only improves the stability of the composition, but also improves the optical performance of the article produced therefrom, either in the production of an OLED device or in the production of a 3D article.It is believed that the compound of formula (VIII) or (IX) functions, among other functions, as a UV blocker, thereby providing the composition with greater stability during UV exposure of the composition, for example, during ambient contact with any UV light when the composition is drawn out of the vat to form the intended 3D object.

[0088] Therefore, any compound that can function similarly to the compound of formula (VIII) or (IX), such as any other known UV blocking agent, can also be used in the composition of the present invention. Any amount of the compound of formula (VIII) or (IX) that provides the desired benefit can be used in the composition of the present invention. Generally, such amount can vary from about 1:200 molar parts of the compound of formula (VIII) or (IX) to the compound of formula (II). In some other embodiments, such amount can be from about 1:100 molar parts of the compound of formula (VIII) or (IX) to the compound of formula (II); or 1:50 molar parts of the compound of formula (VIII) or (IX) to the compound of formula (II). However, it should be noted that it is not necessary to use the same amount of the compound of formula (VIII) or (IX), and various amounts of the compound of formula (VIII) can be used in combination with the appropriate amount of the compound of formula (IX), approximately in the amounts described above.

[0089] Representative examples of compounds of formula (VIII) are: [ka] 2,5-bis(5-(tert-butyl)benzo[d]oxazol-2-yl)thiophene (BTBBT), commercially available from Mayzo as Benetex OB Plus; [ka] 5-(tert-butyl)-2-(5-(5-isopropylbenzo[d]oxazol-2-yl)thiophen-2-yl)benzo[d]oxazole; [ka] 2,5-bis(5-isopropylbenzo[d]oxazol-2-yl)thiophene; [ka] 5-ethyl-2-(5-(5-isopropylbenzo[d]oxazol-2-yl)thiophen-2-yl)benzo[d]oxazole; [ka] 2,5-bis(5-ethylbenzo[d]oxazol-2-yl)thiophene; [ka] 5-ethyl-2-(5-(5-methylbenzo[d]oxazol-2-yl)thiophen-2-yl)benzo[d]oxazole; and [ka] 2-(5-(benzo[d]oxazol-2-yl)thiophen-2-yl)-5-(tert-butyl)benzo[d]oxazole,

[0090] Representative examples of compounds of formula (IX) are: [ka] 6-butyl-2-(2-hydroxy-3-(2-phenylpropan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-[1,2,3]triazolo[4,5-f]isoindole-5,7(2H,6H)-dione; and [ka] 2-(2-hydroxy-3-(2-phenylpropan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-6-propyl-[1,2,3]triazolo[4,5-f]isoindole-5,7(2H,6H)-dione, but not limited thereto.

[0091] Various other UV light blocking compounds and / or UV light absorbers that can be used in the compositions of the present invention include: [ka] [ka] [Wherein, n and R 32 is the same as defined in formula (VIII).

[0092] Representative compounds within the scope of compounds of formula (VIIIa) and (VIIIb) can be represented as follows: [ka] 1,2-bis(4-(benzo[d]oxazol-2-yl)phenyl)ethene, commercially available from Mayzo as Benetex OB-1; and [ka] Sodium 2,2'-([1,1'-biphenyl]-4,4'-diylbis(ethene-2,1-diyl))dibenzenesulfonate, commercially available from Mayzo as Benetex OB-M1.

[0093] As used herein, aryl includes the following: Substituted or unsubstituted biphenyls of the formula: [ka] Substituted or unsubstituted naphthyl of the formula: [ka] Substituted or unsubstituted terphenyls of the formula: [ka] Substituted or unsubstituted anthracenyl of the formula: [ka] Substituted or unsubstituted fluorenyl of the formula: [ka] [In the formula, R x In each occurrence, methyl, ethyl, straight or branched chain (C3-C 12 ) alkyl or (C6-C 10 ) aryl].

[0094] Monomer Crosslinker Advantageously, it has now further been discovered that the use of one or more monomeric crosslinkers in appropriate amounts can dramatically improve the mechanical properties of the resulting three-dimensional objects formed from the compositions of the present invention. Representative examples of such suitable monomeric crosslinkers include: i) A compound of formula (Xa): [ka] ii) A compound of formula (Xb): [ka] iii) A compound of formula (Xc): [ka] [In the formula, m is an integer of 0, 1, or 2; b is an integer from 1 to 10; K is selected from the group consisting of CH2, CH2-CH2, O, and S; X is a bond, or O, S, or NR a , SiR b R c, SiR b R c O(SiR b R c O) n SiR b R c , SiR b R c (C6~C 10 )ArylSiR b R c , -C(O)-, -C(O)O-, -OC(O)-, -OC(O)-O-, -SC(O)-, -C(O)-S-, -CH=CH and [ka] a moiety selected from the group consisting of: R a , R b and R c are each independently hydrogen, methyl, ethyl, or a straight or branched chain (C3 to C 12 ) alkyl, (C3-C8) cycloalkyl, (C5-C 12 ) bicycloalkyl, (C5-C 12 ) bicycloalkenyl and (C5-C 12 ) selected from the group consisting of bicycloalkenyl(C1-C3)alkylSi(CH3)2, wherein the O, NRa and / or S atoms are not directly bonded to each other; and n is an integer from 0 to 10.

[0095] It has now been found that, advantageously, the incorporation of one or more compounds of formula (Xa), (Xb), or (Xc) can tailor the properties of a composition to suit an intended purpose. For example, by appropriately combining one or more compounds of formula (Xa), (Xb), or (Xc) with the composition of the present invention, it is possible to improve, among other properties, the mechanical properties of articles formed from the composition of the present invention. More specifically, it has been found that the incorporation of certain siloxane compounds within the scope of compounds of formula (Xa) or (Xb) improves the impact strength of products formed therefrom. One or more compounds of formula (Xa), (Xb), or (Xc) can be used in any amount that provides the intended benefit. Generally, such amount can range from 0 to 20 mole percent of one or more compounds of formula (Xa), (Xb), or (Xc) in combination with one or more monomers of formula (V) or (VI) (if used) and one or more compounds of formula (Xa), (Xb), or (Xc), based on the total moles of monomer of formula (I). In some embodiments, such amount may range from 1 to 15 mole percent, in some other embodiments, such amount may range from 0.5 to 10 mole percent, and in still other embodiments, such amount may range from 0.5 to 5 mole percent.

[0096] Thus, in some embodiments, the impact strength of the polymer formed from the composition of the present invention is at least 40 J / m. In some other embodiments, the impact strength of the polymer formed from the composition of the present invention is at least 60 J / m. In still other embodiments, the impact strength of the polymer formed from the composition of the present invention is at least 80 J / m, 100 J / m or more, 140 J / m or more, or even greater than 160 J / m, e.g., greater than 170 J / m, greater than 180 J / m, greater than 200, 220, or 240 J / m, or even greater than 500, 550, 600, 700, or 800 J / m, depending on the type of monomer used as described herein. In some embodiments, the polymer formed from the composition of the present invention comprising one or more monomers of Formula (I) itself may exhibit extraordinary impact strength, such as may be in the range of 50 to 800 J / m.

[0097] In some embodiments, the compound of Formula (Xa), (Xb), or (Xc) each has m=0 and K=CH2. In some embodiments, the compound of Formula (Xa), (Xb), or (Xc) each has m=1 and K=CH2. In yet some other embodiments, the compound of Formula (Xa), (Xb), or (Xc) each has m=2 and K=CH2.

[0098] Representative examples of compounds within the scope of formula (Xa) or (Xb) include the following: [ka] 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (BisENBTMDS); [ka] 1,1,3,3-tetramethyl-1,3-bis(2-(1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalen-2-yl)ethyl)disiloxane; [ka] 1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane (BisENBHMTS); [ka] 1,1,3,3,5,5-hexamethyl-1,5-bis(2-(1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalen-2-yl)ethyl)trisiloxane; [ka] 1,4-bis((2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)dimethylsilyl)benzene; [ka] 3,3'-oxybis(1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-3-cyclohexyl-1,1,5,5-tetramethyltrisiloxane) (TeTENBOMSS) [ka] (bicycloheptenyl)ethyl-terminated polydimethylsiloxane (n is 2 to 4); and [ka] and 3,7,14-tris(((2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)dimethylsilyl)oxy)-1,3,5,7,9,11,14-heptaisobutyl-2,4,6,8,10,12,13,15,16-nonaoxa-1,3,5,7,9,11,14-heptasilatricyclo[7.3.3.15,11]hexadecane (trisnorbornenylisobutyl POSS).

[0099] Additionally, various other oligomeric or polymeric polysiloxanes having polyfunctional cycloolefin pendant groups are suitable as crosslinking molecules in the compositions of the present invention, which may or may not fall within the scope of compounds of formula (XIa). [ka] [In the formula, b is an integer of 1 to 9; n is an integer from 1 to 10; R b and R c are independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and phenyl.

[0100] Various other non-limiting examples of compounds of formula (Xa), (Xb) or (Xc) include the following: [ka] 1,4-Di(bicyclo[2.2.1]hept-5-en-2-yl)butane; [ka] 5,5'-(oxybis(methylene))bis(bicyclo[2.2.1]hept-2-ene); [ka] 5,5'-(oxybis(ethane-2,1-diyl))bis(bicyclo[2.2.1]hept-2-ene); [ka] Bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methane; [ka] 5,5'-((propane-2,2-diylbis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene); [ka] 5,5'-((propane-1,1-diylbis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene); [ka] 5,5'-(((1-phenylethane-1,1-diyl)bis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene); [ka] 1,2-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)ethane; [ka] 1,3-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)propane; [ka] 1,4-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)butane; [ka] 1,6-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)hexane; [ka] 1,8-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)octane; [ka] Bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)dimethylsilane; [ka] [wherein n is 2 to 4]; [ka] [In the formula, R and R′ are each selected from the group consisting of (C1 to C 12 alkyl), (C6-C 10 Aryl) and (C6-C 10 Aryl) (C1-C 12 alkyl); [ka] Bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)(phenyl)silane; [ka] Bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)diphenylsilane; [ka] 1,4-Di(bicyclo[2.2.1]hept-5-en-2-yl)benzene; [ka] 1,3-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)benzene; [ka] Bis(bicyclo[2.2.1]hept-5-en-2-ylmethyl)carbonate; [ka] Bicyclo[2.2.1]hept-5-en-2-ylmethyl bicyclo[2.2.1]hept-5-ene-2-carboxylate; [ka] [wherein b is an integer of 1 to 6]; [ka] Bis(bicyclo[2.2.1]hept-5-en-2-ylmethyl) terephthalate; [ka] Bicyclo[2.2.2]oct-5-en-2-ylmethylbicyclo[2.2.2]oct-5-ene-2-carboxylate; [ka] 5,5'-((((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(2,3,5,6-tetrafluoro-4,1-phenylene))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene); [ka] 5,5'-(((((perfluoropropane-2,2-diyl)bis(4,1-phenylene))bis(oxy))bis(2,3,5,6-tetrafluoro-4,1-phenylene))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene) [ka] 1,4,4a,4b,5,8,8a,8b-Octahydro-1,4:5,8-dimethanobiphenylene; [ka] 4,4a,4b,5,8,8a,9,9a-Octahydro-1H-1,4:5,8-dimethanofluorene; [ka] 1,4,4a,5,8,8a,9,9a,10,10a-Decahydro-1,4:5,8-dimethanoanthracene; [ka] 1,4,4a,5,6,6a,7,10,10a,11,12,12a-dodecahydro-1,4:7,10-dimethanodibenzo[a,e][8]annulene; and [ka] 1,4,4a,5,5a,5b,6,6a,7,10,10a,11,11a,11b,12,12a-hexadecahydro-1,4:5,12:6,11:7,10-tetramethanodibenzo[b,h]biphenylene.

[0101] Various other non-limiting examples within the scope of compounds of formula (Xa), (Xb) or (Xc) include the following: [ka] 1,3-Di(bicyclo[2.2.1]hept-5-en-2-yl)propane; [ka] 5,5'-(2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)propane-1,3-diyl)bis(bicyclo[2.2.1]hept-2-ene); [ka] Bis(4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl)methane; [ka] Tris(4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl)methane; [ka] 5,5'-(((2-((bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl)-2-methylpropane-1,3-diyl)bis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene); [ka] 5,5'-(((bicyclo[2.2.1]hept-5-en-2-ylmethylene)bis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene); [ka] Tris(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)silane; and [ka] Bicyclo[2.2.1]hept-5-en-2-ylbis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)silane may be mentioned.

[0102] In some embodiments of the present invention, the composition of the present invention may further contain another photosensitizer compound capable of activating the organoruthenium compound of formula (II) to promote the bulk polymerization of the monomer of formula (I) and / or the monomer of formula (V) or (VI), if present. Any suitable sensitizer compound can be used in the composition of the present invention for this purpose. Such suitable sensitizer compounds include photosensitizers such as anthracene, phenanthrene, chrysene, benzpyrene, fluoranthene, rubrene, pyrene, xanthone, indanthrene, and mixtures thereof.

[0103] In some exemplary embodiments, suitable sensitizer components include mixtures of these. Generally, photosensitizers absorb energy from a radiation source and transfer that energy to the desired substrate / reactant used in the compositions of the present invention.

[0104] The compositions according to the present invention may further contain optional additives that may be useful for improving the properties of both the composition and the object made therefrom, such optional additives may include, for example, antioxidants and synergists.

[0105] In another aspect, the present invention further provides a method of making a film, comprising the steps of: (X a1 11.) providing the composition according to any one of claims 1 to 10 on the outermost surface of a substrate, layer or device to obtain a coated layer; (X a2 ) irradiating the coated layer with light (applying light irradiation) to form a cured film, preferably the light has a peak maximum wavelength in the range of 360 to 430 nm, and preferably the dose of light irradiated on the composition is 1 to 5 J / cm. 2 The present invention relates to a method in which

[0106] In another aspect of this embodiment of the invention, the compositions of the present invention undergo bulk polymerization when subjected to appropriate radiation for a sufficient length of time to form a polymer film or solid object.

[0107] That is, the compositions of the present invention are poured onto the surface or substrate that needs to be encapsulated and exposed to appropriate radiation to cause the monomers to polymerize and form a solid transparent polymer that can be in the form of a transparent film or solid object.

[0108] Generally, as already mentioned above, such polymerization can occur when exposed to actinic radiation having a wavelength of about 240 nm to 410 nm. The composition can also be subjected to appropriate radiation and heat simultaneously to cause bulk polymerization. By practicing the present invention, it is now possible to obtain polymer films on such substrates that are substantially transparent films or solid bodies, depending on the manufacturing method used.

[0109] As used herein, "substantially transparent film" means that the film formed from the composition of the present invention is optically transparent in visible light. Thus, in some embodiments of the present invention, such films have a visible light transmittance of at least 90 percent, and in some other embodiments, films formed from the composition of the present invention exhibit a visible light transmittance of at least 95 percent.

[0110] Coating of the desired substrate to form a film using the composition of the present invention can be carried out by any of the coating or printing procedures described herein and / or known to those skilled in the art, such as spin coating. Other suitable coating methods include, but are not limited to, spraying, doctor blading, meniscus coating, inkjet coating, and slot coating. The composition can also be inkjet printed onto the substrate, as is known in the art. The mixture can also be poured onto the substrate to form a film. Suitable substrates include substrates that can be used directly in electrical, electronic, or optoelectronic devices, or any suitable substrate that can be used, such as semiconductor substrates, ceramic substrates, glass substrates, etc.

[0111] The coated substrate is then exposed to suitable actinic radiation, i.e., radiation at wavelengths between 240 nm and 410 nm as described herein, to promote bulk polymerization. In some embodiments, the substrate is exposed to radiation and baked at a temperature between about 40° C. and about 90° C. for about 2 minutes to 30 minutes. In some other embodiments, the substrate is exposed to radiation and baked at a temperature between about 60° C. and about 90° C. for 5 minutes to 20 minutes.

[0112] The films thus formed are then evaluated for their optical properties using any method known in the art. For example, the refractive index of the film across the visible spectrum can be measured by ellipsometry. The optical quality of the film can be determined visually. The transparency percentage can be quantitatively measured by visible spectroscopy. Generally, films formed according to the present invention exhibit excellent optical transparency and can be tailored to a desired refractive index as described herein.

[0113] The compositions of the present invention are also useful as protective layers in various electronic or optoelectronic devices, particularly organic electronic devices, that are susceptible to damage from environmental conditions, particularly oxygen and moisture. The compositions of the present invention serve as protective layers that provide the necessary protection against environmental conditions. Generally, in such applications, such as organic light-emitting diode (OLED) devices, multiple OLED layers or OLED stacks are formed on a suitable substrate and then encapsulated with the compositions of the present invention.

[0114] The OLED stack can be encapsulated by any known method, including, but not limited to, dip coating, inkjet coating, spin coating, and the like. The coated OLED stack is then subjected to appropriate actinic radiation to form a transparent polymer layer on the OLED stack by ROMP. A conductive layer is deposited on the polymer layer either before or after the transparent polymer layer is formed. Such a conductive layer can be deposited by any known method, such as, for example, chemical vapor deposition (CVD), among others. Polymer layers formed from the compositions of the present invention are stable to such CVD processes and retain their properties, such as transparency, among other properties described herein. Finally, the OLED device can optionally be protected by coating another polymer layer with the compositions of the present invention, as described above, and then subjecting it to appropriate actinic radiation. Such a lamination process can involve multiple steps of transparent polymer layer formation and / or conductive layer deposition.

[0115] In another aspect, the present invention further relates to a film formed from the composition of the present invention.

[0116] In another aspect, the present invention further relates to a film obtained or obtainable by the method of the present invention. Preferably, the film is optically clear.

[0117] In a preferred embodiment of the present invention, the film has a layer thickness in the range of 0.1 to 100 μm, preferably 1 to 20 μm, more preferably 5 to 10 μm.

[0118] In a preferred embodiment of the present invention, the film has a relative dielectric constant value ε r <2.5, preferably 1.5 ≤ ε r <2.5, more preferably 2.0≦ε r ≦2.4.

[0119] In a preferred embodiment of the present invention, the film has a haze value of 46 or less, preferably 20 or less, more preferably 3 or less, and preferably 0 or more.

[0120] According to the present invention, the haze value is measured in air at room temperature according to the procedure described in ASTM D1003-21. The measurement can be carried out using a commercially available haze meter, for example, a BYK Gardner Haze-Gard plus 4725.

[0121] In another aspect, the present invention further relates to a device comprising at least the film of the present invention, preferably the device is an optical device, more preferably the device is a display device, preferably the device further comprises a functional module, more preferably the device comprises a functional module selected from an OLED, an LCD and a μLED.

[0122] In another aspect, the present invention also provides a photocurable composition for forming a protective layer on a device, comprising a compound of formula (IV): [ka] [In the formula, p is an integer 0, 1 or 2; R e1 , R e2 , R e3 and R e4 are each independently hydrogen, halogen, methyl, ethyl, straight chain (C1-C 16 ) Alkyl or branched chain (C3-C 16 ) alkyl, perfluoro(C1-C 12 ) alkyl, hydroxy (C1-C 16 ) Alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) Bicycloalkyl, (C7-C 14 ) tricycloalkyl, (C6-C 10 ) Aryl, (C6-C 10 ) aryl(C1-C6) alkyl, perfluoro(C6-C 10 ) Aryl, Perfluoro(C6-C 10 ) aryl(C1-C6) alkyl, tri(C1-C6) alkoxysilyl, vinyl group, acrylate group, methacrylate group and allyl group, linear (C1-C) alkyl having a vinyl group, acrylate group, methacrylate group or allyl group as a terminal group 16 ) Alkyl or branched chain (C3-C 16 ) alkyl; R e1 , R e2 , R e3 and R e4 At least one of the above is a vinyl group, an acrylate group, a methacrylate group, an allyl group, or a linear (C1-C) copolymer having a vinyl group, an acrylate group, a methacrylate group, or an allyl group as a terminal group. 16 ) Alkyl or branched chain (C3-C 16 ) alkyl].

[0123] Further details of compounds of formula (IV) are provided above in the section on compounds of formula (IV).

[0124] Technical Effects of the Invention The present invention has the following effects: The present invention provides one or more of: higher transparency of the composition and / or resulting film at visible light wavelengths; lower haze value of the resulting film; lower dielectric constant of the composition and resulting film; lower dielectric constant of the composition and resulting film; improved touch sensitivity of a touch screen separated from an OLED device by a film according to the present invention; high refractive index; good mechanical properties of the resulting film against mechanical stresses such as folding and bending; good cure rate of the composition; and good thermal properties.

[0125] The following examples provide an explanation of the present invention as well as detailed descriptions of their preparation, but the present invention is not limited to the examples. [Example]

[0126] The following abbreviations have been used herein above and below in describing some of the compounds, devices and / or methods used to exemplify certain embodiments of the present invention: HexylTD: 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene; PETD: 2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene CL1: 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane [ka] [ka] NBMeOPhPh: 5-(([1,1'-biphenyl]-2-yloxy)methyl)bicyclo[2.2.1]hept-2-ene VinylNB: 5-vinyl-2-norbornene [ka] CPTX: 1-chloro-4-propoxy-9H-thioxanthen-9-one; Catalyst Ru-I: [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxide-κO}[2-(oxide-κO)benzylidene-κC]ruthenium(II); The various monomers used herein are either commercially available or can be readily prepared according to the procedures described in US Pat. No. 9,944,818.

[0127] Comparative Example 1: Preparation of the composition In a brown glass bottle, CPTX (0.1 wt%) is dissolved in HexylTD (99.87 wt%) and sonicated at 30°C for 20 minutes to form a clear solution. The solution is purged with nitrogen for 8 hours. Ru-1 catalyst (0.03 wt%) is added to the purged solution in a glove box and sonicated for 30 minutes to completely dissolve the catalyst. The sample is optically checked for complete dissolution and filtered before further experiments. A comparative sample (Sample 0) is then obtained.

[0128] Examples 1-10: Preparation of Compositions Samples 1 to 10 (Examples 1 to 10) were obtained in the same manner as in Comparative Example 1 above, except that the following materials listed in Table 1 were used instead of the materials used in Comparative Example 1.

[0129] [Table 1] Comparative Example - No Vinylnorbornene

[0130] Example 11 - Thin Film Preparation (Spin Coating + UV Curing) Thin film samples 1-10 of the compositions of Examples 1-10 are prepared by spin-coating each composition separately onto a pre-cleaned quartz substrate in a glove box under nitrogen. The wet films are then irradiated with 395 nm UV light to cure the films. The applied dose is approximately 1-5 J / cm. 2 The exact doses used are summarized in Table 2. The spin-coating parameters are optimized to obtain a cured film thickness of 8 μm. After the film is cured, the film thickness is determined by profilometry using a stylus profilometer as the height difference between the film surface and the substrate surface (after scratching with a scalpel). Film samples 1 to 10 are then obtained.

[0131] Comparative Example 2 - Thin Film Preparation (Spin Coating + UV Curing) A thin film sample 1 of the comparative composition of Comparative Example 1 was produced in the same manner as in Example 11, except that the comparative composition of Comparative Example 1 was used instead of the composition used in Example 11. In this way, film sample 1 was obtained.

[0132] Curing rate measurement The cured material of each film sample is collected by scraping the prepared film off the substrate, and the material is analyzed by ATR-FTIR spectroscopy. The spectra are baseline corrected and have a peak at 2851 cm -1 The curing rate is normalized to the peak at 3058 cm -1 It is determined by integrating the characteristic vibrations of the monomer at and comparing it to the integral of the signal of the uncured formulation.

[0133] HIT and EIT measurements Thin films on quartz substrates are further analyzed by nanoindentation to determine material properties such as the elastic indentation modulus (EIT) and indentation hardness (HIT). The indenter is pressed into the test object using a defined force curve, and the penetration depth is recorded. From the registered indentation depth, applied force, and indenter geometry, various parameters can be calculated. Measurements are performed using a Fischerscope HM2000S (load force = 1 mN, load time = 8 s, creep = 20 s), and EIT and HIT are calculated using the instrument software.

[0134] Silicon nitride deposition and haze measurement On the thin film samples from the spin-coating experiments, 700 nm of silicon nitride (SiNx) is deposited by CVD.

[0135] After the deposition of silicon nitride, the haze of the resulting stack (quartz glass / cured polymer / SiNx) is determined according to ASTM D1003-21. The measurement is carried out using a BYK Gardner Haze-Gard plus 4725 haze meter. The measurement is carried out in air at room temperature.

[0136] Table 2 shows the measurement results.

[0137] [Table 2]

[0138] The present invention has been illustrated by some of the foregoing examples, but should not be construed as being limited thereby. However, the present invention encompasses the general scope as disclosed above. Various modifications and embodiments can be made without departing from the spirit and scope of the present invention.

Claims

1. a) Formula (I): 【Chemical 1】 [In the formula, m is an integer of 0, 1 or 2; R １ , R ２ , R ３ and R ４ are the same or different and are hydrogen, halogen, methyl, ethyl, straight or branched chain (C ３ ~C １６ ) alkyl, perfluoro(C １ ~C １２ ) alkyl, hydroxy (C １ ~C １６ ) alkyl, (C ３ ~C １２ ) cycloalkyl, (C ６ ~C １２ ) bicycloalkyl, (C ７ ~C １４ ) tricycloalkyl, (C ６ ~C １０ ) aryl, (C ６ ~C １０ ) aryl (C １ ~C ６ ) alkyl, perfluoro(C ６ ~C １０ ) aryl, perfluoro(C ６ ~C １０ ) aryl (C １ ~C ６ ) alkyl, tri(C １ ~C ６ ) alkoxysilyl, and a compound of formula (A): -Z １ -aryl (A) (In the formula, Z １ is a bond, or (CR ５ R ６ ) ａ , O(CR ５ R ６ ) ａ , (CR ５ R ６ ) ａ O, (CR ５ R ６ ) ａ -O-(CR ５ R ６ ) ｂ , (CR ５ R ６ ) ａ —O—(SiR ５ R ６ ) ｂ , (CR ５ R ６ ) ａ -(CO)O-(CR ５ R ６ ) ｂ , (CR ５ R ６ ) ａ -O(CO)-(CR ５ R ６ ) ｂ , (CR ５ R ６ ) ａ -(CO)-(CR ５ R ６ ) ｂ wherein a and b are integers which may be the same or different and each independently range from 1 to 12; R ５ and R ６ are the same or different and are hydrogen, methyl, ethyl, straight or branched chain (C ３ ~C ６ ) alkyl, hydroxy, methoxy, ethoxy, straight or branched chain (C ３ ~C ６ ) alkyloxy, acetoxy, (C ２ ~C ６ ) acyl, hydroxymethyl, hydroxyethyl, straight or branched chain hydroxy (C ３ ~C ６ ) each independently selected from the group consisting of alkyl, phenyl, and phenoxy; Aryl is phenyl, or methyl, ethyl, straight or branched chain (C ３ ~C ６ ) alkyl, hydroxy, methoxy, ethoxy, straight or branched chain (C ３ ~C ６ ) alkyloxy, acetoxy, (C ２ ~C ６ ) acyl, hydroxymethyl, hydroxyethyl, straight or branched chain hydroxy (C ３ ~C ６ ) phenyl substituted with one or more groups selected from the group consisting of alkyl, phenyl, and phenoxy; b) an organoruthenium compound, preferably of formula (II): 【Chemistry 2】 [In the formula, c and d are integers from 0 to 5; Z is oxygen or sulfur; R ７ is hydrogen, (C １ ~C ２０ ) alkyl, (C ２ ~C ２０ ) alkenyl, (C ２ ~C ２０ ) alkynyl and (C ６ ~C １０ ) aryl; R ８ , R ９ , R １０ and R １１ are the same or different and are hydrogen, halogen, (C １ ~C １６ ) alkyl, (C １ ~C １６ ) alkoxy, (C １ ~C １６ ) perfluoroalkyl, (C ３ ~C ７ ) cycloalkyl, (C ２ ~C １６ ) alkenyl, (C ６ ~C １４ ) aryl, (C ６ ~C １４ ) perfluoroaryl, (C ３ ~C １２ ) heterocyclyl, —OR １６ , -NO ２ , -COOH, -COOR １６ , -CONR １６ R １７ , -SO ２ NR １６ R １７ , -SO ２ R １６ , -CHO, -COR １６ and R １６ and R １７ are the same or different, and (C １ ~C ６ ) alkyl, (C １ ~C ６ ) perfluoroalkyl, (C ６ ~C １４ ) aryl, (C ６ ~C １４ ) perfluoroaryl; or R ８ , R ９ , R １０ and R １１ two or more of which, together with the carbon atoms to which they are attached, form a substituted or unsubstituted fused (C ４ ~C ８ ) forming a carbocyclic ring or a substituted or unsubstituted fused aromatic ring; Each R １２ , R １３ and R １４ may be the same or different and independently represent hydrogen, halogen, (C １ ~C １６ ) alkyl, (C １ ~C １６ ) alkoxy, (C １ ~C １６ ) perfluoroalkyl, (C ３ ~C ７ ) cycloalkyl, (C ２ ~C １６ ) alkenyl, (C ６ ~C １４ ) aryl, (C ６ ~C １４ ) perfluoroaryl, (C ３ ~C １２ ) heterocyclyl, —OR １６ , -NO ２ , -COOH, -COOR １６ , -CONR １６ R １７ , -SO ２ NR １６ R １７ , -SO ２ R １６ , -CHO, -COR １６ and R １６ and R １７ are the same or different, and (C １ ~C ６ ) alkyl, (C １ ~C ６ ) perfluoroalkyl, (C ６ ~C １４ ) aryl, (C ６ ~C １４ ) perfluoroaryl; R １５ is (C １ ~C １６ ) alkyl, (C １ ~C １６ ) perfluoroalkyl, (C ３ ~C １６ ) cycloalkyl, (C ６ ~C １４ ) aryl, (C ６ ~C １４ ) perfluoroaryl and (C ３ ~C １２ ) heterocyclyl; Ar １ and Ar ２ are the same or different and are each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthyl, each of said substituents being selected from the group consisting of methyl, ethyl, and straight or branched chain (C ３ ~C ６ an organoruthenium compound represented by the formula (I) wherein each of the alkyl groups is independently selected from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, c) a photosensitizer, preferably of formula (III): 【Chemistry 3】 [In the formula, Y is a halogen; R ３０ and R ３１ are the same or different and independently represent hydrogen, methyl, ethyl, straight or branched chain (C ３ ~C １２ ) alkyl, (C ３ ~C １２ ) cycloalkyl, (C ６ ~C １２ ) bicycloalkyl, (C ７ ~C １４ ) tricycloalkyl, (C ６ ~C １０ ) aryl, (C ６ ~C １０ ) aryl (C １ ~C ３ ) alkyl, (C １ ~C １２ ) alkoxy, (C ３ ~C １２ ) cycloalkoxy, (C ６ ~C １２ ) bicycloalkoxy, (C ７ ~C １４ ) tricycloalkoxy, (C ６ ~C １０ ) aryloxy(C １ ~C ３ ) alkyl and (C ６ ~C １０ a photosensitizer represented by the formula (I) selected from the group consisting of aryloxy, d) Formula (IV): 【Chemistry 4】 [In the formula, p is an integer 0, 1 or 2; R ｅ１ , R ｅ２ , R ｅ３ and R ｅ４ are each independently hydrogen, halogen, methyl, ethyl, straight chain (C １ ~C １６ ) alkyl or branched chain (C ３ ~C １６ ) alkyl, perfluoro(C １ ~C １２ ) alkyl, hydroxy (C １ ~C １６ ) alkyl, (C ３ ~C １２ ) cycloalkyl, (C ６ ~C １２ ) bicycloalkyl, (C ７ ~C １４ ) tricycloalkyl, (C ６ ~C １０ ) aryl, (C ６ ~C １０ ) aryl (C １ ~C ６ ) alkyl, perfluoro(C ６ ~C １０ ) aryl, perfluoro(C ６ ~C １０ ) aryl (C １ ~C ６ ) alkyl, tri(C １ ~C ６ ) alkoxysilyl, vinyl group, acrylate group, methacrylate group and allyl group, linear (C １ ~C １６ ) alkyl or branched chain (C ３ ~C １６ ) alkyl; R ｅ１ , R ｅ２ , R ｅ３ and R ｅ４ At least one of the above is a vinyl group, an acrylate group, a methacrylate group, an allyl group, or a linear (C １ ~C １６ ) alkyl or branched chain (C ３ ~C １６ ) alkyl.

2. The monomer of formula (IV) 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 【Chemistry 9】 10. The composition of claim 1, selected from the group consisting of:

3. The monomer of formula (I) 【Chemistry 10】 【Chemistry 11】 5-(4-phenylbutyl)bicyclo[2.2.1]hept-2-ene; 【Chemistry 12】 5-(3-phenylpropyl)bicyclo[2.2.1]hept-2-ene; 【Chemistry 13】 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB); 【Chemistry 14】 5-(benzyloxy)bicyclo[2.2.1]hept-2-ene; 【Chemistry 15】 5-(2-([1,1'-biphenyl]-4-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene; 【Chemistry 16】 5-(2-([1,1'-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtO-2-PhPh); 【Chemistry 17】 5-butylbicyclo[2.2.1]hept-2-ene (BuNB); 【Chemistry 18】 5-hexylbicyclo[2.2.1]hept-2-ene (HexylNB); 【Chemistry 19】 5-octylbicyclo[2.2.1]hept-2-ene (OctNB); 【Chemistry 20】 5-decylbicyclo[2.2.1]hept-2-ene (DecNB); 【Chemical 21】 5-ethylidenebicyclo[2.2.1]hept-2-ene; 【Chemical 22】 2-ethylidene-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene; 【Chemical 23】 3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene (one of the trimers of cyclopentadiene, also known as TCPD1 and CPD3); 【Chemistry 24】 5-norbornenylmethyleugenyl acetate (EuAcNB); 【Chemistry 25】 5-norbornenylmethyleugenol (EuOHNB); 【Chemical Formula 26】 NB(MeOH) ２ ; 【Chemical 27】 PhAcNB; 【Chemical formula 28】 Tetracyclododecene (TD); 【Chemical Formula 29】 5-(phenoxymethyl)bicyclo[2.2.1]hept-2-ene (NBMeOPh); 【Chemistry 30】 5-(([1,1'-biphenyl]-2-yloxy)methyl)bicyclo[2.2.1]hept-2-ene (NBMeOPhPh); 【Chemical 31】 2-phenyl-tetracyclododecene (PhTD); 【Chemical 32】 2-benzyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene; 【Chemical 33】 2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD); 【Chemical 34】 2-butyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (ButylTD); 【Chemistry 35】 2-Hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (HexylTD); 【Chemical 36】 2-Octyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (OctylTD); 【Chemical 37】 2-decyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (DecylTD); 【Chemical 38】 2-Cyclohexyl-tetracyclododecene (CyclohexylTD); 【Chemical Formula 39】 2-cyclohexylmethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene; 【Chemistry 40】 2-cyclohexylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene; 【Chemistry 41】 (1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalen-2-yl)methyl acetate (TDMeOAc); and 【Chemistry 42】 3. The composition of claim 1, wherein the cyclohexanediene is selected from the group consisting of tetracyclododecadiene (TDD).

4. Z is oxygen; R ７ is hydrogen; R ８ , R ９ , R １０ and R １１ are the same or different and are hydrogen, methyl, ethyl and —NO ２ each independently selected from the group consisting of: R １２ , R １３ and R １４ are the same or different and are hydrogen, methyl, ethyl and —NO ２ each independently selected from the group consisting of: R １５ is selected from the group consisting of methyl, ethyl, and cyclohexyl; Ar １ and Ar ２ are the same or different and are each independently selected from the group consisting of phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di(isopropyl)phenyl, and 2,4,6-trimethylphenyl.

5. The organoruthenium compound is 【Chemistry 43】 [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxide-κO}[2-(oxide-κO)benzylidene-κC]ruthenium(II) (Ru-I); 【Chemical 44】 [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]{2-[(E)-({2-[isopropylthio-κS]phenyl}imino-κN)methyl]phenoxide-κO}[2-(oxide-κO)benzylidene-κC]ruthenium(II); 【Chemistry 45】 [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]{2-[(E)-({2-[cyclohexylthio-κS]phenyl}imino-κN)methyl]phenoxide-κO}[2-(oxide-κO)benzylidene-κC]ruthenium(II); and 【Chemistry 46】 5. The composition of any one of claims 1 to 4, represented by formula (II) selected from the group consisting of: [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxide-κO}[2-(oxide-κO)benzylidene-κC]ruthenium(II).

6. Y is chlorine or bromine; R ３０ and R ３１ are the same or different and are independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, phenyl, cyclohexyl, methoxy, ethoxy, n-propoxy and phenoxy.

7. The compound of formula (III) 【Chemistry 47】 1-chloro-4-methoxy-9H-thioxanthen-9-one; 【Chemistry 48】 1-chloro-4-ethoxy-9H-thioxanthen-9-one; 【Chemistry 49】 1-chloro-4-propoxy-9H-thioxanthen-9-one; 【Chemistry 50】 1-chloro-2-propoxy-9H-thioxanthen-9-one; 【Chemistry 51】 1-chloro-2-ethoxy-9H-thioxanthen-9-one; 【Chemistry 52】 1-chloro-2-methoxy-9H-thioxanthen-9-one; 【Chemistry 53】 1-chloro-4-methyl-9H-thioxanthen-9-one; 【Chemical 54】 1-chloro-4-ethyl-9H-thioxanthen-9-one; 【Chemistry 55】 1-bromo-4-propoxy-9H-thioxanthen-9-one; and 【Chemical 56】 7. The composition of claim 1, wherein the hydroxybenzoate is selected from the group consisting of 1-chloro-4-phenoxy-9H-thioxanthen-9-one.

8. The composition of any one of claims 1 to 7, further comprising a UV absorber and / or a crosslinker.

9. 【Chemical 57】 and / or 【Chemistry 58】 The composition of any one of claims 1 to 8, further comprising an additive selected from:

10. 1. A method for producing a film, comprising: (X ａ１ 11.) providing a composition according to any one of claims 1 to 10 on the outermost surface of a substrate, layer or device to obtain a coated layer; (X ａ２ and b) applying light to the coated layer to form a cured film, preferably the light having a peak maximum wavelength in the range of 360 to 430 nm, and preferably the dose of light applied to the composition is 1 to 5 J / cm. ２ The method is in the range of

11. A film formed from the composition of any one of claims 1 to 9.

12. 11. A film obtained or obtainable by the method of claim 10.

13. 13. The film according to claim 11 or 12, having a layer thickness in the range of 0.1 to 100 μm, preferably 1 to 20 μm, more preferably 5 to 10 μm.

14. Relative permittivity value ε ｒ <2.5, preferably 1.5≦ε ｒ <2.5, more preferably 2.0≦ε ｒ 14. The film of any one of claims 11 to 13, having a modulus of elasticity < 2.

4.

15. The film according to any one of claims 11 to 14, having a haze value of 46 or less, preferably 20 or less, more preferably 3 or less, preferably 0 or more.

16. A device comprising at least the film according to any one of claims 11 to 15, preferably the device is an optical device, more preferably the device is a display device, preferably the device further comprises a functional module, more preferably the device comprises a functional module selected from an OLED, an LCD and a μLED.

17. In a photocurable composition for forming a protective layer for a device, a compound represented by formula (IV): 【Chemical Formula 59】 [In the formula, p is an integer 0, 1 or 2; R ｅ１ , R ｅ２ , R ｅ３ and R ｅ４ are each independently hydrogen, halogen, methyl, ethyl, straight chain (C １ ~C １６ ) alkyl or branched chain (C ３ ~C １６ ) alkyl, perfluoro(C １ ~C １２ ) alkyl, hydroxy (C １ ~C １６ ) alkyl, (C ３ ~C １２ ) cycloalkyl, (C ６ ~C １２ ) bicycloalkyl, (C ７ ~C １４ ) tricycloalkyl, (C ６ ~C １０ ) aryl, (C ６ ~C １０ ) aryl (C １ ~C ６ ) alkyl, perfluoro(C ６ ~C １０ ) aryl, perfluoro(C ６ ~C １０ ) aryl (C １ ~C ６ ) alkyl, tri(C １ ~C ６ ) alkoxysilyl, vinyl group, acrylate group, methacrylate group and allyl group, linear (C １ ~C １６ ) alkyl or branched chain (C ３ ~C １６ ) alkyl; R ｅ１ , R ｅ２ , R ｅ３ and R ｅ４ At least one of the above is a vinyl group, an acrylate group, a methacrylate group, an allyl group, or a linear (C １ ~C １６ ) alkyl or branched chain (C ３ ~C １６ ) alkyl.

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