Articles, methods, and compositions comprising cyclic olefin, catalyst, and second polymerizable material

Abstract

Articles, such as adhesive articles, electronic articles, and abrasive articles, including compositions disposed on a substrate are described. The composition comprises i) a cyclic olefin; ii) a ring-opening metathesis polymerization catalyst; iii) a second polymerizable material; and iv) 10 an initiator for the second polymerizable material. The second polymerizable material is selected from the group consisting of: a) an epoxide-containing component; and b) a (meth) acrylate monomer. The (meth) acrylate monomer contains an alicyclic or heteroalicyclic group. The composition comprises greater than 25% by weight of i) and greater than 25% by weight of at least one of a) or b), based on the total of i) and iii). The cyclic olefin and / or the second polymerizable 15 material is at least partially cured. Compositions and methods are also described.

Description

SUMMARY OF THE INVENTION

[0001] In one embodiment, an article is described that includes a composition disposed on a substrate. The composition includes i) a cyclic olefin; ii) a ring-opening metathesis polymerization catalyst; iii) a second polymerizable material; and iv) an initiator for the second polymerizable material. The second polymerizable material is selected from the group consisting of: a) an epoxy-containing component; and b) a (meth)acrylate monomer. The (meth)acrylate monomer includes an alicyclic or heteroalicyclic group. Based on the total amount of i) and iii), the composition includes greater than 25 wt% of i) and greater than 25 wt% of at least one of a) or b). In some embodiments, the composition includes greater than 25 wt% of the cyclic olefin and greater than 25 wt% of the epoxy-containing component. In other embodiments, the composition includes greater than 25 wt% of the cyclic olefin and greater than 25 wt% of the (meth)acrylate monomer that includes an alicyclic or heteroalicyclic group. The initiator is selected such that the second polymerizable material cures under curing conditions different from those of the cyclic olefin. In some embodiments, the concentrations of the cyclic olefin and the second polymerizable material are sufficient such that an interpenetrating polymer network is formed. The cyclic olefin and / or the second polymerizable material is at least partially cured. In the case of (e.g., transfer) film / tape articles, the cyclic olefin and / or the second polymerizable material is typically partially cured. In the case of other articles such as abrasive articles and electronic articles, the cyclic olefin and / or the second polymerizable material is typically fully cured in the final article.

[0002] In another embodiment, a method of manufacturing an electronic article is described that includes A) applying a composition as described herein to a substrate. The method further includes B) polymerizing the cyclic olefin, and C) curing the second polymerizable material. The method may include polymerizing the cyclic olefin before or after curing the second polymerizable material. Curing of the second polymerizable material may be achieved by exposing the composition to actinic (e.g., ultraviolet) radiation. In some embodiments, the method further includes contacting the composition with a second substrate before curing.

[0003] A polymerizable composition is also described that includes greater than 25 wt% of i) and greater than 25 wt% of at least one of a) or b) based on the total amount of i) and iii). In some embodiments, the total amount of i) and iii) is at least 60 wt% of the total composition. In other embodiments, the second polymerizable material is an epoxy-containing component or a (meth)acrylate monomer that includes a heteroalicyclic (e.g., isocyanurate) group. DETAILED DESCRIPTION

[0004] Cyclic olefin

[0005] Compositions (such as compositions of articles and methods) typically comprise one or more cyclic olefins. The cyclic olefins can be characterized as monomers. As used herein, the term monomer refers to monomers and oligomers that contain cyclic olefins and generally have a molecular weight of no greater than about 10,000 g / mol. When the cyclic olefins are cured, polymers are formed from the polymerized cyclic olefins. The cyclic olefin monomers are generally mono-unsaturated (i.e., mono-olefins) or poly-unsaturated (i.e., contain two or more carbon-carbon double bonds, or in other words, olefin groups). The double bonds, or in other words, the ethylenically unsaturated groups are not part of (meth)acrylate or vinyl ether groups. The cyclic olefin monomers can be monocyclic or polycyclic (i.e., contain two or more cyclic groups). The cyclic olefin monomers can generally be strained or unstrained cyclic olefins, provided that the cyclic olefins are capable of participating in a ROMP reaction either alone or as part of a ROMP cyclic olefin composition. The polymerized cyclic olefins are polymers made via ROMP of cyclic olefin monomers. The polymerized cyclic olefins may or may not contain unreacted cyclic olefin moieties, since at least one cyclic olefin moiety of each cyclic olefin monomer is converted into a non-cyclic olefin during ROMP.

[0006] The composition can comprise cyclic diene monomers, including for example 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, norbornadiene, cyclohexenyl norbornene, including their oligomers such as dimers, trimers, tetramers, pentamers, etc. The polyolefin cyclic materials are suitable for thermosetting.

[0007] In some embodiments, the composition comprises dicyclopentadiene (DCPD), depicted as follows:

[0008]

[0009] Various DCPD suppliers and purities can be used, such as Lyondell 108 (94.6% purity), Veliscol UHP (99% purity), Cymetech Ultrene (97% and 99% purity), and Hitachi (99+% purity).

[0010] In some embodiments, the composition comprises cyclopentadiene oligomers, including trimers, tetramers, pentamers, etc.; depicted as follows:

[0011]

[0012] For cyclopentadiene oligomers, n is generally 3, 4, or 5.

[0013] In some embodiments, the composition comprises cyclic diene monomers in the absence of mono-olefins.

[0014] In other embodiments, the composition further comprises a cyclic monoolefin. Examples include cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, tricyclodecene, tetracyclodecene, octacyclodecene, and cycloeicosene, and substituted forms thereof, such as 1-methylcyclopentene, 1-ethylcyclopentene, 1-isopropylcyclohexene, 1-chloropentene, 1-fluorocyclopentene, 4-methylcyclopentene, 4-methoxy-cyclopentene, 4-ethoxy-cyclopentene, cyclopent-3-ene-thiol, cyclopent-3-ene, 4-methylthioalkyl-cyclopentene, 3-methylcyclohexene, 1-methylcyclooctene, 1,5-dimethylcyclooctene, etc.

[0015] In some embodiments, the composition further comprises norbornene, depicted as follows:

[0016]

[0017] Suitable norbornene monomers include substituted norbornenes, such as norbornene dicarboxylic anhydride (nadic anhydride); and alkyl and cycloalkyl norbornenes, including butyl norbornene, hexyl norbornene, octyl norbornene, decyl norbornene, etc.

[0018] The cyclic olefin monomers and oligomers may optionally contain substituents, provided that the monomers, oligomers, or mixtures are suitable for metathesis reactions. The carbon atoms of the cyclic olefin moiety may optionally contain substituents derived from radical fragments, which include halogens, pseudohalogens, alkyls, aryls, acyls, carboxyls, alkoxys, alkyl thiolates, and aryl thiolates, amines, aminoalkyls, etc., or one or more of the carbon atoms have been replaced, for example, by silicon, oxygen, sulfur, nitrogen, phosphorus, antimony, or boron. For example, the olefin may be substituted by one or more groups, such as thiols, thioethers, ketones, aldehydes, esters, ethers, amines, amides, nitro groups, carboxylic acids, disulfides, carbonates, isocyanates, phosphates, phosphites, sulfates, sulfites, sulfonyls, carbodiimides, carbalkoxys, carbamates, halogens, or pseudohalogens. Similarly, the olefin may be substituted by one or more groups (such as C1-C20 alkyls, aryls, acyls, C1-C20 alcoholates, aryloxides, C3-C20 alkyl diketonates, aryl diketonates, C1-C20 carboxylates, aryl sulfonates, C1-C20 alkyl sulfonates, C1-C20 alkyl sulfurs, aryl sulfurs, C1-C20 alkyl sulfonyls, C1-C20 alkyl sulfinyls, C-C20 alkyl phosphates, and aryl phosphates).

[0019] Preferred cyclic olefins may include dicyclopentadiene; tricyclopentadiene; dicyclohexadiene; norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbornene; 5-acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethoxycarbonyl-1-norbornene; 5-methyl-5-methoxycarbonylnorbornene; 5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene; cyclohexenylnorbornene; endo,exo-5,6-dimethoxynorbornene; endo,endo-5,6-dimethoxynorbornene; endo,exo-5,6-dimethoxycarbonylnorbornene; endo,endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methyltetracyclododecene; 8-ethyl-tetracyclododecene; 8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclododecene; 8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene; higher oligomers of cyclopentadiene, such as cyclopentadiene tetramer, cyclopentadiene pentamer, etc.; and C2-C12 hydrocarbyl-substituted norbornenes, such as 5-butyl-2-norbornene; 5-hexyl-2-norbornene; 5-octyl-2-norbornene; 5-decyl-2-norbornene; 5-dodecyl-2-norbornene; 5-vinyl-2-norbornene; 5-ethylidene-2-norbornene; 5-isopropenyl-2-norbornene; 5-propenyl-2-norbornene; and 5-butenyl-2-norbornene, etc. More preferred cyclic olefins include dicyclopentadiene, tricyclopentadiene and higher oligomers of cyclopentadiene (such as cyclopentadiene tetramer, cyclopentadiene pentamer, etc.), tetracyclododecene, norbornene and C2-C12 hydrocarbyl-substituted norbornenes, such as 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, 5-butenyl-2-norbornene, etc.

[0020] The cyclic olefins may be used alone or mixed with each other in various combinations to adjust the properties of the olefin monomer composition. For example, a mixture of cyclopentadiene dimer and trimer provides a reduced melting point and produces a cured olefin copolymer with increased mechanical strength and stiffness relative to pure polyDCPD. As another example, the incorporation of norbornene or an alkyl norbornene comonomer tends to produce a relatively soft and rubbery cured olefin copolymer.

[0021] In some embodiments, the cyclic olefin material comprises a mixture of DCPD monomers and cyclopentadiene oligomers. In some embodiments, based on the total amount of cyclic olefin monomers and oligomers, the mixture comprises at least 25 wt%, 30 wt%, 35 wt%, 40 wt% or 45 wt% DCPD. In some embodiments, based on the total amount of cyclic olefin monomers and oligomers, the mixture comprises no greater than 75 wt%, 70 wt%, 65 wt%, 60 wt%, 55 wt% or 50 wt% DCPD. In some embodiments, based on the total amount of cyclic olefin monomers and oligomers, the mixture comprises at least 15 wt%, 20 wt%, 25 wt%, 30 wt% or 35 wt% cyclic olefin oligomers such as cyclopentadiene trimer and / or tetramer. In some embodiments, based on the total amount of cyclic olefin monomers and oligomers, the mixture comprises no greater than 60 wt%, 55 wt%, 50 wt%, 45 wt% or 40 wt% cyclic olefin oligomers such as cyclopentadiene trimer and / or tetramer. In some embodiments, the mixture comprises at least 2 wt%, 3 wt%, 4 wt% or 5 wt% cyclic olefin oligomers having more than four cyclopentadiene repeat units such as cyclopentadiene pentamer. In some embodiments, the mixture comprises no greater than 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt% or 5 wt% cyclic olefin oligomers having more than four cyclopentadiene repeat units such as cyclopentadiene pentamer.

[0022] In some embodiments, in the absence of monoolefins or in combination with low concentrations of monoolefins, the cyclic olefin material comprises a mixture of DCPD monomers and cyclopentadiene oligomers. In this embodiment, based on the total amount of cyclic olefin monomers and oligomers, the amount of monoolefin is less than 25 wt%, 20 wt%, 15 wt%, 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt% or 1 wt%.

[0023] In other embodiments, based on the total amount of cyclic olefin monomers and oligomers, the mixture comprises at least 25 wt%, 30 wt%, 35 wt%, 40 wt% or 45 wt% of monoolefins, such as substituted norbornenes. In some embodiments, based on the total amount of cyclic olefin monomers and oligomers, the mixture comprises no greater than 75 wt%, 70 wt%, 65 wt%, 60 wt%, 55 wt% or 50 wt% of monoolefins (e.g., C4-C12 (e.g., C8) alkyl norbornenes). In some embodiments, based on the total amount of cyclic olefin monomers and oligomers, the mixture comprises at least 15 wt%, 20 wt%, 25 wt%, 30 wt% or 35 wt% of cyclic olefin oligomers, such as cyclopentadiene trimer and / or tetramer. In some embodiments, based on the total amount of cyclic olefin monomers and oligomers, the mixture comprises no greater than 60 wt%, 55 wt%, 50 wt%, 45 wt% or 40 wt% of cyclic olefin oligomers, such as cyclopentadiene trimer and / or tetramer. In some embodiments, the mixture comprises at least 2 wt%, 3 wt%, 4 wt% or 5 wt% of cyclic olefin oligomers having more than four cyclopentadiene repeat units, such as cyclopentadiene pentamer. In some embodiments, the mixture comprises no greater than 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt% or 5 wt% of cyclic olefin oligomers having more than four cyclopentadiene repeat units, such as cyclopentadiene pentamer. In some embodiments, the mixture comprises no greater than 5 wt%, 4 wt%, 3 wt%, 2 wt% or 1 wt% of DCPD monomer. In other embodiments, the mixture comprises no greater than 25 wt% or 20 wt% of DCPD monomer.

[0024] Based on the total amount of cyclic olefin and the second polymerizable material, the compositions described herein (e.g., the composition of the article) comprise greater than 25 wt% of cyclic olefin. When the composition further comprises other polymerizable materials in addition to the cyclic olefin and the second polymerizable material described herein, based on the total amount of polymerizable materials, the composition generally comprises greater than 25 wt% of cyclic olefin. In some embodiments, the composition comprises at least 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt% or 80 wt% of cyclic olefin. In some embodiments, the composition comprises no greater than 80 wt%, 75 wt%, 70 wt%, 65 wt%, 60 wt%, 55 wt%, 50 wt%, 45 wt%, 40 wt%, 35 wt% or 30 wt% of cyclic olefin.

[0025] Cyclic olefins can provide physical properties suitable for electronic products, such as low dielectric constant (Dk), low dielectric loss, and low loss tangent properties, especially when present at higher concentrations or in combination with inorganic fillers. The dielectric constant (Dk) of the cured film at 10 GHz can be less than 2.7, 2.6, 2.5, 2.4, 2.3, or 2.2. The loss tangent of the cured film at 10 GHz can be less than 0.010, 0.0090, 0.0080, 0.0070, 0.0060, 0.0050, 0.0040, 0.0030, or 0.0020. A low loss tangent can be obtained by using cyclic olefins with a higher aliphatic content. Cyclic olefins can also provide higher thermal stability and moisture resistance, which are beneficial for both electronic and abrasive products.

[0026] ROMP catalyst

[0027] The composition (e.g., the composition of the article and method) contains a ring-opening metathesis polymerization (ROMP) catalyst. Such organometallic catalysts are capable of performing ROMP on cyclic olefin monomers to produce polymers therefrom. Group 8 transition metals, such as ruthenium and osmium, carbene compounds have been described as effective catalysts for ring-opening metathesis polymerization (ROMP). See, for example, US 10,239,965; this patent is incorporated herein by reference.

[0028] In a typical embodiment, the catalyst is a metal carbene olefin metathesis catalyst. Such catalysts generally have the following structure:

[0029]

[0030] where

[0031] M is a Group 8 transition metal;

[0032] L 1 、L 2 and L 3 are independently neutral electron donor ligands; n is 0 or 1; m is 0, 1, or 2; k is 0 or 1;

[0033] X 1 and X 2 are independently anionic ligands; and

[0034] R 1 and R 2 are independently selected from hydrogen, hydrocarbon group, substituted hydrocarbon group, heteroatom-containing hydrocarbon group, substituted heteroatom-containing hydrocarbon group, and functional group.

[0035] Typical metal carbene olefin metathesis catalysts contain Ru or Os as the Group 8 transition metal, with Ru being preferred.

[0036] The first group of metal carbene olefin metathesis catalysts are commonly referred to as first-generation Grubbs-type catalysts and have the structure of catalyst formula (I). For the first group of metal carbene olefin metathesis catalysts, M is a Group 8 transition metal, m is 0, 1, or 2, and n, X 1 , X 2 , L 1 , L 2 and L 3 are as described below.

[0037] For the first group of metal carbene olefin metathesis catalysts, n is 0, and L 1 and L 2 are independently selected from phosphines, sulfonated phosphines, phosphites, mono-oxophosphinates, phosphonites, arsine, stibine, ethers (including cyclic ethers), amines, amides, imines, sulfoxides, carboxyl groups, nitrosyls, pyridines, substituted pyridines, imidazoles, substituted imidazoles, pyrazines, substituted pyrazines, and thioethers. Exemplary ligands are trisubstituted phosphines. A typical trisubstituted phosphine has the formula PR H1 R H2 R H3 , where R H1 , R H2 and R H3 are each independently a substituted or unsubstituted aryl or C1-C10 alkyl group, particularly a primary alkyl, secondary alkyl, or cycloalkyl group. In some embodiments, L 1 and L 2 are independently selected from the group consisting of: trimethylphosphine (PMe 3 ), triethylphosphine (PEt 3 ), tri-n-butylphosphine (PBu 3 ), tri(o-tolyl)phosphine (P-o-tolyl 3 ), tri-tert-butylphosphine (P-tert-Bu 3 ), tricyclopentylphosphine (PCyclopentyl 3 ), tricyclohexylphosphine (PCy 3 ), triisopropylphosphine (P-i-Pr 3 ), trioctylphosphine (POct 3 ), triisobutylphosphine (P-i-Bu 3 ), triphenylphosphine (PPh 3 ), tri(pentafluorophenyl)phosphine (P(C 6 F 5 )) 3 ), methyldiphenylphosphine (PMcPlu), dimethylphenylphosphine (PMePh 2 ), and diethylphenylphosphine (PEt 2 Ph). Alternatively, L 1 and L 2may be independently selected from bicyclic phosphates (e.g., monosubstituted 9-bicyclo-[3.3.1]nonyl phosphate or monosubstituted 9-bicyclo[4.2.1]nonyl phosphate), such as cyclohexylphoban, isopropylphosphine ligand, ethylphosphine ligand, methylphosphine ligand, butylphosphine ligand, pentylphosphine ligand, etc.

[0038] X 1 and X 2 are anionic ligands and may be the same or different, or linked together to form a cyclic group, usually although not necessarily a five- to eight-membered ring. In some embodiments, X 1 and X 2 are each independently hydrogen, a halide, or one of the following groups: C1-C20 alkyl, C5-C24 aryl, C1-C20 alkoxy, C5-C24 aryloxy, C2-C20 alkoxycarbonyl, C6-C24 aryloxycarbonyl, C2-C24 acyl, C2-C24 acyloxy, C1-C20 alkylsulfonate, C5-C24 arylsulfonate, C1-C20 alkylthio, C5-C24 arylthio, C1-C20 alkanesulfinyl, NO3, -N=C=O, -N=C=S, or C5-C24 arylsulfinyl. Optionally, X1 and X2 may be substituted by one or more moieties selected from C1-C12 alkyl, C1-C12 alkoxy, C5-C24 aryl, and halide, which (except for halide) may in turn be further substituted by one or more groups selected from halide, C1-C6 alkyl, C1-C6 alkoxy, and phenyl. In some embodiments, X1 and X2 are halide, benzoate, C2-C6 acyl, C2-C6 alkoxycarbonyl, C1-C6 alkyl, phenoxy, C1-C6 alkoxy, C1-C6 alkylthio, aryl, or C1-C6 alkylsulfonyl. In some preferred embodiments, X 1 and X 2 are each halide, CF 3 CO 2 、CH 3 CO 2 、CFH 2 CO 2 、(CH 3 ) 3 CO、(CF 3 ) 2 (CH 3 )CO、(CF 3 )(CH 3 ) 2 CO、PhO、MeO、EtO、 tosylate, mesylate, or triflate. In some preferred embodiments, X 1 and X 2 are each chloride.

[0039] R 1 and R 2 are independently selected from hydrogen, a hydrocarbon group (e.g., C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), a substituted hydrocarbon group (e.g., substituted C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), a heteroatom-containing hydrocarbon group (e.g., heteroatom-containing C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), a substituted heteroatom-containing hydrocarbon group (e.g., substituted heteroatom-containing C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.) and a functional group. R 1 and R 2 may also be linked to form a cyclic group, which may be aliphatic or aromatic and may contain substituents and / or heteroatoms. Generally, such cyclic groups will contain 4 to 12, preferably 5, 6, 7 or 8 ring atoms.

[0040] In some embodiments, R 1 is C1-C6 alkyl, C2-C6 alkenyl and C5-C14 aryl.

[0041] In some embodiments, R 2 is phenyl, vinyl, methyl, isopropyl or tert-butyl, which is optionally partially substituted with one or more selected from C1-C6 alkyl, C1-C6 alkoxy, phenyl and functional group Fn. Suitable functional groups (“Fn”) include phosphonate, phosphoryl, phosphinyl, phosphino, sulfonate, C1-C20 alkylthio, C5-C20 arylthio, C1-C20 alkylsulfonyl, C5-C20 arylsulfonyl, C1-C20 alkylsulfinyl, C5-C20 arylsulfinyl, sulfonamido, amino, amido, imino, nitro, nitroso, hydroxy, C1-C20 alkoxy, C5-C20 aryloxy, C2-C20 alkoxycarbonyl, C5-C20 aryloxycarbonyl, carboxyl, carboxylate, mercapto, formyl, C1-C20 thioester, cyano, cyanato, thiocyanato, isocyanate, thioisocyanate, carbamoyl, epoxy, styryl, silyl, silyloxy, silanyl, siloxazanyl, borate, oxoboronyl or halogen, or a metal-containing or metalloid-containing group (wherein the metal may be, for example, Sn or Ge).

[0042] In some embodiments, R 2is phenyl or vinyl, which is substituted by one or more moieties selected from methyl, ethyl, chlorine, bromine, iodine, fluorine, nitro, dimethylamino, methyl, methoxy and phenyl. In some advantageous embodiments, R 2 is phenyl or -CH═C(CH 3 ) 2 .

[0043] In some embodiments, one or both of R 1 and R 2 may have the structure -(W) n -U + V - , where W is selected from alkylene, substituted alkylene, heteroatom-containing alkylene or substituted heteroatom-containing alkylene; U is a positively charged Group 15 or Group 16 element substituted by hydrogen, hydrocarbon group, substituted hydrocarbon group, heteroatom-containing hydrocarbon group or substituted heteroatom-containing hydrocarbon group; V is a negatively charged counterion; and n is zero or 1. In addition, R 1 and R 2 may combine together to form an indenylidene moiety, such as phenylindenylidene.

[0044] In some embodiments, any one or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 and R 2 may be attached to a carrier, or two or more of these groups (e.g., three or four) may be bonded to each other to form one or more cyclic groups (including bidentate or polydentate ligands), as disclosed, for example, in U.S. Patent Application 5,312,940, which is incorporated herein by reference. When two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 and R 2 are linked to form a cyclic group, these cyclic groups may contain 4 to 12, preferably 4,

[0045] 5, 6, 7 or 8 atoms, or may contain two or three such rings that may be fused or linked. The cyclic groups may be aliphatic or aromatic and may be heteroatom-containing and / or substituted. In some cases, the cyclic groups may form bidentate or tridentate ligands. Examples of bidentate ligands include, but are not limited to, bisphosphines, diolates, alkyl diketonates and aryl diketonates.

[0046] Other metal carbene olefin metathesis catalysts (commonly referred to as second or third generation Grubbs-type catalysts) have a structure of catalyst formula (I), where L 1 is a carbene ligand having a structure of formula (II)

[0047]

[0048] where M, m, n, X 1 、X 2 、L 2 、L 3 、R 1 and R 2 are as defined in formula I previously;

[0049] X and Y are heteroatoms usually selected from N, O, S, and P. Since O and S are divalent, when X is O or S, p must be zero; when Y is O or S, q must be zero; and k is zero or 1. However, when X is N or P, then p is 1, and when Y is N or P, then q is 1. In a preferred embodiment, both X and Y are N;

[0050] Q 1 、Q 2 、Q 3 and Q 4 are linkers, such as a hydrocarbon group (including substituted hydrocarbon groups, heteroatom-containing hydrocarbon groups, and substituted heteroatom-containing hydrocarbon groups, such as substituted and / or heteroatom-containing alkyl groups) or -(CO)-, and w, x, y, and z are independently zero or 1, which means that each linker is optional. Preferably, w, x, y, and z are all zero. In addition, two or more substituents of adjacent atoms within Q 1 、Q 2 、Q 3 and Q 4 can be linked to form additional cyclic groups;

[0051] R 3 、R 3A 、R 4 and R 4A are independently selected from hydrogen, hydrocarbon groups, substituted hydrocarbon groups, heteroatom-containing hydrocarbon groups, and substituted heteroatom-containing hydrocarbon groups. In addition, X and Y can be independently selected from carbon and one of the above heteroatoms, and preferably no more than one of X or Y is carbon. Additionally, L 2 and L 3 can combine to form a single bidentate electron-donating heterocyclic ligand. In addition, R 1 and R 2 can combine to form an indenylidene moiety, preferably phenylindenylidene. In addition, X 1 、X 2 、L 2 、L3 、X and Y can be further coordinated with boron or carboxylate;

[0052] X 1 、X 2 、L 1 、L 2 、L 3 、R 1 、R 2 、R 3 、R 3A 、R 4 、R 4A 、Q 1 、Q 2 、Q 3 and Q 4 Any two or more of them can bond to each other to form one or more cyclic groups or can also be regarded as -A-Fn, where "A" is a divalent hydrocarbon moiety and Fn is a functional group as described previously.

[0053] In addition, in addition to L 1 , such groups can be bonded to a carrier.

[0054] Such carbenes of a specific class are generally referred to as N-heterocyclic carbene (NHC) ligands.

[0055] Therefore, examples of N-heterocyclic carbene (NHC) ligands and acyclic diamino carbene ligands suitable as L 1 include, but are not limited to, the following, where DIPP or DiPP is diisopropylphenyl and Mes is 2,4,6-trimethylphenyl:

[0056]

[0057] Representative metal carbene olefin metathesis catalysts include, for example, benzylidene bis(tricyclohexylphosphine) ruthenium dichloride, dimethylvinylidene bis(tricyclohexylphosphine) ruthenium dichloride, dimethylvinylidene bis(tricyclopentylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine)(1,3-bis(trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) ruthenium dichloride, dimethylvinylidene (tricyclopentylphosphine)(1,3-bis(trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) ruthenium dichloride, dimethylvinylidene (tricyclohexylphosphine)(1,3-bis(trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) ruthenium dichloride, benzylidene (tricyclohexylphosphine)(1,3-bis(trimethylphenyl)imidazol-2-ylidene) ruthenium dichloride, dimethylvinylidene (tricyclopentylphosphine)(1,3-bis(trimethylphenyl)imidazol-2-ylidene) ruthenium dichloride, and dimethylvinylidene (tricyclohexylphosphine)(1,3-bis(trimethylphenyl)imidazol-2-ylidene) ruthenium dichloride.

[0058] Multiple metal carbene olefin metathesis catalysts are known, such as those described in the previously cited US 10,239,965.

[0059] In some embodiments, the composition (e.g., the composition of an article) comprises a latent ring-opening metathesis polymerization catalyst. The latent ring-opening metathesis polymerization catalyst exhibits little or no catalytic activity (e.g., polymerization of a cyclic olefin) at room temperature for at least 24 hours. The composition or article can be stored at a low temperature to prevent premature activation of the thermally activated catalyst. Similarly, the composition or the coated (e.g., adhesive tape) article can be stored in a dark box or a dark packaging material to prevent premature activation of the photoactivated catalyst. The latent ring-opening metathesis polymerization catalyst can be triggered, or in other words, activated, using heat (i.e., thermal activation), actinic (e.g., ultraviolet) radiation, a compound, or a combination thereof. Actinic radiation-activated catalysts can be preferably used for bonding heat-sensitive substrates composed of organic polymeric materials.

[0060] However, for bonding other substrates, the (e.g., latent) catalyst can be thermally activated. In typical embodiments, the thermal activation temperature is well above room temperature. For example, the thermal activation temperature is at least 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, or 100 °C. The thermal activation temperature can range up to 130 °C, 140 °C, or 150 °C. In one embodiment, the thermally latent catalyst comprises an isomer that is inactive at room temperature but is active at temperatures in the range of 50 °C to 90 °C. Several thermally activatable ROMP catalysts are available from Materia, Inc (Pasadena, CA, USA), including those obtained under the trade names "Proxima CT-762" and "Proxima CT-714".

[0061] Based on the total weight of the composition, the composition typically comprises an amount of ROMP catalyst in the range of about 0.0001 wt% to 2 wt% of the catalyst. In some embodiments, the composition typically comprises at least 0.0005 wt%, 0.001 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.10 wt%, 0.15 wt%, or 0.20 wt% of the catalyst. In some embodiments, the composition typically comprises no more than 1.5 wt%, 1 wt%, or 0.5 wt% of the catalyst.

[0062] Second polymerizable material

[0063] The composition (e.g., the composition of an article and a method) comprises a second polymerizable material. The second polymerizable material can be characterized as a monomer. As used herein, the term monomer refers to monomers and oligomers containing polymerizable (e.g., epoxy or (meth)acrylate groups) typically having a molecular weight of no greater than about 10,000 g / mol. The second polymerizable material polymerizes or, in other words, cures under curing conditions different from those of cyclic olefins. In typical embodiments, the second polymerizable material cures via a mechanism different from ROMP. When the second polymerizable material cures, a polymer is formed from the polymerized second material.

[0064] In some embodiments, the second polymerizable material is an epoxy-containing component, i.e., an organic compound having one or more oxirane rings that can be polymerized by a ring-opening mechanism. The epoxy functional group can be cationically polymerized or, in other words, cured.

[0065] The epoxy-containing component can be aliphatic, alicyclic, heterocyclic, aromatic, hydrogenated, or a mixture thereof. Preferred epoxides contain more than 1.5 or 2 epoxy groups per molecule.

[0066] The epoxy-containing component includes compounds having the following general formula:

[0067]

[0068] wherein R 1 is an alkyl, alkyl ether, or aryl group, and n ranges from 1 to 6.

[0069] The epoxy-containing component includes aromatic glycidyl ethers (e.g., aromatic glycidyl ethers prepared by reacting a polyphenol with an excess of epichlorohydrin), alicyclic glycidyl ethers, hydrogenated glycidyl ethers, and mixtures thereof. Such polyphenols can include resorcinol, catechol, hydroquinone, and polynuclear phenols such as p,p'-dihydroxydibenzyl sulfone, p,p'-dihydroxydiphenyl sulfone, p,p'-dihydroxyphenyl sulfone, p,p'-dihydroxybenzophenone, 2,2'-dihydroxy-1,1-dinaphthylmethane, and the 2,2', 2,3', 2,4', 3,3', 3,4', and 4,4' isomers of dihydroxydiphenylmethane, dihydroxydiphenyldimethylmethane, dihydroxydiphenylethylmethylmethane, dihydroxydiphenylmethylpropylmethane, dihydroxydiphenylethylphenylmethane, dihydroxydiphenylpropylphenylmethane, dihydroxydiphenylbutylphenylmethane, dihydroxydiphenyltolylethane, dihydroxydiphenyltolylmethylmethane, dihydroxydiphenyl dicyclohexylmethane, and dihydroxydiphenyl cyclohexane.

[0070] The epoxy-containing component may include a straight-chain polymeric epoxide having terminal epoxy groups (e.g., diglycidyl ethers of polyalkylene glycols), a polymeric epoxide having backbone epoxy groups (e.g., polybutadiene polyepoxide), a polymeric epoxide having epoxy side groups (e.g., glycidyl methacrylate polymer or copolymer), or a mixture thereof.

[0071] Other available epoxy-containing components are polyphenol formaldehyde condensation products and glycidyl ethers containing only epoxy groups or in combination with hydroxyl groups as reactive groups. Available curable epoxy resins are also described in various publications, including, for example, "Handbook of Epoxy Resins" by Lee and Nevill (1967), published by McGraw-Hill Book Co., New York, and "Encyclopedia of Polymer Science and Technology", 6, page 322 (1986).

[0072] Examples of commercially available epoxy-containing components include diglycidyl ethers of bisphenol A (e.g., those available under the trade names EPON 828, EPON 1001, EPON 1004, EPON 2004, EPON 1510, and EPON 1310 from Momentive Specialty Chemicals, Inc. (Waterford, NY, USA)), and those available under the trade names D.E.R. 331, D.E.R. 332, D.E.R. 334, and D.E.N. 439 from Dow Chemical Co. (Midland, MI, USA)); diglycidyl ethers of bisphenol F (which can be obtained, for example, under the trade name ARALDITE GY 281, from Huntsman Corporation (The Woodlands, TX, USA)); silicone resins containing diglycidyl functional groups; flame-retardant epoxy resins (e.g., brominated bisphenol-type epoxy resins available under the trade name D.E.R. 560 from Dow Chemical Co.); and 1,4-butanediol diglycidyl ether.

[0073] In some embodiments, the composition further comprises a hydroxyl-containing component. When the epoxy groups react via a cationic mechanism, the hydroxyl-containing component can act as a chain transfer agent for the epoxy-containing component.

[0074] Suitable hydroxyl-containing components include liquid polyols and polymeric hydroxyl-containing (e.g., end-capped) components, including polyester polyols known in the art. In typical embodiments, the hydroxyl-containing component can have on average at least 1.5, 2, 2.5, and typically no more than 3, 2.5, or 2 hydroxyl groups per molecule (chain). The hydroxyl-containing component can have a molecular weight (Mn) of at least 500 g / mol, 750 g / mol, or 1,000 g / mol. In some embodiments, the hydroxyl-containing component has a molecular weight (Mn) of no more than 5,000 g / mol; 4,000 g / mol; 3,000 g / mol; 2,500 g / mol; 2,000 g / mol; or 1,500 g / mol.

[0075] In one embodiment, the hydroxyl-containing component is a hydroxyl-terminated polyolefin (e.g., butadiene). In some embodiments, the polyolefin contains ethylenically unsaturated groups (e.g., 1,2 vinyl), such as in the case of polybutadiene. The 1,2 vinyl content is typically 60 wt% - 70 wt% of the hydroxyl-containing polyolefin (e.g., butadiene). In other embodiments, the polyolefin (e.g., butadiene) can be partially or fully hydrogenated. When partially hydrogenated, the 1,2 vinyl content can be less than 60 wt%, 50 wt%, 40 wt%, 30 wt%, 20 wt%, or 10 wt% of the hydroxyl-containing polyolefin (e.g., butadiene). It is speculated that the vinyl groups can copolymerize with cyclic olefins. Hydroxyl-containing (e.g., end-capped) polyolefin (e.g., butadiene) materials are available from Cray Valley (Exton, PA, USA) under the trade names "Krasol LBH 2000", "Krasol LBH-P 2000", "Krasol LBH 3000", "KrasolLBH-P3000", "Krasol HLBH-P 2000", and "Krasol HLBH-P 3000".

[0076] As shown in Example 11, in the absence of the hydroxyl-containing component, the curing of the epoxy resin may be incomplete, as evidenced by the presence of liquid after thermal curing. It is speculated that by including a hydroxyl-containing component, such as hydroxyl-terminated polybutadiene, the curing efficiency of the epoxy resin can be improved. The curing of the epoxy resin can also be improved by adjusting the curing conditions (such as increasing time and / or increasing temperature).

[0077] In some embodiments, the second polymerizable material is an epoxidized polyolefin, such as epoxidized polybutadiene, in which one or more of the carbon-carbon double bonds in the oligomer or polymer have been epoxidized (i.e., converted to an ethylene oxide ring). In some embodiments, the epoxidized polyolefin (e.g., butadiene) has an epoxy equivalent weight of at least 100 g / equivalent, 150 g / equivalent, 200 g / equivalent, 250 g / equivalent, or 300 g / equivalent (as determined by ATO-822). In some embodiments, the epoxy equivalent weight is not greater than 1000 g / equivalent, 900 g / equivalent, 700 g / equivalent, 600 g / equivalent, 500 g / equivalent, 400 g / equivalent, or 300 g / equivalent.

[0078] In some embodiments, the epoxidized polyolefin (e.g., butadiene) further comprises hydroxyl groups. The epoxidized polyolefin (e.g., butadiene) can have the same average hydroxyl group and molecular weight per molecule (chain), as described just for the hydroxyl-containing component.

[0079] In some embodiments, the epoxidized polyolefin (e.g., butadiene) can further comprise an ethylenically unsaturated moiety, such as a 1,2 vinyl group. Based on the total weight of the epoxidized polyolefin (e.g., butadiene), the weight % of the vinyl group can be at least 5 wt%, 10 wt%, 15 wt%, or 20 wt% (as determined by proton NMR / IR). In some embodiments, the weight % of vinyl is not greater than 25 wt%. It is speculated that the vinyl group can copolymerize with cyclic olefins. The epoxidized polyolefin (e.g., butadiene) can have the following formula:

[0080]

[0081] Examples of epoxidized polyolefins (e.g., butadiene) that further comprise hydroxyl groups and ethylenically unsaturated moieties can be obtained as “Poly bd 605E” and “Poly bd 700S”, available from Cray Valley (Exton, Pennsylvania, USA).

[0082] Functionalized polyolefins, including polymerized hydrocarbons having 4 or more carbon atoms, such as butadiene, typically have a Tg of less than 25 °C, 0 °C, -25 °C, or -50 °C. In some embodiments, the functionalized polybutadiene has a Tg of at least -80 °C, -75 °C, -70 °C, -65 °C, -60 °C, -55 °C, -50 °C, -45 °C, -40 °C, or -35 °C. Adding a second polymerizable material with a low Tg can improve the flexibility of the polymerized cyclic olefin.

[0083] The composition can have a combination of different epoxy-containing components. For example, the composition can have a combination of a first epoxy resin that does not contain a polybutadiene moiety and epoxidized polybutadiene.

[0084] In other embodiments, the second polymerizable material is a (meth)acrylate monomer containing an alicyclic or heteroalicyclic group. Such monomers are free-radically polymerizable and capable of addition polymerization. Such monomers contain at least one, and typically two or more, (meth)acrylate groups. The number of (meth)acrylate groups is usually no greater than 3, 4, 5, or 6.

[0085] Monomers having an alicyclic or heteroalicyclic group are generally high glass transition temperature (Tg) monomers. In some embodiments, the homopolymer of the (meth)acrylate monomer has a Tg of at least 50 °C, 75 °C, 100 °C, 125 °C, 150 °C, or 175 °C. In some embodiments, the Tg of other ethylenically unsaturated monomers is no greater than about 200 °C. When the composition contains a sufficient amount of the high-Tg second polymerizable material, the composition can be dimensionally more stable at elevated temperatures.

[0086] Exemplary mono(meth)acrylates containing an alicyclic group include, for example, isobornyl acrylate (Tg = 94 °C), isobornyl methacrylate (Tg = 110 °C), cyclohexyl methacrylate (Tg = 116 °C), tert-butyl cyclohexyl acrylate (Tg = 65 °C), and tert-butyl cyclohexyl methacrylate (Tg = 117 °C).

[0087] A representative di(meth)acrylate monomer containing an alicyclic group is tricyclodecane dimethanol diacrylate (shown below), and its Tg measured by dynamic mechanical analysis is reported to be 186 °C.

[0088]

[0089] Other di(meth)acrylate monomers containing an alicyclic group include cyclohexyl acrylate (Tg = 19 °C), cyclohexyl methacrylate (Tg = 92 °C), isobornyl acrylate (Tg = 94 °C), isobornyl methacrylate (Tg = 110 °C), tetrahydrofurfuryl acrylate, and (meth)acrylate monomers containing a norbornene moiety.

[0090] Another representative (meth)acrylate monomer containing a heterocyclic group (such as isocyanurate) is tris[(2-acryloyloxy)ethyl] isocyanurate (shown below)

[0091]

[0092] In some embodiments, particularly in combination with cyclo(hetero)aliphatic (meth)acrylate monomers, the composition may optionally comprise other ethylenically unsaturated free-radically polymerizable monomers comprising (meth)acrylate groups. For example, the composition may comprise a total of 40 wt% of (meth)acrylate monomers, where 30 wt% are (hetero)-alicyclic (meth)acrylate monomers and 10 wt% are different (meth)acrylate monomers without (hetero)alicyclic moieties.

[0093] (Hetero)cyclic (meth)acrylate monomers generally do not contain acidic groups (such as carboxylic acids). In some embodiments, the composition does not contain components (such as monomers) having acidic groups (such as acrylic acid) because acidic groups can be corrosive, particularly when applied to a metal substrate.

[0094] Available (meth)acrylates include, for example, monoacrylates, diacrylates or polyacrylates and monomethacrylates, dimethacrylates or polymethacrylates, such as methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, octadecyl acrylate, allyl acrylate, glycerol diacrylate, glycerol triacrylate, hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, trimethylolpropane triacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, sorbitol hexaacrylate, polyurethane acrylate and (meth)acrylates of polyethylene glycols having a molecular weight in the range of 200 g / mol - 500 g / mol.

[0095] The composition (e.g., the composition of an article and a method) comprises at least one second polymerizable material in an amount greater than 25% by weight, based on the total amount of the cyclic olefin and the second polymerizable material, and the amount is greater than 25% by weight. Thus, the composition may comprise a component monomer containing an epoxide in an amount greater than 25% by weight or a (hetero)alicyclic (meth)acrylate monomer in an amount greater than 25% by weight. In another embodiment, the composition may comprise a component containing an epoxide in an amount greater than 25% by weight and a (hetero)alicyclic (meth)acrylate monomer in an amount greater than 25% by weight. In some embodiments, the composition comprises at least 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80% by weight of the component containing an epoxide and / or the (hetero)alicyclic (meth)acrylate monomer. In some embodiments, the composition comprises no more than 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35% or 30% by weight of the component containing an epoxide and / or the (hetero)alicyclic (meth)acrylate monomer. When the composition comprises other polymerizable materials in addition to the cyclic olefin and the second polymerizable material described herein, the composition generally comprises the second polymerizable material in an amount greater than 25% by weight, based on the total amount of the polymerizable materials.

[0096] When the component containing an epoxide and / or the (hetero)alicyclic (meth)acrylate monomer is present in a sufficient amount, such a second polymerizable material can independently form a polymer different from the polymer of the polymerized cyclic olefin. In a typical embodiment, an interpenetrating network (IPN) is formed. An interpenetrating polymer network is a polymer comprising two or more networks that are at least partially interlaced on a polymer scale but do not covalently bond to each other. The entanglement of the polymer networks can affect the physical properties. In some embodiments, the polymer networks can also be crosslinked. For example, the vinyl groups of the above epoxidized butadiene can be copolymerized during the polymerization of the cyclic olefin. In this embodiment, the networks cannot be separated unless the chemical bonds are broken.

[0097] In some embodiments, each polymer network can have a different Tg. Thus, the composition can have a first Tg of the polymerized cyclic olefin and a second Tg of the cured second polymerizable material. It is also speculated that the composition can have at least three polymer networks: a polymer network of the polymerized cyclic olefin, a polymer network of the polymerized epoxy component, and a polymer network of the polymerized (hetero)alicyclic monomer. For example, this can occur when the composition comprises at least 30% by weight of the cyclic olefin, at least 30% by weight of the component containing an epoxide, and at least 30% by weight of the hetero(cyclo)aliphatic monomer.

[0098] Initiator for the second polymerizable material

[0099] Compositions (such as compositions of articles) typically contain an initiator for a second polymerizable material. The composition is typically provided for manufacturing an article that contains the initiator premixed with other components. The initiator can be added immediately before use. The initiator is typically selected such that the second polymerizable material cures under curing conditions different from those of the cyclic olefin. In some embodiments, the initiator is a cationic initiator, such as a thermally or photoacid generator for curing epoxy groups or a free radical initiator for curing (meth)acrylate groups. ROMP catalysts are typically thermally activated.

[0100] The free radical initiator can be a thermal initiator or a photoinitiator, and the type and amount thereof can effectively polymerize the (meth)acrylic portion of the second polymerizable material. The initiator is typically used at a concentration in the range of from about 0.0001 parts by weight to about 3.0 parts by weight, preferably from about 0.001 parts by weight to about 1.0 parts by weight, and more preferably from about 0.005 parts by weight to about 0.5 parts by weight of the composition.

[0101] Suitable thermal initiators include, but are not limited to, those selected from the group consisting of: azo compounds (such as VAZO 64 (2,2'-azobis(isobutyronitrile)), VAZO 52 (2,2'-azobis(2,4-dimethylpentanenitrile)), and VAZO 67 (2,2'-azobis-(2-methylbutyronitrile)) available from Chemours (Wilmington, DE, USA)); peroxides (such as benzoyl peroxide and lauroyl peroxide); and mixtures thereof. A preferred oil-soluble thermal initiator is (2,2'-azobis-(2-methylbutyronitrile)).

[0102] Examples of photoinitiators that can be used include benzoin ethers (e.g., benzoin methyl ether or benzoin butyl ether); acetophenone derivatives (e.g., 2,2-dimethoxy-2-phenylacetophenone or 2,2-diethoxyacetophenone); 1-hydroxycyclohexyl phenyl ketone; and acylphosphine oxide derivatives and acylphosphonate derivatives (e.g., bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, diphenyl-2,4,6-trimethylbenzoylphosphine oxide, isopropoxyphenyl-2,4,6-trimethylbenzoylphosphine oxide, or dimethylpivaloylphosphonate). Many photoinitiators are available, for example, under the trade name "OMNIRAD" from IGM Resins (Charlotte, NC, USA). The photoinitiator can be selected, for example, based on the desired curing wavelength and compatibility with the monomer.

[0103] Description of photoacid generator

[0104] Some of the articles and compositions described herein contain a photoacid generator as an initiator for a second polymerizable material. The type and amount of the photoacid generator are effective for cationic polymerization on the epoxy groups of the second polymerizable material. Preferred photoacid generators are generally ionic photoacid generators or triazine compounds.

[0105] When irradiated with light energy, the photoacid generator undergoes a cleavage reaction and releases one or more Lewis acid or Bronsted acid molecules, which induce the polymerization of the epoxy moiety of the second polymerizable material. The photoacid generators available are thermally stable, do not undergo thermally induced reactions with the composition, and are readily soluble or dispersible in the composition. Typical photoacid generators are those in which the pKa value of the initial acid is <0. Photoacid generators are known and reference is made to "Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints" by K. Dietliker, Volume Ill, SITA Technology Ltd., London, 1991. Reference is also made to the "Kirk-Othmer Encyclopedia of Chemical Technology", 4th Edition, Supplement Volume, John Wiley and Sons, New York, 1992, pages 253 - 255.

[0106] Cations that can be used as the cationic moiety of an ionic photoinitiator include organic onium cations, such as those described in U.S. Patent Nos. 4,250,311, 3,708,296, 4,069,055, 4,216,288, 5,084,586, 5,124,417, 5,554,664, and such descriptions are incorporated herein by reference, including onium salts centered on aliphatic or aromatic groups IVAVIIA (CAS version), preferably onium salts centered on I-, S-, P-, Se-, N-, and C-, such as those selected from sulfoxonium, iodonium, sulfonium, selenonium, pyridinium, carbonium, and phosphonium salts, and most preferably onium salts centered on I- and S-, such as those selected from sulfoxonium, diaryliodonium, triarylsulfonium, diarylalkylsulfonium, dialkylarylsulfonium, and trialkylsulfonium salts, where "aryl" and "alkyl" are as defined and have up to four independently selected substituents. Substituents on the aryl and alkyl moieties preferably will have fewer than 30 carbon atoms and up to 10 heteroatoms selected from N, S, non-peroxidized O, P, As, Si, Sn, B, Ge, Te, Se. Examples include hydrocarbyl groups, such as methyl, ethyl, butyl, dodecyl, tetracosyl, benzyl, allyl, benzylidene, vinyl, and ethynyl; hydrocarbyloxy groups, such as methoxy, butoxy, and phenoxy; hydrocarbylthio groups, such as methylthio and phenylthio; hydrocarbyloxycarbonyl groups, such as methoxycarbonyl and phenoxycarbonyl; hydrocarbylcarbonyl groups, such as formyl, acetyl, and benzoyl; hydrocarbylcarbonyloxy groups, such as acetoxy and cyclohexylcarbonyloxy; hydrocarbylamide groups, such as acetamido and benzamido; azo; oxoboron; halogen groups, such as chlorine, bromine, iodine, and fluorine; hydroxy; oxy; diphenylarsino; diphenylstibino; trimethylgermyl; trimethylsiloxy; and aromatic groups, such as cyclopentadienyl, phenyl, tolyl, naphthyl, and indenyl. For sulfonium salts, the substituents can be further substituted by a dialkyl or diarylsulfonium cation; an example thereof will be 1,4-phenylene bis(diphenylsulfonium).

[0107] Useful onium salt photoacid generators include diazonium salts, such as aryl diazonium salts; halonium salts, such as diaryliodonium salts; sulfonium salts, such as triarylsulfonium salts, such as triphenylsulfonium trifluoromethanesulfonate; selenonium salts, such as triarylselenonium salts; sulfoxonium salts, such as triarylsulfoxonium salts; and other miscellaneous onium salts, such as triarylphosphonium and arsonium salts, and pyranylium and thiopyranylium salts.

[0108] Ionic photoacid generators include, for example, bis(4-tert-butylphenyl)iodonium hexafluoroantimonate (FP5034 from Hampford Research Inc., Stratford, CT, USA) TM )、under the name Syna PI-6976TM A mixture of triarylsulfonium salts (diphenyl(4-phenylthio)phenylsulfonium hexafluoroantimonate, bis(4-(diphenylsulfonium)phenyl)sulfide hexafluoroantimonate), (4-methoxyphenyl)phenyl iodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium hexafluoroantimonate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium tetraphenylborate, bis(4-tert-butylphenyl)iodonium tosylate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, ([4-(octyloxy)phenyl]phenyliodonium hexafluorophosphate), ([4-(octyloxy)phenyl]phenyliodonium hexafluoroantimonate), (4-isopropylphenyl)(4-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate (available as Rhodorsil 2074 TM purchased from Bluestar Silicones, East Brunswick, NJ, USA), bis(4-methylphenyl)iodonium hexafluorophosphate (available as Omnicat 440 from IGM Resins, Charlotte, NC, USA), 4-(2-hydroxy-l-tetradecyloxy)phenyl]phenyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate (available as CT-548 from Chitec Technology Corp., Taipei, Taiwan, China), diphenyl(4-phenylthio)phenylsulfonium hexafluorophosphate, bis(4-(diphenylsulfonium)phenyl)sulfide bis(hexafluorophosphate), diphenyl(4-phenylthio)phenylsulfonium hexafluoroantimonate, bis(4-(diphenylsulfonium)phenyl)sulfide hexafluoroantimonate and blends of these triarylsulfonium salts available under the trade names Syna PI-6992 and Syna PI-6976 (for PF 6 and SbF 6 salts) purchased from Synasia.

[0109] A preferred photoacid generator is triphenylsulfonium hexafluoroantimonate, obtained from Aceto Corporation (Port Washington, NY, USA) under the name "CPI-6976" as a 50% solution in propylene carbonate. The solution can be dried to produce the pure solid salt, which is also a preferred photoacid generator.

[0110] Other photoacid generators are triazine compounds having the following formula.

[0111]

[0112] wherein R of the triazine crosslinker 1 、R 2 、R 3 and R 4 are independently hydrogen or alkoxy groups, and 1 to 3 of R 1 、R 2 、R 3 and R 4 are hydrogen. The alkoxy group generally has no more than 12 carbon atoms. In a preferred embodiment, the alkoxy groups are independently methoxy or ethoxy. A representative substance is 2,4-bis(trichloromethyl)-6-(3,4-bis(methoxy)phenyl)-triazine. Such triazine compounds are further described in U.S. Patent 4,330,590.

[0113] In some embodiments, the ROMP catalyst is thermally activated; and the initiator for the second polymerizable material is activated by exposure to actinic radiation. In one embodiment, as demonstrated in the following examples (e.g., triarylsulfonium hexafluoroantimonate), a cationic (CPI-6976) photoacid generator initiator can initiate the curing of epoxy groups at a lower wavelength. In another embodiment, (e.g., (2,4,6-trimethylbenzoyl) phenylphosphinic acid ethyl ester free radical photoinitiator (OMNIRAD TPO-L) can initiate the curing of (meth)acrylate monomers at a higher light wavelength. Heat can accelerate the curing reaction of the cationic photoacid generator.

[0114] Alternatively or in combination with a photoacid generator, a thermoacid generator can be used to initiate epoxy polymerization. In this embodiment, the thermoacid generator is generally activated at a temperature higher or lower than the thermal activation temperature of the ROMP catalyst. For example, cyclic olefins can be polymerized using a ROMP catalyst at room temperature or lower (less than 100 °C), and the epoxy groups are cured via thermal activation (without light) using the aforementioned iodonium salt at an elevated temperature.

[0115] The thermal and / or photoacid generator is generally used at a concentration in the range of about 0.0001 parts by weight to about 3.0 parts by weight, preferably about 0.001 parts by weight to about 1.0 parts by weight, and more preferably about 0.005 parts by weight to about 0.5 parts by weight of the organic portion of the total composition.

[0116] Optional other components

[0117] In some embodiments, the total amount of the cyclic olefin and the second polymerizable material is typically at least 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 95 wt% of the total composition. The composition typically comprises a homogeneous mixture of the second polymerizable material and the cyclic olefin.

[0118] The mixture of the cyclic olefin and the second polymerizable material has a viscosity suitable for various application methods. The complex viscosity is typically greater than that of the cyclic olefin. In some embodiments, the complex viscosity is at least 1 Pa·s or 2 Pa·s at various frequencies (such as 200 rad / sec, 126.2 rad / sec, 79.6 rad / sec, 20 rad / sec, 5 rad / sec, 2 rad / sec, 0.8 rad / sec or 0.1 rad / sec). In some embodiments, the complex viscosity is less than 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4 or 3 at various frequencies (such as 200 rad / sec, 126.2 rad / sec, 79.6 rad / sec, 20 rad / sec, 5 rad / sec, 2 rad / sec, 0.8 rad / sec or 0.1 rad / sec). The mixture can be shear-thinning. The ratio of the complex viscosity at 0.1 rad / sec to the complex viscosity at 200 rad / sec can be at least 2, 3 or 4, and can be less than 5.

[0119] The composition (such as the composition of the article and the method) can optionally comprise other components (such as non-polymerizable components) that can be described as additives. Additives include adhesion promoters, tackifiers, plasticizers, antioxidants, UV stabilizers, colorants and (such as inorganic) fillers.

[0120] When the composition further comprises other components, the total amount of the cyclic olefin and the second polymerizable material is typically less than 90 wt%, 80 wt%, 70 wt%, 60 wt%, 50 wt%, 40 wt% or 30 wt% of the total composition. For example, the total amount of the cyclic olefin and the second polymerizable material can be 50 wt%, and the composition (such as the composition of the article) can comprise 50 wt% of additives such as inorganic fillers.

[0121] The composition can further comprise an adhesion promoter. Various adhesion promoters have been described in the literature. See, for example, WO2021 / 074734 and WO2021 / 074749, which are incorporated by reference.

[0122] In some embodiments, the adhesion promoter is a compound or polymer containing at least two isocyanate groups.

[0123] Representative polymeric polyisocyanates (e.g., diisocyanates) include, for example, polyisocyanate prepolymers available from Covestro (Elgin, IL, USA), including the trade names DESMODUR E-28 (based on MDI) and Baytec ME-230 (modified MDI based on polytetramethylene ether glycol (PTMEG)). Such polymeric polyisocyanates (e.g., diisocyanates) contain C2-C4 alkylene oxide repeat units. In addition, the average equivalent weight of such polymeric polyisocyanates is typically in the range of 200 g / mol / isocyanate group to 5000 g / mol / isocyanate group.

[0124] Other polymeric isocyanates include, for example, PM200 (polymeric MDI), Lupranate TM (polymeric MDI from BASF), various isocyanate-terminated polybutadiene prepolymers available from Creanova, including Krasol TM LBD2000 (based on TDI), Krasol TM LBD3000 (based on TDI), Krasol TM NN-22 (based on MDI), Krasol TM NN-23 (based on MDI) and Krasol TM NN-25 (based on MDI).

[0125] In other embodiments, the composition may contain a maleic anhydride-grafted polymer as an adhesion promoter, such as those available under the trade name "POLYVEST MA 75" from Evonik (Essen, Germany), and those available under the trade name "RICON 131 maleated polybutadiene 131MA10" from Creanova (Exton, PA) or under the trademarks "Kraton FG1901G" and "Kraton FG1924G" from Kraton Performance Polymers.

[0126] In other embodiments, the composition can include a compound or polymer having an alkoxysilyl group as an adhesion promoter. Several trialkoxysilane compounds are available from Gelest (Morrisville, PA, USA), such as 3-(trimethoxysilyl)propyl methacrylate, which is available from Alfa Aesar (Ward Hill, MA, USA) under the name "A174". A trimethoxysilane-capped polybutadiene oligomer is available from Evonik in Essen, Germany under the name "STM".

[0127] When present, the composition typically includes at least 0.005 wt%, 0.010 wt%, 0.050 wt%, 0.10 wt%, 0.50 wt% or 1 wt% of the adhesion promoter, based on the total weight of the composition. In some embodiments, the amount of the adhesion promoter is no greater than 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt% or 1 wt% of the total weight of the composition.

[0128] In some embodiments, the composition further includes an inorganic filler, including, for example, silica (such as fumed silica, glass bubbles), metal oxides, hydroxides, oxyhydroxides, silicates, borides, carbides, and nitrides.

[0129] In some embodiments, the composition of the (e.g., electronic) article includes thermally conductive inorganic particles that are preferably non-conductive materials, as described in WO2021 / 074734; this patent is incorporated herein by reference. Suitable non-conductive thermally conductive materials include ceramics, such as metal oxides, hydroxides, oxyhydroxides, silicates, borides, carbides, and nitrides. Suitable ceramic fillers include, for example, silica, zinc oxide, aluminum trihydroxide (ATH) (also known as hydrated alumina, alumina, and aluminum trihydroxide), aluminum nitride, boron nitride, silicon carbide, and beryllium oxide. Other thermally conductive fillers include carbon-based materials (such as graphite) and metals (such as aluminum and copper). Combinations of different thermally conductive materials can be utilized. Such materials are not conductive, i.e., have an electron bandgap greater than 0 eV and in some embodiments at least 1 eV, 2 eV, 3 eV, 4 eV, or 5 eV. In some embodiments, such materials have an electron bandgap no greater than 15 eV or 20 eV.

[0130] Thermal conductive particles can be obtained in a variety of shapes, such as spherical and needle-like shapes, which can be irregular or plate-like. In some embodiments, the thermal conductive particles are crystals and generally have a geometric shape. For example, hexagonal boron nitride crystals are commercially available from Momentive. In addition, aluminum oxide trihydrate is described as hexagonal platelets. Combinations of particles with different shapes can be utilized. The thermal conductive particles generally have an aspect ratio of less than 100:1, 75:1, or 50:1. In some embodiments, the thermal conductive particles have an aspect ratio of less than 3:1, 2.5:1, 2:1, or 1.5:1. In some embodiments, substantially symmetric (e.g., spherical, hemispherical) particles can be employed.

[0131] In some embodiments, the thermal conductive particles include a combination of smaller particles and larger particles. The combination of particle sizes can provide a higher thermal conductivity than thermal conductive particles having an intermediate median particle size and a normal particle size distribution. Without being bound by theory, it is speculated that including a sufficient amount of smaller particles with an appropriate particle size improves the thermal conductivity between the larger particles.

[0132] The composition of the abrasive article includes abrasive particles. Suitable abrasive particles can include any abrasive particles used in the grinding industry. Preferably, the Mohs hardness of the abrasive particles is 8.5 or greater, more preferably 9 or greater, and most preferably 9 to 10. In certain embodiments, the abrasive particles include superabrasive particles. As used herein, the term "superabrasive" refers to any abrasive particle having a hardness greater than or equal to the hardness of silicon carbide (e.g., silicon carbide, boron carbide, cubic boron nitride, and diamond).

[0133] Generally, the abrasive particles include at least one of diamond particles, metal oxide ceramic particles, or non-oxide ceramic particles. Examples of suitable abrasive particles include, for example but not limited to, cubic boron nitride, fused alumina, ceramic alumina, heat-treated alumina, white fused alumina, black silicon carbide, green silicon carbide, titanium diboride, boron carbide, silicon nitride, tungsten carbide, titanium carbide, diamond, cubic boron nitride, hexagonal boron nitride, alumina, zirconia, iron oxide, cerium dioxide, garnet, fused alumina zirconia, alumina-based sol-gel derived abrasive particles, etc. The alumina abrasive particles can contain metal oxide modifiers. The diamond and cubic boron nitride abrasive particles can be single crystal or polycrystalline. Other examples of suitable inorganic abrasive particles include silica, iron oxide, chromium oxide, cerium dioxide, zirconia, titanium dioxide, tin oxide, γ-alumina, etc.

[0134] The abrasive particles may include abrasive agglomerate particles. Abrasive agglomerate particles typically comprise a plurality of abrasive particles, a binder, and optionally additives. The binder can be organic and / or inorganic. The abrasive agglomerates can be of random shape or have a predetermined shape associated therewith. Optionally, the abrasive agglomerates include ceramic abrasive agglomerates that comprise individual abrasive particles dispersed in a porous ceramic matrix, wherein at least a portion of the porous ceramic matrix comprises a vitreous ceramic material.

[0135] In some embodiments, the abrasive particles may include at least one of cubic boron nitride, silicon carbide, titanium diboride, titanium nitride, boron carbide, tungsten carbide, titanium carbide, aluminum nitride, alumina, diamond, garnet, fused alumina-zirconia, sol-gel derived abrasive particles, cerium oxide, zirconia, titanium oxide, silicon dioxide, or silicon nitride particles.

[0136] Various abrasive particles are described in the literature. See, for example, WO2022 / 101746; which is incorporated herein by reference.

[0137] When present, based on the total weight of the composition, the composition typically comprises at least 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt% of an inorganic filler. In some embodiments, the amount of the inorganic filler is not greater than 70 wt%, 65 wt%, 60 wt%, 55 wt%, 50 wt%, 45 wt%, 40 wt%, 35 wt%, 30 wt%, 25 wt%, 20 wt%, 15 wt%, or 10 wt% of the total weight of the composition.

[0138] Description of substrate and article

[0139] A variety of articles can be formed from the composition, including electronic articles, abrasive articles, and components thereof.

[0140] In some embodiments, the article is a bilayer article that includes a layer of the composition disposed on a substrate. The composition typically has a thickness of at least 1 micron, 2 microns, 3 microns, 4 microns, or 5 microns. In some embodiments, the composition has a thickness of not greater than 10 mils, 5 mils, 1 mil (1000 microns), 500 microns, 250 microns, 100 microns, or 50 microns.

[0141] The available substrates can be inorganic, organic, or a combination thereof. Representative examples of available substrates include ceramics, siliceous substrates including glass, metals (e.g., aluminum or steel), natural and artificial stones, woven and non-woven products, polymeric materials including thermoplastic and thermosetting polymer materials (such as poly(methyl)methacrylate, polycarbonate, polystyrene, styrene copolymers such as styrene acrylonitrile copolymer, polyester, polyethylene terephthalate), and composite materials of the above materials.

[0142] In some embodiments, the substrate is a film or a release liner (e.g., PET). In this embodiment, the article can be a transfer belt or a transfer film.

[0143] Due to the low Dk value, the composition is suitable for use as a structural adhesive, an insulating layer, or a protective layer, including sealants for electronic telecommunication articles (such as printed circuit boards, integrated circuits, antennas, and optical cables).

[0144] Abrasive articles generally comprise a plurality of abrasive grains and a binder. Many different types of abrasive articles are available. Among them are: (1) coated abrasive articles, where an adhesive primer coating bonds the abrasive grains to a backing material (e.g., "sandpaper"); (2) buffed coated abrasive articles, where the abrasive grains are dispersed in a binder to form an abrasive composite, which is bonded to a backing to form an abrasive article; (3) three-dimensionally shaped composite abrasive articles, where the abrasive grains are dispersed in a binder to form a plurality of abrasive composites, which are bonded to a backing to form an abrasive article; (4) bonded abrasive articles, where the binder bonds the grains together to form a shaped mass, such as a grinding wheel or a brush; and (5) non-woven abrasive articles, where the binder bonds the abrasive grains to the fibers of a non-woven fibrous substrate in the form of a primer coating or a dispersion. A variety of abrasive article backing substrates can be used, such as cloth, film, foil, paper, fibrous materials, polymeric films, etc.

[0145] Method for manufacturing an article

[0146] The present invention describes a method for manufacturing an article, which method comprises

[0147] A) applying the composition as described herein to a substrate; B) polymerizing the cyclic olefin; and

[0148] C) curing the second polymerizable material.

[0149] Compositions (such as compositions of articles and methods) are typically polymerized / cured in two separate steps. In one step, when the composition is heated and / or allowed to stand at room temperature, the cyclic olefin is at least partially polymerized / cured via ROMP. In another step, the second polymerizable material may be polymerized via free radical polymerization (in the case of (meth)acrylic components). In the case of epoxy components, the second polymerizable material may be polymerized via cationic polymerization. In some embodiments, the composition is irradiated with external UV light sufficient to activate the free radical photoinitiator and / or photoacid generator.

[0150] The heat source for the heating step can be an oven, a flame, a hot plate, or any other heat source. The heating step can be carried out at at least 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, or 120 °C. The heating step can last for at least 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 10 minutes, 30 minutes, 60 minutes, or 120 minutes. The light source for the irradiation step can be a photochemical light source (e.g., at least one of a blue light source or a UV light source). There are two types of UV light sources: 1) a light source with relatively low light intensity such as a black light source, which provides a light intensity of generally 10 mW / cm2 or lower in the wavelength range of 280 nm to 400 nm (measured according to procedures recognized by the National Institute of Standards and Technology of the United States, e.g., measured with a Uvimap TM UM 365L-S radiometer manufactured by Electronic Instrumentation & Technology, Inc., Sterling, VA, USA), and 2) a light source with relatively high light intensity such as a medium-pressure mercury lamp, which provides a light intensity of generally higher than 10 mW / cm2, preferably in the range of 15 mW / cm2 to 450 mW / cm2. The irradiation step can last for at least 5 seconds, 10 seconds, 15 seconds, 30 seconds, or 60 seconds; or at least 2 minutes, 3 minutes, 4 minutes, 5 minutes, 10 minutes, or 30 minutes.

[0151] The compositions described herein can be cured via a variety of methods. In some embodiments, step B is carried out before step A. In other embodiments, step A is carried out before step B. In some embodiments, the curing method includes first subjecting the composition to a heating step, followed by an irradiation step. In other embodiments, the curing method includes first subjecting the composition to an irradiation step, followed by a heating step. In other embodiments, the curing method includes subjecting the composition to both a heating and an irradiation step simultaneously. In other embodiments, the curing method includes allowing the composition to stand for a period of time under ambient conditions (which serves as a "heating step" using only ambient heat), followed by subjecting the composition to an irradiation step.

[0152] The articles described herein can be reaction products of compositions that have undergone any of the above curing methods. The articles described herein can also be compositions that do not undergo the steps of the above curing method or undergo some of the steps of the above curing method. In some embodiments, (e.g., structural adhesive tapes or transfer tapes) the articles comprise reaction products of compositions in which the cyclic olefin or the second polymerizable material is at least partially cured. The term "partially cured" means that some of the reactive polymerizable groups (e.g., cyclic olefins, (meth)acrylates, epoxides) in the composition have polymerized, while some have not.

[0153] In some embodiments, a film or release liner is provided that comprises a layer of the composition described herein, wherein the cyclic olefin is at least partially cured and the second polymerizable material is uncured. In another embodiment, a film or release liner is provided that comprises a layer of the composition described herein, wherein the cyclic olefin is uncured and the second polymerizable material is at least partially cured.

[0154] When both the cyclic olefin and the second polymerizable material are fully cured, the cured composition is generally a hard solid. In some embodiments, the Shore A hardness is greater than 30, 40, or 50, and can be in a range up to 75, 80, 85, or greater. The Shore A hardness of the partially cured composition can be less than 30 or 25, and is generally at least 5, 10, or 15.

[0155] The advantages and embodiments of the present disclosure are further illustrated by the following examples, but the specific materials and their amounts, as well as other conditions and details set forth in these examples, should not be construed as undue limitations on the present invention. Unless otherwise specified, in these examples, all percentages, ratios, and proportions are by weight.

[0156] Examples

[0157] Unless otherwise stated, all parts, percentages, ratios, etc. in the examples and the remainder of this specification are by weight. Unless otherwise indicated, all other reagents are obtained from or purchased from fine chemical suppliers, such as MilliporeSigma (Burlington, MA, USA), or can be synthesized by known methods. Table 1 (below) lists the materials used in the examples and their sources.

[0158] Table 1. Material list

[0159]

[0160]

[0161] Test methods

[0162] Hardness

[0163] A Shore hardness tester (Model #408, obtained from PTC Instruments, Los Angeles, CA, USA) was used to measure the hardness of the cured material. The tester has a conical tip with a 35-degree angle and a force of 821 grams-force. The result is the average of 3 readings, and the procedure is in accordance with ASTM D2240.

[0164] Dielectric properties

[0165] The dielectric properties were measured at 23 °C and 35% relative humidity. The sample size was: 30 mm × 50 mm, with a maximum thickness of 0.85 mm. At each frequency, all split-post dielectric resonator measurements were performed in accordance with the standard IEC 61189-2-721. Each material was inserted between two fixed dielectric resonators. The resonant frequency and quality factor of the post are affected by the presence of the sample, and this enables the direct calculation of the complex dielectric constant (dielectric constant and dielectric loss). The geometry of the split dielectric resonator fixture used in our measurements was designed by Company QWED (Warsaw, Poland). These resonators operate in the TE01d mode with only an azimuthal electric field component, such that the electric field remains continuous at the dielectric interface. The split-post dielectric resonator measures the dielectric constant component in the plane of the sample. Ring coupling (critical coupling) was used in each of these dielectric resonator measurements. This split-post resonator measurement system was combined with a Keysight VNA (Vector Network Analyzer Model PNA N5222B and Millimeter Wave Test Set Model N5292A, 900 Hz - 110 GHz). Calculations were performed using the commercial analysis split-post resonator software from QWED to provide a powerful measurement tool for determining the complex dielectric constant of each sample at a specific frequency. The error analysis was from QWED. The eps' error was calculated by the equation (+ / -(0.0015 + Δh / h)*ε); the loss tangent error was 3% of the measured loss tangent value.

[0166] Rheological properties

[0167] A rheometer of model DHR-3 (TA Instruments, New Castle, DE, USA) was used to measure the complex viscosity. This rheometer was equipped with a Peltier plate temperature control attachment and a 25-mm geometry (TA Instruments SMART SWAP fixture), and had no solvent trap. All of the above products were available from TA Instruments (New Castle, DE, USA). The same rheometer with a Peltier plate assembly was used to measure the complex viscosity. Measurements were performed at room temperature using a frequency sweep mode (frequency range).

[0168] Examples EX-1 to EX-7: ROMP-acrylate interpenetrating network

[0169] In a 20-mL screw-capped glass vial, the components shown in Table 2 were combined and shaken until the solids dissolved.

[0170] Table 2. Compositions of EX-1 to EX-7

[0171]

[0172] Each of the compositions in Table 2 was irradiated in its vial by placing the vial in the chamber of a 36-watt UV nail lamp (NailStar Professional, London, England) and turning on the lamp for 30 seconds (s). After this irradiation step, the appearance of the composition was recorded (see Table 3 below). After irradiation, EX-1, EX-2, and EX-3 were placed in an oven at 120 °C for 20 minutes. The appearance of these compositions was also recorded in Table 3.

[0173] Table 3. Curing research results of EX-1 to EX-7

[0174] Examples Appearance after irradiation Appearance after irradiation + heating EX-1 Soft gel Soft gel EX-2 Liquid Soft gel EX-3 Soft gel Hard solid EX-4 Liquid - EX-5 Soft gel - EX-6 Soft gel - EX-7 Soft gel -

[0175] * EX-4 to EX-7 are intermediate compositions as they do not contain a ROMP catalyst (e.g., CT762). However, their curing behavior (see Table 3) indicates that the compositions require a minimum concentration of acrylate monomer (e.g., SR833S) to form a solid upon ultraviolet (UV) irradiation. If these examples contained a similar amount of ROMP catalyst, they would be expected to behave similarly to EX-3 upon heating (i.e., further curing / hardening).

[0176] Examples EX-8 to EX-9: ROMP-acrylate interpenetrating network

[0177] Stock solution 1 was prepared by mixing 97 parts by weight (pbw) of HPR2029, 1 pbw of CT762, and 2 pbw of STM in a polypropylene high-speed mixing cup and mixing at 3500 revolutions per minute (rpm) for 15 s in a high-shear mixer (SpeedMixer DAC 150.1FVZ-k, Hauschild & Co. KG, Hamm, Germany).

[0178] Stock solution 2 was prepared by mixing 96 pbw of SR368D, 1 pbw of TPO-L, and 3 pbw of A-174 in a rapid mixing cup and mixing at 3500 rpm for 15 s.

[0179] Stock solution 3 was prepared by combining 30 pbw of stock solution 1 and 70 pbw of stock solution 2 in a rapid mixing cup and mixing at 3500 rpm for 15 s.

[0180] Stock solution 4 was prepared by combining 70 pbw of stock solution 1 and 30 pbw of stock solution 2 in a rapid mixing cup and mixing at 3500 rpm for 15 s.

[0181] EX-8 was prepared by combining 55 pbw of stock solution 3 with 45 pbw of 3MDA in a rapid mixing cup and mixing at 3500 rpm for 15 s.

[0182] EX-9 was prepared by combining 55 pbw of stock solution 4 with 45 pbw of 3MDA in a rapid mixing cup and mixing at 3500 rpm for 15 s.

[0183] The overall compositions of EX-8 to EX-9 are shown in Table 4.

[0184] Table 4. Compositions of EX-8 and EX-9

[0185]

[0186] EX-8 and EX-9 become slurries directly after mixing. Each slurry is coated onto a micro-replicated polypropylene tool (as described in column 19, lines 19-24 of US6923840). An 8 mil (0.2 mm) ESTANE 58887 polyurethane backing film (Lubrizol, Brecksville, OH, USA) is added to cover the slurry in the tool. A tongue depressor is used to spread the slurry under the polyurethane backing to remove excess resin. The sandwich is then placed between two glass plates and irradiated with UV by exposing it twice at a speed of 20 feet per minute (0.1 m / s) from a FUSION LIGHT HAMMER 10 (Heraeus Noblelight America, Gaithersburg, MD, USA) equipped with a D lamp set to 100% intensity. The sandwich structure is disassembled and the EX-8 and EX-9 materials are inspected. The EX-8 material can be easily removed as a freestanding film with a micro-replicated structure on its surface. The EX-9 material is not easily separated from the polypropylene tool due to some uncured liquid monomers remaining.

[0187] Examples EX-10 to EX-13: ROMP-epoxide interpenetrating network

[0188] The compositions shown in Table 5 are combined in a glass jar and manually mixed with a tongue depressor. In each case, two premixes are made in a glass jar and manually mixed (each dissolving the catalyst in one resin component), then combined and similarly mixed to obtain the example compositions.

[0189] EX-10 is manufactured by combining all of premix 10A and premix 10B.

[0190] EX-11 is manufactured by combining all of premix 11A and premix 11B.

[0191] EX-12 is manufactured by combining 4 g of premix 12A with 6 g of premix 12B.

[0192] EX-13 is manufactured by combining 8 g of premix 13A with 12 g of premix 13B.

[0193] The final overall composition is shown in Table 5.

[0194] Table 5. Compositions of EX-10 to EX-13

[0195]

[0196] In all of the following examples, UV irradiation was carried out using a BLK-Ray model XX-15L lamp (UVP, San Gabriel, CA, USA) at 150 V, 60 Hz, 0.68 A. The bulb in the lamp was a 350 nm black light bulb F15T8 / BLB 15 W (OSRAM Sylvania, Wilmington, MA, USA). The light source was placed at a distance of 1 inch (2.54 cm) from the sample composition.

[0197] Approximately 3 grams of each of EX-10 and EX-11, freshly prepared, were deposited separately on silicone-treated polyethylene terephthalate (PET) release liners. These samples were irradiated for 1 hour, after which there was neither gelling nor curing. The samples were then heated in an oven at 80 °C for 16 h, after which EX-10 had hardened into a uniform solid and EX-11 had become a white solid with a liquid on top. Separately, an approximately 3 gram sample of EX-10 was left standing at room temperature for 5 days, after which it was irradiated for 5 minutes. This treatment produced a hard, uniform solid.

[0198] Approximately 1 gram of premix 12A was deposited on a PET release liner and irradiated for 30 minutes, after which it had become a viscous liquid. The viscous liquid was heated in an oven at 80 °C for 1 hour, after which it was a hard solid. Separately, two approximately 3 gram samples of EX-12 were placed on PET release liners. The first of these was irradiated for 30 minutes and then heated in an oven at 80 °C for 2 hours, after which it was a white solid with a Shore A hardness of 72. The second of these was heated in an oven at 80 °C for 30 minutes and then irradiated for 15 minutes, after which it was a brown solid with dark spots and a measured Shore A hardness of 24.

[0199] Approximately half of EX-13 was placed between glass slides using 0.4 mm thick polytetrafluoroethylene (PTFE) spacers. The other half of EX-13 was deposited on a PET release liner. The two halves were heated in an oven at 80 °C for 1 hour and then irradiated for 15 minutes. The sample between the glass slides was flipped and irradiated for another 15 minutes on the other side (total irradiation 30 minutes). The measurement of the dielectric properties of the sample cured between the glass slides was carried out according to the general procedure. Separately, another batch of EX-13 was manufactured according to the component amounts in Table 5 and divided into several parts in small aluminum trays. One portion of such EX-13 was heated in an oven at 80 °C for 30 minutes and then irradiated for 15 minutes. Another portion of such EX-13 was irradiated for 15 minutes and then heated in an oven at 80 °C for 30 minutes. A third portion of such EX-13 was heated on a hot plate at 80 °C for 15 minutes while being irradiated for the same time. Separately, small portions (about 0.1 g) of premix 13A and premix 13B were placed in aluminum trays. A small portion of premix 13A was irradiated for 30 minutes. A small portion of premix 13B was irradiated for 30 minutes and then heated in an oven at 80 °C for 30 minutes.

[0200] The curing conditions, measured hardness, and measured dielectric properties of all parts of EX-10 to EX-13 (and related premixes) are shown in Table 6. After all steps of the processing and curing conditions were completed, hardness and dielectric measurements were carried out.

[0201] Table 6. Curing conditions and results of EX-10 to EX-13

[0202]

[0203]

[0204] Table 7. Rheological measurements

[0205]

Claims

1. An article, the article comprising a composition disposed on a substrate, wherein the composition comprises: i) a cyclic olefin; ii) a ring-opening metathesis polymerization catalyst; iii) a second polymerizable material selected from the group consisting of: a) an epoxide-containing component; and b) a (meth)acrylate monomer comprising an alicyclic or heteroalicyclic group; iv) an initiator for the second polymerizable material; wherein based on the total amount of i) and iii), the composition comprises greater than 25 wt% of i) and greater than 25 wt% of at least one of a) or b); and wherein the cyclic olefin and / or the second polymerizable material is at least partially cured.

2. The article according to claim 1, wherein iv) is selected such that the second polymerizable material cures under curing conditions different from those of the cyclic olefin.

3. The article according to claim 2, wherein iv) is a photoacid generator or a free radical photoinitiator.

4. The article according to claims 1 to 2, wherein a) has a Tg of less than 25 °C, 0 °C or -25 °C.

5. The article according to claim 4, wherein a) comprises polybutadiene.

6. The article according to claims 4 to 5, wherein the composition comprises a hydroxyl group-containing moiety.

7. The article according to claims 4 to 6, wherein a) further comprises an ethylenically unsaturated moiety.

8. The article according to claims 1 to 6, wherein b) has a Tg of greater than 25 °C, 50 °C, 75 °C, 100 °C, 125 °C, 150 °C, 175 °C.

9. The article according to claims 1 to 8, wherein b) comprises an isocyanate group.

10. The article according to claims 1 to 9, wherein b) comprises a cyclic group having greater than 6 carbon atoms.

11. The article according to claims 1 to 10, wherein b) comprises at least three (meth)acrylate groups.

12. The article according to claims 1 to 11, wherein the composition further comprises an inorganic filler.

13. The article according to claims 1 to 12, wherein the reaction product of i) and ii) is an interpenetrating network.

14. The article according to claims 1 to 13, wherein the cyclic olefin is at least partially cured and the second polymerizable material is uncured.

15. The article according to claims 1 to 13, wherein the cyclic olefin is uncured and the second polymerizable material is at least partially cured.

16. The article according to claims 14 to 15, wherein the substrate is a film or a release liner.

17. The article according to claims 1 to 16, wherein both the cyclic olefin and the second polymerizable material are cured.

18. The article according to claim 17, wherein the article is an electronic article.

19. The article according to claim 17, wherein the article is an abrasive article.

20. A method of manufacturing an article, the method comprising: A) applying a composition to a substrate, wherein the composition comprises i) a cyclic olefin; ii) a ring-opening metathesis polymerization catalyst; iii) A second polymerizable material selected from the group consisting of: a) an epoxy-containing component; and b) a (meth)acrylate monomer containing an alicyclic or heteroalicyclic group; iv) an initiator for the second polymerizable material; wherein, based on the total amount of i) and iii), the composition comprises more than 25% by weight of i) and at least one of more than 25% by weight of a) or b); B) polymerizing the cyclic olefin; and C) curing the second polymerizable material.

21. The method according to claim 20, wherein the method comprises polymerizing the cyclic olefin before curing the second polymerizable material.

22. The method according to claim 20, wherein the method comprises curing the second polymerizable material before polymerizing the cyclic olefin.

23. The method according to claims 20 to 22, wherein the method comprises curing the second polymerizable material by exposing the composition to actinic (e.g., ultraviolet) radiation.

24. The method according to claims 20 to 23, further comprising contacting the composition with a second substrate before curing.

25. The method or the polymerizable composition according to claims 20 to 24, wherein the composition or the article is further characterized by claims 2 to 19.

26. A polymerizable composition comprising: i) a cyclic olefin; ii) a ring-opening metathesis polymerization catalyst; iii) a second polymerizable material selected from the group consisting of: a) an epoxy monomer; and b) a (meth)acrylate monomer containing an alicyclic or heteroalicyclic group; iv) an initiator for the second polymerizable material; wherein the composition comprises more than 25% by weight of i) and at least one of more than 25% by weight of a) or b), and the total amount of i) and iii) is at least 60% by weight of the total composition.

27. A polymerizable composition comprising: i) a cyclic olefin; ii) a ring-opening metathesis polymerization catalyst; iii) a second polymerizable material selected from the group consisting of: a) an epoxy-containing component; and b) a (meth)acrylate monomer containing a heteroalicyclic group; iv) an initiator for the second polymerizable material; wherein, based on the total amount of i) and iii), the composition comprises more than 25% by weight of i) and at least one of more than 25% by weight of a) or b).

28. The polymerizable composition according to claims 26 to 27, wherein the polymerizable composition is further characterized by claims 1 to 15.

29. The method or the polymerizable composition according to claims 20 to 28, wherein the ratio of the first complex viscosity of the mixture of the cyclic olefin and the second polymerizable material at 0.1 rad / sec to the complex viscosity at 200 rad / sec is at least 2, 3 or 4.

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