Composition

Abstract

The invention relates to a composition containing a monocyclic olefin compound or a polycyclic olefin compound.

Description

Technical Field

[0001] The present invention relates to a composition comprising a monocyclic olefin compound or a polycyclic olefin compound. The present invention also relates to a method for manufacturing a film, a film, a device, and the use of the compound. Background Art

[0002] Electronic devices, especially organic electronic devices, have become thinner and thinner in recent years. These devices are generally encapsulated with optically transparent insulating materials.

[0003] US 9944818 B2 discloses a two-component bulk-polymerizable composition that can be adjusted to a desired refractive index and is suitable for use as a filler and a protective coating material.

[0004] US 11230624 B2 discloses a polycyclic olefin monomer and a catalyst activated by a compound capable of generating a photoacid as a 3D printing material.

[0005] Patent Document

[0006] 1. US 9944818 B2

[0007] 2. US 11230624 B2 Summary of the Invention

[0008] However, the inventors of the present application have recently found that there are still one or more problems worthy of consideration that need to be improved, as listed below: The composition and / or the resulting film have higher transparency at visible light wavelengths, the resulting film has a lower haze value, the composition and the resulting film have a lower dielectric constant, for example, the dielectric constant is less than 3 and the low loss is less than 0.001 at high frequencies such as greater than 50 GHz, the composition and the resulting film have a lower dielectric constant, the resulting film has improved touch sensitivity, a high refractive index, the resulting film has good mechanical properties to resist mechanical stresses such as folding and bending, the composition has a good curing rate, and good thermal properties.

[0009] The inventors aim to solve the above one or more problems.

[0010] The inventors of the present application have unexpectedly found that the above one or more technical problems can be solved by the features defined in the claims.

[0011] That is, a novel composition has been found, which at least comprises:

[0012] a) a compound of formula (I):

[0013]

[0014] Wherein:

[0015] m is an integer 0, 1 or 2;

[0016] R 1 、R 2 、R 3 and R 4 are the same or different and are each independently selected from the group consisting of: hydrogen, halogen, methyl, ethyl, straight-chain or branched (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, tris (C 1 -C 6 ) alkoxysilyl and group of formula (A):

[0017] -Z 1 -Aryl (A)

[0018] wherein:

[0019] Z 1 is a bond or a group selected from the group consisting of:

[0020] (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 , where a and b are integers which may be the same or different and are each independently 1 to 12;

[0021] R 5 and R 6 are the same or different and are each independently selected from the group consisting of: hydrogen, methyl, ethyl, straight-chain or branched (C 3 -C 6 ) alkyl, hydroxy, methoxy, ethoxy, straight-chain or branched (C 3 -C 6 ) alkoxy, acetoxy, (C 2 -C 6 ) acyl, hydroxymethyl, hydroxyethyl, straight-chain or branched hydroxy (C 3 -C 6 ) alkyl, phenyl and phenoxy;

[0022] Aryl is phenyl or phenyl substituted by one or more groups selected from the following: methyl, ethyl, straight-chain or branched (C 3 -C 6 ) alkyl, hydroxy, methoxy, ethoxy, straight-chain or branched (C 3 -C 6 ) alkoxy, acetoxy, (C 2 -C 6 ) acyl, hydroxymethyl, hydroxyethyl, straight-chain or branched hydroxy (C 3 -C 6 ) alkyl, phenyl and phenoxy;

[0023] b) an organoruthenium compound, preferably represented by formula (II):

[0024]

[0025] wherein

[0026] c and d are integers from 0 to 5;

[0027] Z is oxygen or sulfur;

[0028] R 7 is selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, and (C 6 -C 10 )aryl; and

[0029] R 8 、R 9 、R 10 and R 11 are the same or different and are each independently selected from the group consisting of: 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 )heterocyclic group, -OR 16 、-NO 2 、-COOH、-COOR 16 、-CONR 16 R 17 、-SO 2 NR 16 R 17 、-SO 2 R 16 、-CHO、-COR 16 , wherein R 16 and R 17 are the same or different and are each independently selected from (C 1 -C 6 )alkyl, (C1 -C 6 ) perfluoroalkyl, (C 6 -C 14 ) aryl, (C 6 -C 14 ) perfluoroaryl selected from the group consisting of; or wherein

[0030] R 8 , R 9 , R 10 and R 11 two or more of which together with the carbon atom to which they are attached form a substituted or unsubstituted fused (C 4 -C 8 ) carbocycle, or a substituted or unsubstituted fused aromatic ring;

[0031] R 12 , R 13 and R 14 may each be the same or different and are each independently selected from the group consisting of: 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 ) heterocyclic group, -OR 16 , -NO 2 , -COOH, -COOR 16 , -CONR 16 R 17 , -SO 2 NR 16 R 17 , -SO 2 R 16 , -CHO, -COR 16 , wherein R 16 and R 17 are the same or different and are each independently selected from (C 1 -C 6 ) alkyl, (C 1 -C 6 ) perfluoroalkyl, (C 6 -C 14)Selected from the group consisting of aryl, (C 6 -C 14 ) perfluoroaryl;

[0032] R 15 Selected from the group consisting of (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 ) heterocyclic group;

[0033] 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, wherein the substituents are each independently selected from the group consisting of methyl, ethyl, and linear or branched (C 3 -C 6 ) alkyl;

[0034] c) A photosensitizer, preferably constructed such that the organoruthenium compound is its active form, preferably represented by formula (III):

[0035]

[0036] wherein

[0037] Y is a halogen; and

[0038] R 30 and R 31 are the same or different and are each independently selected from the group consisting of: hydrogen, methyl, ethyl, linear or branched (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, (C1 -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 )aryloxy; and

[0039] d) Compound of formula (IV):

[0040]

[0041] wherein

[0042] p is an integer 0, 1 or 2;

[0043] R e1 , R e2 , R e3 and R e4 are each independently selected from the group consisting of: 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, acrylate, methacrylate, and allyl, a straight-chain (C with vinyl, acrylate, methacrylate, or allyl as the end group 1 -C 16 )alkyl or a branched-chain (C 3 -C 16 )alkyl;

[0044] wherein at least one of R e1 , R e2 , R e3 , and R e4 is vinyl, acrylate, methacrylate, allyl, a straight-chain (C with vinyl, acrylate, methacrylate, or allyl as the end group 1 -C 16 )alkyl or a branched-chain (C 3 -C 16 )alkyl. Detailed embodiments

[0045] The terms used herein have the following meanings:

[0046] As used herein, the articles "a," "an," and "the" include plural referents unless otherwise expressly and unambiguously limited to one referent.

[0047] Since all numbers, values, and / or expressions representing the amounts of ingredients, reaction conditions, etc. used herein are subject to various measurement uncertainties encountered in obtaining these values, all content should be understood to be modified in all instances by the term "about" unless otherwise stated.

[0048] When a numerical range is disclosed herein, the range is continuous, including the minimum and maximum values of the range and each value therebetween. In addition, when the range refers to integers, each integer between the minimum and maximum values of the range is included. In addition, when multiple ranges are provided to describe a feature or characteristic, these ranges can be combined. That is, unless otherwise stated, all ranges disclosed herein should be understood to cover any and all sub-ranges subsumed therein.

[0049] For example, the claimed range of "1 to 10" should be considered to include any and all sub-ranges between the minimum value of 1 and the maximum value of 10. Exemplary sub-ranges 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, etc.

[0050] As used herein, "hydrocarbyl" refers to a group containing carbon and hydrogen atoms, non-limiting examples of which include alkyl, cycloalkyl, aryl, arylalkyl, alkaryl, and alkenyl. The term "halohydrocarbyl" refers to a hydrocarbyl group in which at least one hydrogen has been replaced by a halogen. The term perhalohydrocarbyl refers to a hydrocarbyl group in which all hydrogens have been replaced by halogens.

[0051] As used herein, the expression "alkyl" refers to a saturated straight-chain or branched-chain hydrocarbyl substituent having a specified number of carbon atoms. Specific alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like. Derivative expressions such as "alkoxy", "thioalkyl", "alkoxyalkyl", "hydroxyalkyl", "alkylcarbonyl", "alkoxycarbonylalkyl", "alkoxycarbonyl", "diphenylalkyl", "phenylalkyl", "phenylcarboxyalkyl", and "phenoxyalkyl" shall be construed accordingly.

[0052] As used herein, the expression "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. Derivative expressions such as "cycloalkoxy", "cycloalkylalkyl", "cycloalkylaryl", "cycloalkylcarbonyl" shall be construed accordingly.

[0053] As used herein, the term "perhaloalkyl" means an alkyl group as defined above, wherein all hydrogen atoms in said alkyl group have been replaced by halogen atoms selected from fluorine, chlorine, bromine, or iodine. Exemplary examples include trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl, pentabromoethyl, pentaiodoethyl, and straight-chain or branched-chain heptafluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl, nonachlorobutyl, undecafluoropentyl, undecachloropentyl, tridecafluorohexyl, tridecachlorohexyl, and the like. The derivative expression "perhaloalkoxy" shall be construed accordingly. It should also be noted that some alkyl groups described herein, such as "alkyl", may be partially fluorinated, that is, only some of the hydrogen atoms in said alkyl group have been replaced by fluorine atoms, and shall be construed accordingly.

[0054] As used herein, the expression "acyl" shall have the same meaning as "alkanoyl", and its structure can also be represented as "R-CO-", where R is an "alkyl" as defined herein having a specified number of carbon atoms. In addition, "alkylcarbonyl" shall have the same meaning as "acyl" as defined herein. Specifically, "(C 1 -C 4 ) acyl" shall represent formyl, acetyl (acetyl or ethanoyl), propionyl, n-butyryl, and the like. Derivative expressions such as "acyloxy" and "acyloxyalkyl" shall be construed accordingly.

[0055] As used herein, the term "aryl" refers to a substituted or unsubstituted phenyl or naphthyl group. Specific examples of substituted phenyl or naphthyl groups include o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylenyl, 1-methylnaphthyl, 2-methylnaphthyl, and the like. "Substituted phenyl" or "substituted naphthyl" also includes any possible substituents as further defined herein or any possible substituents known in the art.

[0056] As used herein, the expression "arylalkyl" means an aryl group as defined herein further attached to an alkyl group as defined herein. Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like.

[0057] As used herein, the term "alkenyl" refers to an acyclic, straight-chain or branched hydrocarbon chain having a specified number of carbon atoms and containing at least one carbon-carbon double bond, including vinyl and straight-chain or branched propenyl, butenyl, pentenyl, hexenyl, and the like. The derived terms "arylalkenyl" and five- or six-membered "heteroarylalkenyl" shall be construed accordingly. Exemplary examples of such derived terms include furan-2-vinyl, phenylvinyl, 4-methoxyphenylvinyl, and the like.

[0058] As used herein, the term "heteroaryl" includes all known aromatic groups containing heteroatoms. Representative five-membered heteroaryl groups include furyl, thienyl (thienyl or thiophenyl), pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl, and the like.

[0059] Representative six-membered heteroaryl groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like groups. Representative bicyclic heteroaryl groups include benzofuryl, benzothienyl, indolyl, quinolinyl, isoquinolinyl, cinnolyl, benzimidazolyl, indazolyl, pyridino[2,3-b]furan-2-yl, pyridino[2,3-b]thiophen-2-yl, and the like groups.

[0060] "Halogen" or "halo" refers to chlorine, fluorine, bromine, and iodine.

[0061] Broadly speaking, the term "substituted" is meant to include all permissible substituents of organic compounds. In several specific embodiments disclosed herein, the term "substituted" means substituted by one or more substituents independently selected from the group consisting of (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 1 -C 6 )perfluoroalkyl, phenyl, hydroxy, -CO 2 H, ester, amide, (C 1 -C 6 )alkoxy, (C1 -C 6 ) selected from the group consisting of thioalkyl and (C 1 -C 6 ). However, any other suitable substituents known to those skilled in the art can also be used in these embodiments.

[0062] It should be noted that any atom with unsatisfied valence in the text, schemes, examples, and tables herein is assumed to have an appropriate number of hydrogen atoms to satisfy these valences.

[0063] By the term "latent organotransition metal catalyst", it refers to an organotransition metal compound that has little or no catalytic activity at a specific temperature (usually under ambient atmospheric conditions) and starts to have catalytic activity when heated or irradiated with light or both heated and irradiated with light. Generally, the catalytic activity of the catalyst can be maintained for a long time, up to five days or longer, especially when stored in the dark at room temperature or lower temperatures. Higher temperatures and / or light may accelerate the catalytic activity.

[0064] By the terms "actinic radiation" or "photolytic conditions", it means subjecting the compositions of the present invention to appropriate "electromagnetic radiation", which can be emitted by lasers, digital light processing (DLP) projectors, lamps, light-emitting diodes (LEDs), mercury arc lamps, optical fibers, or liquid crystal displays (LCDs), etc.

[0065] It should be understood that the terms "dielectric" and "insulating" can be used interchangeably herein. Thus, referring to an insulating material or layer includes a dielectric material or layer, and vice versa. In addition, as used herein, the term "organic electronic device" should be understood to include the term "organic semiconductor device" and several specific embodiments of such devices used in the electronics, automotive, or other industries.

[0066] 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 could be stored if the insulating material were replaced by a vacuum or air. It is also known as the electric permittivity or simply the permittivity. Sometimes it is also called the relative dielectric constant because it is measured relative to the dielectric constant of free space.

[0067] 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, or electromechanical) in a dissipative system. It is the reciprocal of the quality factor and represents the "quality" or persistence of the vibration.

[0068] By the term "derived", it means that the polymer repeating unit is polymerized (formed) from, for example, a polycyclic norbornene monomer according to formula (I), formula (V) or formula (VI), wherein the resulting polymer is ring-opening metathesis polymerization (ROMP). For example, the 2,3-double bond of the norbornene monomer is ring-opened and polymerized as described below:

[0069]

[0070] Thus, in accordance with the practice of the present invention, there is provided a composition comprising at least, consisting essentially of, or consisting of the following substances:

[0071] a) A compound of formula (I):

[0072]

[0073] Wherein:

[0074] m is an integer of 0, 1 or 2;

[0075] R 1 、R 2 、R 3 And R 4 Are the same or different and are each independently selected from the group consisting of: hydrogen, halogen, methyl, ethyl, linear or branched (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, tris (C 1 -C 6 ) alkoxysilyl and a group of formula (A):

[0076] -Z-Aryl (A)

[0077] Wherein:

[0078] Z is a bond or a group selected from the group consisting of:

[0079] (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 , where a and b are integers that can be the same or different, and each independently is from 1 to 12;

[0080] R 5 and R 6 are the same or different, and each independently is selected from the group consisting of: hydrogen, methyl, ethyl, linear or branched (C 3 -C 6 ) alkyl, hydroxy, methoxy, ethoxy, linear or branched (C 3 -C 6 ) alkoxy, acetoxy, (C 2 -C 6 ) acyl, hydroxymethyl, hydroxyethyl, linear or branched hydroxy (C 3 -C6 ) alkyl, phenyl and phenoxy;

[0081] Aryl is phenyl or phenyl substituted by one or more groups selected from the following: methyl, ethyl, straight or branched (C 3 -C 6 ) alkyl, hydroxy, methoxy, ethoxy, straight or branched (C 3 -C 6 ) alkoxy, acetoxy, (C 2 -C 6 ) acyl, hydroxymethyl, hydroxyethyl, straight or branched hydroxy(C 3 -C 6 ) alkyl, phenyl and phenoxy;

[0082] b) an organoruthenium compound, preferably represented by formula (II):

[0083]

[0084] wherein

[0085] c and d are integers from 0 to 5;

[0086] Z is oxygen or sulfur;

[0087] R 7 is selected from the group consisting of hydrogen, (C 1 -C 20 ) alkyl, (C 2 -C 20 ) alkenyl, (C 2 -C 20 ) alkynyl and (C 6 -C 10 ) aryl; and

[0088] R 8 、R 9 、R 10 and R 11 are the same or different and are each independently selected from the group consisting of: 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 )heterocyclic group, -OR 16 、-NO 2 、-COOH, -COOR 16 、-CONR 16 R 17 、-SO 2 NR 16 R 17 、-SO 2 R 16 、-CHO, -COR 16 , where R 16 and R 17 are the same or different and each independently selected from the group consisting of (C 1 -C 6 )alkyl, (C 1 -C 6 )perfluoroalkyl, (C 6 -C 14 )aryl, (C 6 -C 14 )perfluoroaryl; or where

[0089] R 8 , R 9 , R 10 and R 11 two or more of which together with the carbon atom to which they are attached form a substituted or unsubstituted fused (C 4 -C 8 )carbocycle, or a substituted or unsubstituted fused aromatic ring;

[0090] R 12 , R 13 and R 14 may each be the same or different and are each independently selected from the group consisting of: 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 )heterocyclic group, -OR 16 、-NO2 ,-COOH, -COOR 16 , -CONR 16 R 17 , -SO 2 NR 16 R 17 , -SO 2 R 16 , -CHO, -COR 16 , wherein R 16 and R 17 are the same or different and each independently selected from the group consisting of (C 1 -C 6 )alkyl, (C 1 -C 6 )perfluoroalkyl, (C 6 -C 14 )aryl, (C 6 -C 14 )perfluoroaryl;

[0091] R 15 is selected from the group consisting of (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 )heterocyclic group;

[0092] Ar 1 and Ar 2 are the same or different and each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl, wherein the substituents are each independently selected from the group consisting of methyl, ethyl and linear or branched (C 3 -C 6 )alkyl;

[0093] c) a photosensitizer, preferably constructed such that the organoruthenium compound is its active form, preferably represented by formula (III):

[0094]

[0095] wherein

[0096] Y is a halogen; and

[0097] R30 and R 31 are the same or different and are each independently selected from the group consisting of: hydrogen, methyl, ethyl, straight-chain or branched (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 )aryloxy; and

[0098] d) a compound of formula (IV):

[0099]

[0100] wherein

[0101] p is an integer 0, 1 or 2;

[0102] R e1 , R e2 , R e3 and R e4 are each independently selected from the group consisting of: hydrogen, halogen, methyl, ethyl, straight-chain (C 1 -C 16 )alkyl or branched (C 3 -C 16 )alkyl, perfluoro (C 1 -C 12 )alkyl, hydroxy (C 1 -C 16 )alkyl, (C 3 -C 12 )cycloalkyl, (C6 -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, acrylate, methacrylate and allyl, a straight-chain (C 1 -C 16 ) alkyl or a branched-chain (C 3 -C 16 ) alkyl having vinyl, acrylate, methacrylate or allyl as a terminal group;

[0103] wherein at least one of R e1 , R e2 , R e3 and R e4 is vinyl, acrylate, methacrylate, allyl, a straight-chain (C 1 -C 16 ) alkyl or a branched-chain (C 3 -C 16 ) alkyl having vinyl, acrylate, methacrylate or allyl as a terminal group.

[0104] Composition

[0105] It is believed that the composition of the present invention is preferably stable in the temperature range from room temperature to 80 °C, thereby providing excellent storage stability. As used herein, "stable" means that the composition of the present invention remains clear at temperatures from room temperature to 80 °C and the viscosity does not increase, especially when stored in a dark environment, such as when stored in an amber or brown container without any light. Thus, in some embodiments, the composition of the present invention does not exhibit a viscosity change when stored at a temperature below 80 °C for more than thirty (30) days.

[0106] Thus, in some embodiments, when the composition of the present invention is stored at a temperature below 80 °C for more than forty (40) days, it exhibits an increase in viscosity of less than five (5) percent. In some other embodiments, when the composition of the present invention is stored at a temperature below 80 °C for sixty (60) to ninety (90) days, it exhibits a change in viscosity of less than ten (10) percent.

[0107] In some other embodiments, when the composition of the present invention is stored at a temperature below 80 °C for one hundred twenty (120) to one hundred eighty (180) days, it exhibits a change in viscosity of less than twenty (20) percent. In some other embodiments, when the composition of the present invention is stored at ambient temperature, for example, stored at about 20 °C to 25 °C for a longer time, the range can be about one hundred twenty (120) days to three hundred (300) days or longer, it exhibits a change in viscosity of less than two (2) percent.

[0108] That is, when stored under ambient temperature conditions, the viscosity of the composition remains substantially unchanged, but the composition undergoes bulk polymerization once exposed to suitable actinic radiation, which can be confirmed by UV-DSC measurements, indicating that, as disclosed above, even after the composition is stored for a long time, the heat of polymerization remains unchanged.

[0109] The monomers employed in the composition of the present invention are known per se in the literature or can be prepared by any known method in the art for this or similar types of monomers.

[0110] Furthermore, the monomers described herein are prone to bulk polymerization, that is, when polymerized under bulk ring-opening metathesis polymerization (ROMP) conditions using certain transition metal catalysts (such as organoruthenium and organoosmium compounds), they are used in their pure form without the use of any solvent. See, for example, Handbook of Metathesis, Ed.: Wiley-VCH, Weinheim, Germany, 2003 by R.H. Grubbs et al., Acc. Chem. Res. 2001, 34, 18 - 29 by R.H. Grubbs et al., Angew. Chem. Int. Ed., 2006, 45, 3760 - 3765 by R.H. Grubbs et al. See also U.S. Patent No. 6,838,489, the relevant portions of which are incorporated herein by reference. The term "bulk polymerization" as used herein shall have the meaning generally accepted in the art. That is, a polymerization reaction generally carried out substantially without a solvent.

[0111] However, in some cases, a small amount of solvent is present in the reaction medium. For example, such a small amount of solvent can be used to dissolve the potential catalyst and / or activator or to transport them to the reaction medium. In addition, some solvents can be used to reduce the viscosity of the monomers. The amount of solvent that can be used in the reaction medium can range from 0 to 5 weight percent of the total weight of the monomers used. Any suitable solvent that can dissolve the catalyst, activator, and / or monomer can be used in the present invention. Examples of such solvents include alkanes, cycloalkanes, toluene, THF, dichloromethane, dichloroethane, etc.

[0112] Advantageously, it has now been found that one or more of the monomers themselves can be used to dissolve the potential catalyst as well as the activator, thus avoiding the use of a solvent. In addition, one monomer itself can be used as a solvent for another monomer, thus eliminating the need for an additional solvent. For example, if the first monomer of formula (I) is a solid at room temperature, the second monomer of formula (I) (which is a liquid at room temperature) can be used as a solvent for the first monomer of formula (I) (which is a solid), and vice versa. Thus, in such cases, more than one monomer can be used in the compositions of the present invention.

[0113] Generally, the compositions of the present invention exhibit a low viscosity at room temperature, which can be less than 100 centipoise or lower. 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 ranges from about 10 to 100 centipoise. In 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, less than 20 cP. In some other embodiments, it can even be less than 10 cP and can vary from as low as 3 cP to 9 cP at room temperature.

[0114] Therefore, the compositions of the present invention can also include other high refractive index polymer materials and / or nanoparticles, which will bring such desired 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 having a size range of 1 to 100 nm, including crosslinked poly(styrene), crosslinked poly(methacrylate), metal oxides (such as zinc oxide, magnesium oxide, titanium oxide), silicon, silica, silicon nitride, and luminescent materials (such as III-V semiconductor nanoparticles, such as indium phosphide).

[0115] Compound of formula (I):

[0116] 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 still 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 can even be 1.7 or greater. And preferably it is 2.0 or less.

[0117] It is believed that the monomer of formula (I) can also be used as a high refractive index material, which imparts a high refractive index to the resulting polymer film when bulk polymerized at a temperature and / or conditions different from those at which the composition is applied to the desired substrate.

[0118] For example, when the composition of the present invention contains two or more monomers, they can be present in any desired amounts to bring about the desired benefits, including refractive index improvement or viscosity improvement or both.

[0119] Generally, the composition according to the present invention comprises one or more of the above-mentioned monomers of formula (I), and if desired, it can also contain additional monomers of formula (I) that are different from each other. As will be seen below, various composition embodiments are selected to provide properties suitable for and desirable for the uses targeted by these embodiments, and thus these embodiments can be adjusted for various specific applications.

[0120] For example, as described above, appropriate combination of different monomers of formula (I) enables the customization of compositions having the desired refractive index, viscosity, and optical transmission characteristics. In addition, as further described herein, it may be desirable to include other polymeric or monomeric materials, such as inorganic nanoparticles, which are compatible to provide the desired optical properties, depending on the end use.

[0121] Therefore, in a preferred embodiment of the present invention, the monomer of formula (I) is selected from the group consisting of:

[0122]

[0123] 5-(4-phenylbutyl)bicyclo[2.2.1]hept-2-ene;

[0124]

[0125] 5-(3-phenylpropyl)bicyclo[2.2.1]hept-2-ene;

[0126]

[0127] 5-phenylethylbicyclo[2.2.1]hept-2-ene (PENB);

[0128]

[0129] 5-(Benzyloxy)bicyclo[2.2.1]hept-2-ene;

[0130]

[0131] 5-(2-([1,1'-Biphenyl]-4-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene;

[0132]

[0133] 5-(2-([1,1'-Biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtO-2-PhPh);

[0134]

[0135] 5-Butylbicyclo[2.2.1]hept-2-ene (BuNB);

[0136]

[0137] 5-Hexylbicyclo[2.2.1]hept-2-ene (HexylNB);

[0138]

[0139] 5-Octylbicyclo[2.2.1]hept-2-ene (OctNB);

[0140]

[0141] 5-Decylbicyclo[2.2.1]hept-2-ene (DecNB);

[0142]

[0143] 5-Ethylidenebicyclo[2.2.1]hept-2-ene;

[0144]

[0145] 2-Ethylidene-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;

[0146]

[0147] 3a,4,4a,5,8,8a,9,9a-Octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene (one of the cyclopentadiene trimers, TCPD1, also known as CPD3)

[0148]

[0149] 5-Norbornenylmethyl Eugenol Acetate (EuAcNB);

[0150]

[0151] 5-Norbornenylmethyl Eugenol (EuOHNB);

[0152]

[0153] NB(MeOH) 2 ;

[0154]

[0155] PhAcNB;

[0156]

[0157] Tetracyclododecene (TD);

[0158]

[0159] 5-(Phenoxymethyl)bicyclo[2.2.1]hept-2-ene (NBMeOPh);

[0160]

[0161] 5-(([1,1'-Biphenyl]-2-yloxy)methyl)bicyclo[2.2.1]hept-2-ene (NBMeOPhPh);

[0162]

[0163] 2-Phenyltetracyclododecene (PhTD);

[0164]

[0165] 2-Benzyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;

[0166]

[0167] 2-Phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD);

[0168]

[0169] 2-Butyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (ButylTD);

[0170]

[0171] 2-Hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (HexylTD);

[0172]

[0173] 2-Octyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (OctylTD);

[0174]

[0175] 2-Decyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (DecylTD);

[0176]

[0177] 2-Cyclohexyltetracyclododecene (CyclohexylTD);

[0178]

[0179] 2-(Cyclohexylmethyl)-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;

[0180]

[0181] 2-(Cyclohexylethyl)-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;

[0182]

[0183] Methyl (1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalen-2-yl) acetate (TDMeOAc); and

[0184]

[0185] Tetracyclododecadiene (TDD).

[0186] As described 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.

[0187] Organic ruthenium compound

[0188] As described above, the composition of the present invention contains at least one organoruthenium compound, preferably represented by formula (II), which, when the composition is subjected to appropriate actinic radiation, will cause bulk polymerization as described herein under ROMP conditions. Generally, such an organoruthenium compound represented by formula (II) is "latent" and becomes active only under certain conditions. Also, as used herein, the term "latent" means that when the composition of the present invention is stored at ambient conditions up to a temperature of 80 °C, the organoruthenium catalyst used in the composition of the present invention remains inactive for an extended period of time. Thus, in some embodiments, when stored at a temperature below 80 °C, the organoruthenium catalyst remains latent for more than thirty (30) days. In some other embodiments, when stored at a temperature below 50 °C, the organoruthenium catalyst remains latent for forty (40) to ninety (90) days.

[0189] Generally, any latent organoruthenium compound capable of causing ring-opening metathesis polymerization of monomers of formula (I) or formula (V) or formula (VI), preferably represented by formula (II), can be used in the composition of the present invention. Interestingly, it has now been found that the organoruthenium compound of formula (II) is very stable at temperatures from about 25 °C (i.e., ambient conditions) to about 80 °C and can be stored for several days, even up to three to six months or longer, either as such or in the presence of one or more monomers of formula (I) or formula (V) or formula (VI). That is, the organoruthenium compound of formula (II) is preferably used as a latent catalyst, which is stable at room temperature or near room temperature up to a high temperature of 80 °C and can be easily activated by various conditions, including but not limited to heat, acid, light, and chemical activation only when needed. Chemical activation can include the use of a thermal acid generator or a photoacid generator.

[0190] Several potential catalysts known in the literature are unstable under the conditions specified herein, and most of them do not exhibit the desired storage stability described herein. See, for example, Organometallics, 2011, 30(24):6713 - 6717 by Grubbs et al.; Angew. Chem. Int. Ed. 2016, 55, 764 - 767 by Sutar et al.; Monatsh Chem (2014) 145:1513 - 15177 by Leitgeh et al.; J. Mater. Chem. C. 2015, 3, 693 - 702 by van Hensbergen et al.; J. Am. Chem. Soc., 2009, 131, 203802039 by Grubbs et al.; Eur. J. Inorg. Chem., 2014, 1131 - 1136 by Zak et al.; ACS Catal. 2017, 7, 5443 - 5449 by Gawin et al. More 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, the composition comprising the organoruthenium compound of formula (II) provides advantages heretofore unattainable in the various applications described herein.

[0191] According to the present invention, the organoruthenium compound can be any publicly available organoruthenium compound, or the organoruthenium compound described in US11230624 B2 can be used. Preferably, it is a compound of formula (II), wherein:

[0192] Z is oxygen;

[0193] R 7 is hydrogen;

[0194] R 8 、R 9 、R 10 and R 11 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, and NO 2 ;

[0195] R 12 、R 13 and R 14 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, and NO 2 ;

[0196] R 15 is selected from the group consisting of methyl, ethyl, and cyclohexyl;

[0197] Ar 1 and Ar 2identical or different and 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.

[0198] Thus, within the scope of the organoruthenium compounds of formula (II), some exemplary potential catalysts can be selected without any limitation from the group consisting of the following:

[0199]

[0200] [1,3-Bis(2,6-diisopropylphenyl)-2-imidazolidinylidene]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxo-bridged-κO}[2-(oxido-bridged-κO)phenylmethylene-κC]ruthenium(II) (Ru-1);

[0201]

[0202] [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]{2-[(E)-({2-[isopropylthio-κS]phenyl}imino-κN)methyl]phenoxo-bridged-κO}[2-(oxido-bridged-κO)phenylmethylene-κC]ruthenium(II) (Ru-2);

[0203]

[0204] [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]{2-[(E)-({2-[cyclohexylthio-κS]phenyl}imino-κN)methyl]phenoxo-bridged-κO}[2-(oxido-bridged-κO)phenylmethylene-κC]ruthenium(II) (Ru-3); and

[0205]

[0206] [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxo-bridged-κO}[2-(oxido-bridged-κO)phenylmethylene-κC]ruthenium(II) (Ru-4).

[0207] Interestingly, it has now been found that when subjected to appropriate photolysis conditions, certain known photoactive compounds (photosensitizers) can activate the organoruthenium compounds of formula (II), thereby promoting the bulk polymerization of one or more monomers of formula (I) or formula (V) or formula (VI) contained in the composition of the present invention under the ROMP conditions described herein.

[0208] Based on the total amount of the compound of formula (I), the total amount of the organoruthenium compound ranges from 0.001% by weight to 1% by weight. Preferably, it ranges from 0.005 to 0.5% by weight, more preferably from 0.01 to 0.1% by weight, and even more preferably from 0.02 to 0.05% by weight.

[0209] Photosensitizer

[0210] According to the present invention, the composition contains a photosensitizer, preferably configured to render the organoruthenium compound in its active form, preferably represented by formula (III).

[0211] As the photosensitizer, known photoactive compounds can be used, such as a class of substituted xanthene derivatives. Preferably, the photosensitizer is represented by structural formula (III):

[0212]

[0213] where

[0214] Y is a halogen; and

[0215] R 30 and R 31 are the same or different and are each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (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 ) aryloxy.

[0216] In some embodiments, the compound of formula (III) has the following characteristics:

[0217] Y is chlorine or bromine; and

[0218] R 30 and R 31 are the same or different and are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, phenyl, cyclohexyl, methoxy, ethoxy, n-propoxy, and phenoxy.

[0219] Representative examples of the compound of formula (VII) are listed below, but are not limited thereto:

[0220]

[0221] 1-chloro-4-methoxy-9H-thioxanthen-9-one;

[0222]

[0223] 1-chloro-4-ethoxy-9H-thioxanthen-9-one;

[0224]

[0225] 1-chloro-4-propoxy-9H-thioxanthen-9-one (sold by Lambson under the trade name CPTX);

[0226]

[0227] 1-chloro-2-propoxy-9H-thioxanthen-9-one;

[0228]

[0229] 1-chloro-2-ethoxy-9H-thioxanthen-9-one;

[0230]

[0231] 1-chloro-2-methoxy-9H-thioxanthen-9-one;

[0232]

[0233] 1-chloro-4-methyl-9H-thioxanthen-9-one;

[0234]

[0235] 1-chloro-4-ethyl-9H-thioxanthen-9-one;

[0236]

[0237] 1-Bromo-4-propoxy-9H-thioxanthen-9-one; and

[0238]

[0239] 1-Chloro-4-phenoxy-9H-thioxanthen-9-one.

[0240] It is believed that the bulk polymerization of monomers can be initiated by the combination of a suitable organoruthenium compound with one or more photosensitizers (photosensitizers). When the composition is subjected to appropriate actinic radiation, typically at wavelengths from about 240 nm to 410 nm, the composition undergoes bulk ring-opening metathesis polymerization (ROMP) to form a transparent film or object. For this purpose, the combination of the organoruthenium compound of formula (II) and the photosensitizer of formula (III) is particularly suitable.

[0241] Preferably, based on the total amount of the compound of formula (I), the total amount of the photosensitizer (preferably represented by formula (III)) is in the range of 0.01 to 5% by weight. More preferably in the range of 0.05 to 1% by weight, even more preferably 0.08 to 0.5% by weight.

[0242] In some embodiments, the composition of the present invention undergoes bulk polymerization upon exposure to suitable ultraviolet radiation to form a substantially transparent film. The monomers undergo bulk polymerization to form a film that is substantially transparent to visible light. That is, most of the visible light passes through the film. In some embodiments, such a film formed from the composition of the present invention exhibits a transmittance equal to or higher than 90% of visible light. In some other embodiments, such a film formed from the composition of the present invention exhibits a transmittance equal to or higher than 95% of visible light.

[0243] Thus, in some embodiments, the composition of the present invention can undergo bulk polymerization to form a solid object, such as a transparent film, in less than five seconds after exposure to suitable actinic radiation. In some other embodiments, the composition of the present invention can undergo bulk polymerization to form a solid object, such as a transparent film, in less than ten seconds after exposure to suitable actinic radiation. In some other embodiments, the composition of the present invention can undergo bulk polymerization to form a solid object, such as a transparent film, in one to ten seconds, two to nine seconds, three to eight seconds, four to seven seconds, etc. after exposure to suitable actinic radiation.

[0244] In still other embodiments, the composition of the present invention undergoes bulk polymerization upon exposure to suitable ultraviolet radiation at a temperature of 80 °C to 100 °C to form a substantially transparent film or object.

[0245] In some embodiments, the photosensitizer preferably represented by formula (III) can be activated at certain wavelengths of electromagnetic radiation, which generally range from about 240 nm to 400 nm. Thus, any compound that is active under this electromagnetic radiation can be used in the compositions of the present invention. In some embodiments, the radiation wavelength that activates the photosensitizer preferably represented by formula (III) is 260 nm. In some other embodiments, the radiation wavelength that activates the photosensitizer is 310 nm. In some other embodiments, the radiation wavelength that activates the photosensitizer is 395 nm.

[0246] However, any other known photosensitizer capable of activating the potential organoruthenium compounds used herein can also be used in the compositions of the present invention. All such compounds are part of the present invention.

[0247] Compound of formula (IV)

[0248] According to the present invention, the composition contains one or more compounds of formula (IV):

[0249]

[0250] wherein

[0251] p is an integer of 0, 1 or 2;

[0252] R e1 、R e2 、R e3 and R e4 are each independently selected from the group consisting of: 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, tris(C 1 -C 6 )alkoxysilyl, vinyl, acrylate, methacrylate and allyl, a linear (C 1 -C 16 )alkyl or a branched (C 3 -C 16 )alkyl having vinyl, acrylate, methacrylate or allyl as a terminal group;

[0253] wherein at least one of R e1 , R e2 , R e3 and R e4 is vinyl, acrylate, methacrylate, allyl, a linear (C 1 -C 16 )alkyl or a branched (C 3 -C 16 )alkyl having vinyl, acrylate, methacrylate or allyl as a terminal group.

[0254] It is believed that a compound of formula (IV) having at least one polymerizable group selected from vinyl, acrylate, methacrylate, allyl or a combination thereof can result in a lower haze value for the compound and the resulting film (layer).

[0255] According to the present invention, as the compound of formula (IV), any publicly available compound belonging to formula (IV) can be used.

[0256] In a preferred embodiment of the present invention, from the perspective of reducing the haze value of the film (layer), the formula (IV) monomer is selected from the group consisting of:

[0257]

[0258]

[0259] Most preferably, the composition contains at least vinyl norbornene as the formula (IV) monomer.

[0260] Based on the total amount of the compound of formula (I), the total amount of the compound of formula (IV) is in the range of 0.1 to 100% by weight. More preferably, from the perspective of achieving good lower haze value of the film (layer) and / or achieving good optical and mechanical properties of the film, the total amount of the compound of formula (IV) is in the range of 1 to 50% by weight, more preferably 5 to 30% by weight, even more preferably 8 to 20% by weight.

[0261] Additional monomers (V), (VI)

[0262] 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 monomers of formula (V) and / or monomers of formula (VI).

[0263] The monomer of formula (V) is:

[0264]

[0265] wherein:

[0266] O is an integer from 0 to 2 (end values included);

[0267] D is SiR 21 R 22 R 23 or a group selected from the following:

[0268] -(CH 2 ) c -O-SiR 21 R 22 R 23 (E); -(CH 2 ) c -SiR 21 R 22 R 23 (F); and

[0269] -(SiR 21 R 22 ) c -O-SiR 21 R 22 R 23 (G); wherein

[0270] c is an integer from 1 to 10 (end values included), where one or more CH 2 are optionally substituted with (C 1 -C 10 ) alkyl, (C 1 -C 10 ) perfluoroalkyl or (C 6 -C 14 ) aryl;

[0271] R 18 、R 19 and R 20 are the same or different and are each independently selected from hydrogen, halogen, and hydrocarbon groups, where the hydrocarbon groups are selected from methyl, ethyl, linear or branched (C 3 -C 12 ) alkyl, (C 3 -C 12 ) cycloalkyl, (C6 -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 or (C 6 -C 10 ) aryloxy; and

[0272] R 21 , R 22 and R 23 are each independently methyl, ethyl, linear or branched (C 3 -C 9 ) alkyl, substituted or unsubstituted (C 6 -C 14 ) aryl, methoxy, ethoxy, linear or branched (C 3 -C 9 ) alkoxy or substituted or unsubstituted (C 6 -C 14 ) aryloxy.

[0273] In this form of the present invention, it has now been found that the monomers of formula (V) provide further advantages. That is, the monomers of formula (V) can impart high or low refractive indices and low or high dielectric constants to the composition depending on the nature of the monomer, and thus can be customized as needed. In addition, the monomers of formula (V) generally improve the adhesion properties and can therefore be used as "adhesion modifiers". Finally, the monomers of formula (V) can exhibit low viscosity and good solubility in potential catalysts and / or activators, as well as various other advantages.

[0274] In some embodiments, the compositions of the present invention comprise first and second monomers of formula (I) that are different from each other, and one of the first and second monomers has a refractive index of at least 1.5 and a viscosity of less than 100 centipoise, wherein the first monomer is completely miscible with the second monomer to form a clear solution. However, as previously described, any one or more monomers of formula (V) can also be used in this embodiment of the present invention.

[0275] The monomers of formula (VI) are:

[0276]

[0277] wherein

[0278] R 24 and R 25 are the same or different and are each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 3 -C 6 ) alkyl, methoxy, ethoxy, linear or branched (C 3 -C 6 ) alkoxy, acetoxy, (C 2 -C 6 ) acyl, phenyl and phenoxy; or

[0279] R 24 together with R 25 and the carbon atom to which they are attached form a (C 5 -C 7 ) carbocyclic ring optionally containing one or more double bonds;

[0280] R 26 is hydrogen, halogen, methyl, ethyl, linear or branched (C 3 -C 16 ) alkyl, (C 6 -C 10 ) aryl, (C 6 -C 10 ) aryl(C 1 -C 6 ) alkyl, hydroxy, methoxy, ethoxy, linear or branched (C 3 -C 16 ) alkoxy, (C 6 -C 10 ) aryloxy, (C 6 -C 10 ) aryl(C 1 -C 6 ) alkoxy, O(CO)R 27 and O(CO)OR 27 , where R 27is methyl, ethyl, a linear or branched (C 3 -C 16 ) alkyl group, (C 6 -C 10 ) aryl group, and (C 6 -C 10 ) aryl(C 1 -C 6 ) alkyl group.

[0281] Similarly, any monomer within the scope of the formula (V) monomer can be used in the composition of the present invention. Representative examples of the formula (V) monomer include, but are not limited to, the following:

[0282]

[0283] (Bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane (NBCH 2 OSiMePh 2 ) ;

[0284]

[0285] (Bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(ethyl)diphenylsilane;

[0286]

[0287] (Bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(ethyl)(methyl)(phenyl)silane;

[0288]

[0289] (Bicyclo[2.2.1]hept-5-en-2-ylmethoxy)dimethyl(phenyl)silane;

[0290]

[0291] Bicyclo[2.2.1]hept-5-en-2-yltrimethoxysilane (TMSNB);

[0292]

[0293] Bicyclo[2.2.1]hept-5-en-2-yltriethoxysilane (NBSi(OC 2 H 5 ) 3 ) ;

[0294]

[0295] Bicyclo[2.2.1]hept-5-en-2-yl(tert-butoxy)dimethoxysilane; and

[0296]

[0297] (2-(Bicyclo[2.2.1]hept-5-en-2-yl)ethyl)trimethoxysilane.

[0298] Representative examples of the monomer of formula (VI) include, but are not limited to, the following:

[0299]

[0300] Dicyclopentadiene (DCPD);

[0301]

[0302] 4,4a,4b,5,8,8a,9,9a-octahydro-1H-1,4:5,8-dimethanoanthracene (one of the cyclopentadiene trimers, TCPD2);

[0303]

[0304] 1-Methoxy-dicyclopentadiene;

[0305]

[0306] 1-(n-Butoxy)-dicyclopentadiene;

[0307]

[0308] 1-(n-Octyloxy)-dicyclopentadiene;

[0309]

[0310] 3a,4,7,7a-Tetrahydro-1H-4,7-methanoinden-1-yl acetate;

[0311]

[0312] 3a,4,7,7a-Tetrahydro-1H-4,7-methanoinden-1-yl benzoate;

[0313]

[0314] 3a,4,7,7a-Tetrahydro-1H-4,7-methanoinden-1-yl 2-phenylacetate; and

[0315]

[0316] 3a,4,7,7a-Tetrahydro-1H-4,7-methanoinden-1-yl 3-phenylpropionate.

[0317] Ultraviolet (UV) light blocker

[0318] It is believed that the addition of certain ultraviolet (UV) light blockers unexpectedly imparts further stability to the compositions of the present invention, especially when used in an ultraviolet irradiation environment, such as in a container of a 3D printer or in the encapsulation of an optical device (such as an OLED). More importantly, it has now been found that the addition of two or more such ultraviolet blocking compounds further provides a synergistic effect, since the compositions of the present invention can cure at a similar or faster rate compared to compositions that do not employ these two or more ultraviolet blocking compounds. Surprisingly, the addition of these two or more ultraviolet blockers does not reduce the bulk polymerization activity of the compositions of the present invention when exposed to suitable actinic radiation, thus providing a synergistic and beneficial effect.

[0319] It should also be noted that when exposed to suitable actinic radiation, the compositions of the present invention undergo bulk polymerization at a rate similar to that of a composition that does not contain either of the two ultraviolet blockers. Similarly, the compositions of the present invention exhibit a similar polymerization rate compared to a composition containing only one ultraviolet blocker. Thus, when exposed to suitable actinic radiation, the polymerization rate activity of the compositions of the present invention is not significantly reduced. In addition, the films formed from the compositions of the present invention exhibit substantially the same transmittance percentage, with the compositions of the present invention exhibiting a transmittance of better than 90% at wavelengths from 370 nm to 800 nm.

[0320] Accordingly, the compositions of the present invention contain at least one compound of formula (VIII):

[0321]

[0322] wherein

[0323] n is an integer from 0 to 4;

[0324] each R 32 is independently selected from the group consisting of: hydrogen, methyl, ethyl, straight-chain or branched (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 -C12 ) 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 ) aryloxy.

[0325] In addition, the composition of the present invention contains at least one compound of formula (IX):

[0326]

[0327] where

[0328] R 33 is selected from the group consisting of methyl, ethyl, linear or branched (C 3 -C 12 ) alkyl and (C 3 -C 12 ) cycloalkyl.

[0329] R 34 and R 35 may each be the same or different and are independently selected from the group consisting of (C 1 -C 10 ) alkyl, (C 6 -C 18 ) aryl, (C 6 -C 12 ) aryl (C 1 -C 5 ) alkyl and (C 1 -C 5 ) alkyl (C 6 -C 12 ) aryl. In some embodiments, R 34 and R 35 are independently selected from the group consisting of (C 4 -C 8 ) alkyl, phenyl and phenyl (C 1 -C 3 ) alkyl. In some other embodiments, R 34 and R 35 are independently selected from the group consisting of (C 5 -C 8 ) alkyl and phenyl (C 1 -C 3) selected from the group consisting of alkyl groups.

[0330] R 34 and R 35 The alkyl moiety can be straight-chain or branched. Similarly, each time it appears, all or part of the alkyl moiety being branched is independently selected. R 34 and R 35 One or more methylenes of the alkyl moiety can be replaced by -CO-, -O-, or -COO-. That is, the -CH 2 - moiety of the alkyl is replaced by one of -CO-, -O-, or -COO-. In some embodiments, one or more hydrogens of the methylene moiety of R 34 and / or R 35 are replaced by -COO-.

[0331] Surprisingly, by including a compound of formula (VIII) and a compound of formula (IX), not only can the stability of the composition be improved, but also the optical properties of the articles made therefrom, whether in the manufacture of OLED devices or in the manufacture of 3D articles. It is believed that the compound of formula (VIII) or formula (IX) acts as an ultraviolet blocker among other functions, thus conferring greater stability to the composition when in contact with any ultraviolet light peripherally during the ultraviolet exposure of the composition, for example when the composition is drawn out of a barrel to form a desired 3D object.

[0332] Therefore, any compound that may have a similar function to the compound of formula (VIII) or formula (IX) can also be used in the composition of the present invention, such as any other known ultraviolet blocker. Any amount of the compound of formula (VIII) or formula (IX) that can achieve the desired effect can be used in the composition of the present invention. Generally, such amounts can be about 1:200 molar parts of the compound of formula (VIII) or formula (IX): compound of formula (II). In some other embodiments, such amounts are about 1:100 molar parts of the compound of formula (VIII) or formula (IX): compound of formula (II); or 1:50 molar parts of the compound of formula (VIII) or formula (IX): compound of formula (II), and so on. However, it should be noted that it is not necessary to use the same amount of the compound of formula (VIII) or formula (IX), but rather a combination of different amounts of the compound of formula (VIII) with a suitable amount (usually in the amounts described above) of the compound of formula (IX) can be used.

[0333] Representative examples of the compound of formula (VIII) are listed below, but are not limited thereto:

[0334]

[0335] 2,5-Bis(5-(tert-butyl)benzo[d]oxazol-2-yl)thiophene (BTBBT), commercially available as Benetex OB Plus from Mayzo;

[0336]

[0337] 5-(tert-Butyl)-2-(5-(5-isopropylbenzo[d]oxazol-2-yl)thiophen-2-yl)benzo[d]oxazole;

[0338]

[0339] 2,5-Bis(5-isopropylbenzo[d]oxazol-2-yl)thiophene;

[0340]

[0341] 5-Ethyl-2-(5-(5-isopropylbenzo[d]oxazol-2-yl)thiophen-2-yl)benzo[d]oxazole;

[0342]

[0343] 2,5-Bis(5-ethylbenzo[d]oxazol-2-yl)thiophene;

[0344]

[0345] 5-Ethyl-2-(5-(5-methylbenzo[d]oxazol-2-yl)thiophen-2-yl)benzo[d]oxazole; and

[0346]

[0347] 2-(5-(Benzo[d]oxazol-2-yl)thiophen-2-yl)-5-(tert-butyl)benzo[d]oxazole.

[0348] Representative examples of the compound of formula (IX) are listed below, but are not limited thereto:

[0349]

[0350] 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

[0351]

[0352] 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.

[0353] Various other UV-blocking compounds and / or UV absorbers for the compositions of the present invention include the following:

[0354]

[0355] wherein n and R 32 are as defined in formula (VIII).

[0356] Representative compounds within the scope of formula (VIIIa) and formula (VIIIb) can be represented as follows:

[0357]

[0358] 1,2-Bis(4-(benz[d]oxazol-2-yl)phenyl)ethylene, which is commercially available from Mayzo as Benetex OB-1; and

[0359]

[0360] Sodium 2,2'-([1,1'-biphenyl]-4,4'-diylbis(ethene-2,1-diyl))dibenzene sulfonate, which is commercially available from Mayzo as Benetex OB-M1.

[0361] As used herein, Aryl can also include the following:

[0362] Substituted or unsubstituted biphenyls of the following formula:

[0363]

[0364] Substituted or unsubstituted naphthalenes of the following formula:

[0365]

[0366] Substituted or unsubstituted terphenyls of the following formula:

[0367]

[0368] Substituted or unsubstituted anthracenes of the following formula

[0369]

[0370] Substituted or unsubstituted fluorenes of the following formula:

[0371]

[0372] wherein R x is independently selected, each time it appears, from methyl, ethyl, linear or branched (C 3 -C 12 )alkyl or (C 6 -C 10 )aryl.

[0373] Monomer crosslinking agent

[0374] Advantageously, it has now also been found that the mechanical properties of the three-dimensional objects formed from the compositions of the present invention can be significantly improved by using a suitable amount of one or more monomer crosslinking agents. Representative examples of such suitable monomer crosslinking agents can be selected from the group consisting of:

[0375] i) Compounds of formula (Xa):

[0376]

[0377] ii) Compounds of formula (Xb):

[0378]

[0379] iii) Compounds of formula (Xc):

[0380]

[0381] wherein

[0382] m is an integer of 0, 1 or 2;

[0383] b is an integer from 1 to 10;

[0384] K is selected from the group consisting of CH 2 、CH 2 -CH 2 、O and S;

[0385] X is a bond or is selected from O, S, 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 (C 6 -C 10 )arylSiR b R c, a moiety selected from the group consisting of -C(O)-, -C(O)O-, -OC(O)-, -OC(O)O-, -SC(O)-, -C(O)-S-, -CH=CH- and -C≡C-;

[0386] R a , R b and R c are each independently selected from the group consisting of hydrogen, methyl, ethyl, or a linear or branched (C 3 -C 12 )alkyl, (C 3 -C 8 )cycloalkyl, (C 5 -C 12 )bicycloalkyl, (C 5 -C 12 )bicycloalkenyl, and (C 5 -C 12 )bicycloalkenyl(C 1 -C 3 )alkylSi(CH 3 ) 2 , and thus the O, NR a and / or S atoms are not directly connected to each other; and

[0387] n is an integer from 0 to 10.

[0388] Advantageously, it has now been found that the addition of one or more compounds of formula (Xa), formula (Xb) or formula (Xc) can adjust the properties of the composition according to the intended purpose. For example, by appropriately combining one or more compounds of formula (Xa), formula (Xb) or formula (Xc) with the composition of the present invention, other properties such as the mechanical properties of the articles formed from the composition of the present invention can now be improved. More specifically, it has now been found that the addition of certain silicone compounds within the scope of the compounds of formula (Xa) or formula (Xb) can improve the impact strength of the products formed therefrom. Any amount of the one or more compounds of formula (Xa), formula (Xb) or formula (Xc) can be employed to bring about the desired benefit. Generally, based on the total moles of the monomer of formula (I), one or more monomers of formula (V) or formula (VI) (if used), and one or more compounds of formula (Xa), formula (Xb) or formula (Xc), the amount of the one or more compounds of formula (Xa), formula (Xb) or formula (Xc) can be from 0 to 20 mol%. In some embodiments, such amount can be from 1 to 15 mol%, in some other embodiments, such amount can be from 0.5 to 10 mol%, and in some other embodiments, such amount can be from 0.5 to 5 mol%.

[0389] Thus, in some embodiments, the impact strength of the polymer formed from the compositions of the present invention is at least 40 J / m. In some other embodiments, the impact strength of the polymer formed from the compositions of the present invention is at least 60 J / m. In still some other embodiments, the impact strength of the polymer formed from the compositions of the present invention is at least 80 J / m, 100 J / m or higher, 140 J / m or higher, or may be higher than 160 J / m, such as higher than 170 J / m, higher than 180 J / m, higher than 200, 220 or 240 J / m, or even higher than 500, 550, 600, 700 or 800 J / m, depending on the type of monomers employed as described herein. In some embodiments, the polymer formed from the compositions of the present invention comprising one or more monomers of formula (I) itself may exhibit such unusual impact strength, which ranges from 50 to 800 J / m.

[0390] In some embodiments, each of the compounds of formula (Xa), formula (Xb) or formula (Xc) complies with m = 0 and K = CH 2 . In some embodiments, each of the compounds of formula (Xa), formula (Xb) or formula (Xc) complies with m = 1 and K = CH 2 . In still some other embodiments, each of the compounds of formula (Xa), formula (Xb) or formula (Xc) complies with m = 2 and K = CH 2 .

[0391] Representative examples of compounds within the scope of formula (Xa) or formula (Xb) include, but are not limited to, the following:

[0392]

[0393] 1,3-Bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (BisENBTMDS);

[0394]

[0395] 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;

[0396]

[0397] 1,5-Bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane (BisENBHMTS);

[0398]

[0399] 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;

[0400]

[0401] 1,4 - bis((2-(bicyclo[2.2.1]hept - 5 - en - 2 - yl)ethyl)dimethylsilyl)benzene;

[0402]

[0403] 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);

[0404]

[0405] (Bicycloheptenyl)ethyl - terminated polydimethylsiloxane, where n is from 2 to 4; and

[0406]

[0407] 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 (trinorbornenylisobutyl POSS).

[0408] In addition, various other oligomeric or polymeric polysiloxanes with polyfunctional cycloalkene side - groups are suitable as cross - linking molecules in the compositions of the present invention, which may or may not be within the scope of the compounds of formula (XIa). Such examples include oligomeric siloxanes of the following formula:

[0409]

[0410] where b is an integer from 1 to 9;

[0411] n is an integer from 1 to 10; and

[0412] R b and R c are each independently selected from the group consisting of methyl, ethyl, n - propyl, isopropyl, n - butyl, isobutyl, and phenyl.

[0413] Various other non-limiting examples of the compound of formula (Xa), formula (Xb) or formula (Xc) can be selected from the group consisting of:

[0414]

[0415] 1,4-bis(bicyclo[2.2.1]hept-5-en-2-yl)butane;

[0416]

[0417] 5,5'-(oxybis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

[0418]

[0419] 5,5'-(oxybis(ethane-2,1-diyl))bis(bicyclo[2.2.1]hept-2-ene);

[0420]

[0421] bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methane;

[0422]

[0423] 5,5'-((propane-2,2-diylbis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

[0424]

[0425] 5,5'-((propane-1,1-diylbis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

[0426]

[0427] 5,5'-((((1-phenylethane-1,1-diyl)bis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

[0428]

[0429] 1,2-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)ethane;

[0430]

[0431] 1,3-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)propane;

[0432]

[0433] 1,4-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)butane;

[0434]

[0435] 1,6-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)hexane;

[0436]

[0437] 1,8-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)octane;

[0438]

[0439] bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)dimethylsilane;

[0440]

[0441] wherein n is from 2 to 4;

[0442]

[0443] wherein R and R' are independently selected from (C 1 -C 12 alkyl), (C 6 -C 10 aryl) and (C 6 -C 10 aryl)(C 1 -C 12 alkyl);

[0444]

[0445] bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)(phenyl)silane;

[0446]

[0447] bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)diphenylsilane;

[0448]

[0449] 1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)benzene;

[0450]

[0451] 1,3-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)benzene;

[0452]

[0453] bis(bicyclo[2.2.1]hept-5-en-2-ylmethyl) carbonate;

[0454]

[0455] bicyclo[2.2.1]hept-5-en-2-ylmethyl bicyclo[2.2.1]hept-5-ene-2-carboxylate;

[0456]

[0457] wherein b is an integer from 1 to 6;

[0458]

[0459] bis(bicyclo[2.2.1]hept-5-en-2-ylmethyl) terephthalate;

[0460]

[0461] bicyclo[2.2.2]oct-5-en-2-ylmethyl bicyclo[2.2.2]oct-5-ene-2-carboxylate;

[0462]

[0463] 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);

[0464]

[0465] 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)

[0466]

[0467] 1,4,4a,4b,5,8,8a,8b-octahydro-1,4:5,8-dimethano-benzene;

[0468]

[0469] 4,4a,4b,5,8,8a,9,9a-octahydro-1H-1,4:5,8-dimethanoanthracene;

[0470]

[0471] 1,4,4a,5,8,8a,9,9a,10,10a-decahydro-1,4:5,8-dimethanoanthracene;

[0472]

[0473] 1,4,4a,5,6,6a,7,10,10a,11,12,12a-dodecahydro-1,4:7,10-dimethanodibenzo[a,e][8]annulene; and

[0474]

[0475] 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]biphenyl.

[0476] Various other non-limiting examples within the scope of the compound of formula (Xa), formula (Xb) or formula (Xc) are listed as follows:

[0477]

[0478] 1,3-bis(bicyclo[2.2.1]hept-5-en-2-yl)propane;

[0479]

[0480] 5,5'-(2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)propane-1,3-diyl)bis(bicyclo[2.2.1]hept-2-ene);

[0481]

[0482] bis(4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl)methane;

[0483]

[0484] tris(4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl)methane;

[0485]

[0486] 5,5'-(((2-((Bicyclo[2.2.1]hept-5-ene-2-ylmethoxy)methyl)-2-methylpropane-1,3-diyl)bis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

[0487]

[0488] 5,5'-(((Bicyclo[2.2.1]hept-5-ene-2-ylmethylene)bis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

[0489]

[0490] Tris(bicyclo[2.2.1]hept-5-ene-2-ylmethoxy)(methyl)silane; and

[0491]

[0492] Bicyclo[2.2.1]hept-5-en-2-ylbis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)silane.

[0493] In some embodiments of the present invention, the compositions of the present invention may further contain other photosensitizer compounds, which can activate the organoruthenium compounds of formula (II) to promote bulk polymerization of the monomers of formula (I) and / or the monomers of formula (V) or (VI) (if present). For this purpose, any suitable sensitizer compound can be used in the compositions of the present invention. Such suitable sensitizer compounds include photosensitizers such as anthracenes, phenanthrenes, perylenes, benzopyrenes, fluoranthenes, rubrenes, pyrenes, xanthones, indanthrenes, and mixtures thereof.

[0494] In some exemplary embodiments, suitable sensitizer components include mixtures thereof. Generally, the photosensitizer absorbs energy from a radiation source and transfers that energy to the desired substrate / reactant employed in the compositions of the present invention.

[0495] The compositions of the present invention may also contain optionally used additives, which can be used to improve the properties of the compositions and the articles made therefrom. Such optionally used additives may include, for example, antioxidants and synergists.

[0496] In another aspect, the present invention also relates to a method of making a film, comprising the following steps;

[0497] (X a1 ) providing the composition according to any one of claims 1 to 10 onto the outermost surface of a substrate, layer or device to obtain a coating,

[0498] (Xa2 )Irradiate the coating (apply light irradiation) to form a cured film. Preferably, light with a maximum peak wavelength in the range of 360 to 430 nm is used. Preferably, the irradiation dose of the light applied to the composition is in the range of 1 to 5 J / cm 2 .

[0499] In another aspect of this embodiment of the present invention, the composition of the present invention undergoes bulk polymerization to form a polymer film or solid object when exposed to suitable radiation for a sufficient period of time.

[0500] That is to say, the composition of the present invention is poured onto the surface or substrate to be encapsulated and exposed to appropriate radiation to polymerize the monomers to form a solid transparent polymer, which can be in the form of a transparent film or a solid object.

[0501] Generally, as described above, such polymerization can occur when exposed to actinic radiation in the wavelength range of about 240 nm to 410 nm. The composition can also be simultaneously subjected to appropriate radiation and heating to cause bulk polymerization. By practicing the present invention, polymer films can now be obtained on such substrates, which are substantially transparent films or solid objects, depending on the manufacturing method employed.

[0502] As used herein, "substantially transparent film" means that the film formed from the composition of the present invention is optically transparent under visible light. Thus, in some embodiments of the present invention, such a film has a visible light transmittance of at least 90%, and in some other embodiments, the film formed from the composition of the present invention has a visible light transmittance of at least 95%.

[0503] Coating the desired substrate with the composition of the present invention to form a film can be carried out by any coating or printing procedure described herein and / or known to those skilled in the art, such as by 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 well known in the art. The mixture can also be poured onto the substrate to form a film. Suitable substrates include any appropriate substrate, or can be used for electrical, electronic, or optoelectronic devices, such as semiconductor substrates, ceramic substrates, and glass substrates.

[0504] Next, the coated substrate is exposed to suitable actinic radiation, that is, exposed to the radiation in the wavelength range of 240 nm to 410 nm described herein to promote bulk polymerization. In some embodiments, the substrate is exposed to radiation and baked at a temperature of about 40 °C to 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 of about 60 °C to about 90 °C for 5 minutes to 20 minutes.

[0505] Then, the optical properties of the film thus formed are evaluated using any method known in the art. For example, the refractive index of the film in the visible spectral range can be measured by ellipsometry. The optical quality of the film can be determined by visual observation. The percentage of transparency can be quantitatively measured in the visible spectrum. Generally, the film formed according to the present invention exhibits excellent optical transparency characteristics and can be adjusted to the desired refractive index as described herein.

[0506] The compositions of the present invention can also be used as protective layers for various electronic or optoelectronic devices, particularly organic electronic devices, which are sensitive to environmental conditions, especially oxygen and moisture. The compositions of the present invention, when used as such protective layers, provide much-needed protection against environmental conditions. Generally, in such applications, for example, in organic light-emitting diode (OLED) devices, a plurality of OLED layers or OLED stacks are formed on a suitable substrate and then encapsulated with the compositions of the present invention.

[0507] The encapsulation of the OLED stack can be carried out by any known method, including but not limited to methods such as dip coating, inkjet coating, spin coating, etc. Then, the coated OLED stack is subjected to appropriate actinic radiation, thereby forming a transparent polymer layer on the OLED stack by ROMP. Before or after the formation of the transparent polymer layer, a conductive layer is deposited on the polymer layer. Such a conductive layer can be deposited by any known method, such as chemical vapor deposition (CVD) methods, etc. The polymer layer formed from the compositions of the present invention is stable to such CVD methods and retains its properties, especially the transparent properties, as well as other properties described herein. Finally, the OLED device can optionally be protected by coating with the compositions of the present invention as described above and subjecting it to appropriate actinic radiation to form another polymer layer. Such a stacking process can employ multiple processes of transparent polymer layer formation and / or conductive layer deposition.

[0508] In another aspect, the present invention also relates to a film formed from the compositions of the present invention.

[0509] In another aspect, the present invention also relates to a film obtained or obtainable by the method of the present invention.

[0510] Preferably, the film is optically transparent.

[0511] In a preferred embodiment of the present invention, the layer thickness of the film is in the range of 0.1 to 100 μm, preferably 1 to 20 μm, more preferably 5 to 10 μm.

[0512] In a preferred embodiment of the present invention, the relative dielectric constant value ε of the film r < 2.5, preferably 1.5 ≤ ε r < 2.5, more preferably 2.0 ≤ ε r ≤ 2.4.

[0513] In a preferred embodiment of the present invention, the haze value of the film is 46 or less, preferably 20 or less, more preferably 3 or less, and preferably 0 or more.

[0514] According to the present invention, the haze value is measured at room temperature in air according to the procedure described in ASTM D1003-21. Measurement can be carried out using a commercial haze meter such as the BYK Gardner Haze-Gard plus 4725.

[0515] In another aspect, the present invention also relates to a device that at least comprises 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, and more preferably, the device comprises a functional module selected from OLED, LCD, and μLED.

[0516] In another aspect, the present invention also relates to the use of the compound of formula (IV) in a photocurable composition for forming a protective layer of a device:

[0517]

[0518] wherein

[0519] p is an integer of 0, 1, or 2;

[0520] R e1 、R e2 、R e3 and R e4 are each independently selected from the group consisting of: hydrogen, halogen, methyl, ethyl, linear (C 1 -C 16 ) alkyl or branched (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 (C6 -C 10 )aryl(C 1 -C 6 )alkyl, tris(C 1 -C 6 )alkoxysilyl, vinyl, acrylate, methacrylate, and allyl, a straight-chain (C 1 -C 16 )alkyl or a branched-chain (C 3 -C 16 )alkyl having vinyl, acrylate, methacrylate, or allyl as a terminal group;

[0521] wherein at least one of R e1 , R e2 , R e3 , and R e4 is vinyl, acrylate, methacrylate, allyl, a straight-chain (C 1 -C 16 )alkyl or a branched-chain (C 3 -C 16 )alkyl having vinyl, acrylate, methacrylate, or allyl as a terminal group.

[0522] More details of the compound of formula (IV) are described in the section of the compound of formula (IV) above.

[0523] Technical Effects of the Present Invention

[0524] The present invention provides one or more of the following effects: the composition and / or the resulting film have higher transparency at visible light wavelengths, the resulting film has a lower haze value, the composition and the resulting film have a lower dielectric constant, the composition and the resulting film have a lower dielectric constant, the touch sensitivity of a touch screen separated from an OLED device by the film of the present invention is improved, the refractive index is high, the resulting film has good mechanical properties for resisting mechanical stresses such as folding and bending, the composition has a good curing rate, and the thermal properties are good.

[0525] The following invention examples will illustrate the present invention and describe in detail its preparation method, but the present invention is not limited to the invention examples.

[0526] Invention Examples

[0527] In the above and below, the following abbreviations are used when describing some compounds, instruments, and / or methods for illustrating certain embodiments of the present invention:

[0528] HexylTD: 2-Hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;

[0529] PETD: 2-Phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene

[0530] CL1: 1,3-Bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane

[0531]

[0532] DiCp:

[0533] NBMeOPhPh: 5-(([1,1'-Biphenyl]-2-yloxy)methyl)bicyclo[2.2.1]hept-2-ene

[0534] VinylNB: 5-Vinyl-2-norbornene

[0535] Compound 1:

[0536] CPTX: 1-Chloro-4-propoxy-9H-thioxanthen-9-one;

[0537] Catalyst Ru-I: [1,3-Bis(2,6-diisopropylphenyl)-2-imidazolinylidene]{2-[(E)-({2-[Methylthio-κS]phenyl}imino-κN)methyl]phenoxo-bridged-κO}[2-(Oxo-bridged-κO)benzylidene-κC]ruthenium(II);

[0538] All monomers used herein are commercially available or can be readily prepared according to the procedures described in U.S. Patent No. 9,944,818.

[0539] Comparative Example 1: Preparation of Composition

[0540] In a brown glass bottle, CPTX (0.1 wt%) was dissolved in HexylTD (99.87 wt%), and the solution was sonicated for 20 minutes at 30 °C to form a clear solution. The solution was purged with nitrogen for 8 hours. The Ru-1 catalyst (0.03 wt%) was added to the purged solution in a glove box and sonicated for 30 minutes to completely dissolve the catalyst. The sample was optically inspected for complete dissolution and filtered before further experiments. Then the comparative sample (Sample 0) was obtained.

[0541] Inventive Examples 1 to 10: Preparation of Composition

[0542] Samples 1 to 10 (Inventive Examples 1 to 10) were obtained in the same manner as Comparative Example 1 above, except that the following materials listed in Table 1 were used instead of the materials used in Comparative Example 1.

[0543] Table 1:

[0544]

[0545] Comparative Example - Without Vinyl Norbornene

[0546] Inventive Example 11 - Film Preparation (Spin Coating + UV Curing)

[0547] Film samples 1 to 10 of the compositions of Inventive Examples 1 to 10 were prepared by spin coating the compositions of Inventive Examples 1 to 10 on a pre-cleaned quartz substrate in a glove box under nitrogen, respectively. Then, the wet film was irradiated with ultraviolet light at 395 nm to cure the film, and the irradiation dose applied was generally 1 to 5 J / cm 2 , and the exact irradiation doses used are summarized in Table 2. The spin coating parameters were optimized to obtain a cured film with a thickness of 8 μm. After the film was cured, the film thickness was determined by profilometry using a probe profilometer as the height difference between the film surface and the substrate surface (after scratching with a scalpel). Then, film samples 1 to 10 were obtained.

[0548] Comparative Example 2 - Film Preparation (Spin Coating + UV Curing)

[0549] Film sample 1 of the mouth and nose composition from Comparative Example 1 was prepared in the same manner as described in Inventive Example 11, except that the comparative composition from Comparative Example 1 was used instead of the composition used in Inventive Example 11. Then, film sample 1 was obtained.

[0550] Measurement of Curing Rate

[0551] By scraping the prepared film from the substrate, the cured material of each film sample was collected, and then the material was analyzed by ATR-FTIR spectroscopy. The spectrum was baseline corrected and normalized at the peak of 2851 cm -1 . The curing rate was determined by integrating the monomer-specific vibration at 3058 cm -1 and comparing it with the signal integration of the uncured formulation.

[0552] HIT and EIT Measurements

[0553] The films on the quartz substrate were further analyzed by nanoindentation to determine material properties such as the elastic indentation modulus EIT and the indentation hardness HIT. The indenter was pressed into the test object with a defined force curve, and the penetration depth was recorded. Various parameters could be calculated based on the recorded indentation depth, the applied force, and the shape of the indenter. The measurements were carried out using a Fischerscope HM2000S (load force = 1 mN, load time = 8 s, creep = 20 s), and the EIT and HIT were calculated using the instrument software.

[0554] Silicon Nitride Deposition and Haze Measurement

[0555] On the thin film samples obtained from the spin coating experiment, 700 nm of silicon nitride (SiNx) was deposited by CVD.

[0556] After silicon nitride deposition, the haze of the resulting stack (quartz glass / cured polymer / SiNx) was determined according to ASTM D1003-21. The measurement was performed using a BYK Gardner Haze-Gard plus 4725 haze meter. The measurement was performed at room temperature in an air environment.

[0557] Table 2 shows the measurement results.

[0558] Table 2:

[0559]

[0560] Although the present invention has been described by certain foregoing embodiments, it should not be construed as being limited thereto; on the contrary, the present invention covers the general area as previously described. Various modifications and specific embodiments may be made without departing from its spirit and scope.

Claims

1. A composition comprising at least: a) A compound of formula (I): Wherein: m is an integer 0, 1 or 2; R 1 、R 2 、R 3 and R 4 are the same or different and are each independently selected from the group consisting of: hydrogen, halogen, methyl, ethyl, straight-chain or branched (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, tris (C 1 -C 6 ) alkoxysilyl and group of formula (A): -Z 1 -Aryl (A) Wherein: Z 1 is a key or a group selected from the group consisting of: (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 , where a and b are integers that can be the same or different, and each independently ranges from 1 to 12; R 5 and R 6 are the same or different and each independently selected from the group consisting of: hydrogen, methyl, ethyl, straight or branched chain (C 3 -C 6 ) alkyl, hydroxy, methoxy, ethoxy, straight or branched chain (C 3 -C 6 ) alkoxy, acetoxy, (C 2 -C 6 ) acyl, hydroxymethyl, hydroxyethyl, straight or branched chain hydroxy (C 3 -C 6 ) alkyl, phenyl and phenoxy; Aryl is phenyl or phenyl substituted by one or more groups selected from the following: methyl, ethyl, straight-chain or branched (C 3 -C 6 ) alkyl, hydroxy, methoxy, ethoxy, straight-chain or branched (C 3 -C 6 ) alkoxy, acetoxy, (C 2 -C 6 ) acyl, hydroxymethyl, hydroxyethyl, straight-chain or branched hydroxy(C 3 -C 6 ) alkyl, phenyl and phenoxy; b) An organoruthenium compound, preferably represented by formula (II): Where c and d are integers from 0 to 5; Z is oxygen or sulfur; R 7 selected from the group consisting of hydrogen, (C 1 -C 20 ) alkyl, (C 2 -C 20 ) alkenyl, (C 2 -C 20 ) alkynyl, and (C 6 -C 10 ) aryl; and R 8 、R 9 、R 10 and R 11 are the same or different and are each independently selected from the group consisting of: 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 )heterocyclic group, -OR 16 、-NO 2 、-COOH、-COOR 16 、-CONR 16 R 17 、-SO 2 NR 16 R 17 、-SO 2 R 16 、-CHO、-COR 16 , where R 16 and R 17 are the same or different and are each independently selected from the group consisting of (C 1 -C 6 )alkyl, (C 1 -C 6 )perfluoroalkyl, (C 6 -C 14 )aryl, (C 6 -C 14 )perfluoroaryl; or where 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 ) carbocyclic ring, or a substituted or unsubstituted fused aromatic ring; R 12 , R 13 and R 14 Each may be the same or different and are independently selected from the group consisting of: 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 ) heterocyclic group, -OR 16 、-NO 2 , -COOH, -COOR 16 、-CONR 16 R 17 、-SO 2 NR 16 R 17 、-SO 2 R 16 、-CHO、-COR 16 , where R 16 and R 17 the same or different, and each independently derived from (C 1 -C 6 ) alkyl, (C 1 -C 6 )perfluoroalkyl, (C 6 -C 14 ) aryl, (C 6 -C 14 ) is selected from the group consisting of perfluoroaryl groups; R 15 selected from the group consisting of (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 ) heterocyclic group; Ar 1 and Ar 2 are the same or different and each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthyl, wherein said substituents are each independently selected from the group consisting of methyl, ethyl, and straight-chain or branched (C 3 -C 6 ) alkyl groups; c) A photosensitizer, preferably represented by formula (III): Where Y is a halogen; and R 30 and R 31 are the same or different and are each independently selected from the group consisting of: hydrogen, methyl, ethyl, linear or branched (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 ) aryloxy; and d) A compound of formula (IV): Where p is an integer 0, 1 or 2; R e1 、R e2 、R e3 and R e4 are each independently selected from the group consisting of: 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, tris (C 1 -C 6 ) alkoxysilyl, vinyl, acrylate, methacrylate and allyl, straight-chain (C 1 -C 16 ) alkyl or branched-chain (C 3 -C 16 ) alkyl having vinyl, acrylate, methacrylate or allyl as a terminal group; wherein R e1 , R e2 , R e3 and R e4 at least one of which is vinyl, acrylate group, methacrylate group, allyl group, a straight-chain (C 1 -C 16 ) alkyl group or a branched-chain (C 3 -C 16 ) alkyl group having vinyl, acrylate group, methacrylate group or allyl group as an end group.

2. The composition according to claim 1, wherein the monomer of formula (IV) is selected from the group consisting of:

3. The composition according to claim 1 or 2, wherein the monomer of formula (I) is selected from the group consisting of: 5-(4-Phenylbutyl)bicyclo[2.2.1]hept-2-ene; 5-(3-Phenylpropyl)bicyclo[2.2.1]hept-2-ene; 5-Phenethylbicyclo[2.2.1]hept-2-ene (PENB); 5-(Benzyloxy)bicyclo[2.2.1]hept-2-ene; 5-(2-([1,1'-Biphenyl]-4-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene; 5-(2-([1,1'-Biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtO-2-PhPh); 5-Butylbicyclo[2.2.1]hept-2-ene (BuNB); 5-Hexylbicyclo[2.2.1]hept-2-ene (HexylNB); 5-Octylbicyclo[2.2.1]hept-2-ene (OctNB); 5-Decylbicyclo[2.2.1]hept-2-ene (DecNB); 5-Ethylidenebicyclo[2.2.1]hept-2-ene; 2-Ethylidene-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene; 3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene (one of the cyclopentadiene trimers, TCPD1, also known as CPD3) 5-Norbornenylmethyl eugenol acetate (EuAcNB); 5-Norbornenylmethyl eugenol (EuOHNB); NB(MeOH) 2 ; PhAcNB; Tetracyclododecene (TD); 5-(Phenoxymethyl)bicyclo[2.2.1]hept-2-ene (NBMeOPh); 5-(([1,1'-Biphenyl]-2-yloxy)methyl)bicyclo[2.2.1]hept-2-ene (NBMeOPhPh); 2-Phenyltetracyclododecene (PhTD); 2-Benzyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene; 2-Phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD); 2-Butyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (ButylTD); 2-Hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (HexylTD); 2 - Octyl - 1,2,3,4,4a,5,8,8a - octahydro - 1,4:5,8 - dimethanonaphthalene (OctylTD); 2 - Decyl - 1,2,3,4,4a,5,8,8a - octahydro - 1,4:5,8 - dimethanonaphthalene (DecylTD); 2 - Cyclohexyltetradecadiene (CyclohexylTD); 2 - (Cyclohexylmethyl) - 1,2,3,4,4a,5,8,8a - octahydro - 1,4:5,8 - dimethanonaphthalene; 2 - (Cyclohexylethyl) - 1,2,3,4,4a,5,8,8a - octahydro - 1,4:5,8 - dimethanonaphthalene; Methyl (1,2,3,4,4a,5,8,8a - octahydro - 1,4:5,8 - dimethanonaphthalen - 2 - yl) acetate (TDMeOAc); and Tetradecadiene (TDD).

4. The composition according to any one of claims 1 to 3, wherein: Z is oxygen; R 7 is hydrogen; R 8 、R 9 、R 10 and R 11 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, and NO 2 ; R 12 , R 13 and R 14 the same or different and each independently selected from hydrogen, methyl, ethyl and NO 2 Selected from the group consisting of; R 15 Selected from the group consisting of methyl, ethyl and cyclohexyl; Ar 1 and Ar 2 are the same or different and 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 composition according to any one of claims 1 to 4, wherein the organoruthenium compound is represented by formula (II) selected from the group consisting of: [1,3 - Bis(2,6 - diisopropylphenyl) - 2 - imidazolinylidene]{2 - [(E) - ({2 - [Methylthio - κS]phenyl}imino - κN)methyl]phenoxo - κO}[2 - (Oxo - κO)benzylidene - κC]ruthenium(II) (Ru - 1); [1,3 - Bis(2,4,6 - trimethylphenyl) - 2 - imidazolinylidene]{2 - [(E) - ({2 - [Isopropylthio - κS]phenyl}imino - κN)methyl]phenoxo - κO}[2 - (Oxo - κO)benzylidene - κC]ruthenium(II); [1,3 - Bis(2,4,6 - trimethylphenyl) - 2 - imidazolinylidene]{2 - [(E) - ({2 - [Cyclohexylthio - κS]phenyl}imino - κN)methyl]phenoxo - κO}[2 - (Oxo - κO)benzylidene - κC]ruthenium(II); and [1,3 - Bis(2,4,6 - trimethylphenyl) - 2 - imidazolinylidene]{2 - [(E) - ({2 - [Methylthio - κS]phenyl}imino - κN)methyl]phenoxo - κO}[2 - (Oxo - κO)benzylidene - κC]ruthenium(II).

6. The composition according to any one of claims 1 to 5, wherein: Y is chlorine or bromine; and R 30 and R 31 are the same or different and are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, phenyl, cyclohexyl, methoxy, ethoxy, n-propoxy and phenoxy.

7. The composition according to any one of claims 1 to 6, wherein the compound of formula (III) is selected from the group consisting of: 1 - Chloro - 4 - methoxy - 9H - thioxanthen - 9 - one; 1 - Chloro - 4 - ethoxy - 9H - thioxanthen - 9 - one; 1 - Chloro - 4 - propoxy - 9H - thioxanthen - 9 - one; 1 - Chloro - 2 - propoxy - 9H - thioxanthen - 9 - one; 1 - Chloro - 2 - ethoxy - 9H - thioxanthen - 9 - one; 1 - Chloro - 2 - methoxy - 9H - thioxanthen - 9 - one; 1 - Chloro - 4 - methyl - 9H - thioxanthen - 9 - one; 1 - Chloro - 4 - ethyl - 9H - thioxanthen - 9 - one; 1 - Bromo - 4 - propoxy - 9H - thioxanthen - 9 - one; and 1 - Chloro - 4 - phenoxy - 9H - thioxanthen - 9 - one.

8. The composition according to any one of claims 1 to 7 further comprises an ultraviolet absorber and / or a crosslinking agent.

9. The composition according to any one of claims 1 to 8 further comprises an additive selected from the following:

10. A method of manufacturing a film, comprising the following steps: (X a1 )Providing the composition according to any one of claims 1 to 10 onto the outermost surface of a substrate, layer or device to obtain a coating, (X a2 )Irradiate the coating (apply light irradiation) to form a cured film. It is preferred to use light with a maximum peak wavelength in the range of 360 to 430 nm, and preferably the irradiation amount of the light applied to the composition is in the range of 1 to 5 J / cm 2 .

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

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

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

14. The film according to any one of claims 11 to 13, having a relative permittivity value ε r < 2.5, preferably 1.5 ≤ ε r < 2.5, more preferably 2.0 ≤ ε r ≤ 2.

4.

15. The film according to any one of claims 11 to 14, wherein the haze value of the film is 46 or less, preferably 20 or less, more preferably 3 or less, preferably 0 or greater.

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 OLED, LCD, and μLED.

17. Use of the compound of formula (IV) in a photocurable composition for forming a device protective layer: wherein p is an integer 0, 1, or 2; R e1 , R e2 , R e3 and R e4 Each is independently selected from the group consisting of: hydrogen, halogen, methyl, ethyl, straight chain (C 1 -C 16 ) alkyl or branched (C 3 -C 16 ) alkyl, perfluoro(C 1 -C 12 ) alkyl, hydroxyl (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, acrylate, methacrylate and allyl, a straight chain (C 1 -C 16 ) alkyl or branched (C 3 -C 16 )alkyl; wherein R e1 , R e2 , R e3 and R e4 at least one of which is vinyl, acrylate, methacrylate, allyl, a linear (C 1 -C 16 ) alkyl or a branched (C 3 -C 16 ) alkyl having vinyl, acrylate, methacrylate or allyl as a terminal group.

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