Free-radically polymerizable compound, composition including the free-radically polymerizable compound, polymerized compound, method of making the polymerized compound and article including the polymerized compound

Abstract

To provide UV-curable polysiloxane-based materials that can provide good wetting of a release-treated nanostructured film and adhesion to an oxide coated substrate.SOLUTION: Free-radically polymerizable compounds having a poly(diakylsiloxane) segment and at least one acryl group are disclosed. Compositions including the free-radically polymerizable compounds, polymerized compounds, methods of making the polymerized compounds, and articles including the polymerized compounds are also disclosed.SELECTED DRAWING: Figure 1

Description

[Background technology]

[0001] "Metasurfaces" are nanopatterned two-dimensional surfaces that can be used to create conventional optical components such as gratings, lenses, mirrors, holograms, wave plates, polarizers, and spectral filters. These materials can be fabricated by a variety of methods, including, for example, electron beam lithography. However, there remains a need for continuous, high-throughput methods for creating patterned nanostructures.

[0002] One continuous roll-to-roll manufacturing method uses nanostructured films as patterned etch masks. Patterned etch masks can be created by coating a precisely controlled thickness of ultraviolet electromagnetic radiation (UV) curable acrylic material into the recesses of a release-treated nanostructured film so that the UV-curable material protrudes slightly above the tooling features (e.g., often 50-200 nanometers above the surface). The resulting coated tooling film is then laminated to a silicone-containing oxide surface, cured by UV exposure to UV radiation, and separated to transfer the structures from the release-treated nanostructured film onto the oxide-coated film. Subsequent processing of this structured film can yield useful metasurfaces. Summary of the Invention

[0003] One challenge associated with the above process is to provide a suitable UV-curable formulation that: 1) can wet out onto the release-treated nanostructured film during coating, and 2) can migrate to the oxide surface upon curing and stripping.

[0004] The present disclosure provides UV-curable polysiloxane-based materials that can provide good wetting and adhesion of release-treated nanostructured films to oxide-coated substrates.

[0005] In one aspect, the present disclosure provides a compound of the formula: [ka] [In the formula, R i is C1 to C with a valence of m+n 60 is an organic group; Each PDMS independently represents a monovalent group having a poly(dialkylsiloxane) segment; each Q is independently a covalent bond or an organic linking group having a valence of at least two; Each X is independently O, S, or NR 1 and each R 1 are independently H or a C1-C4 alkyl group; m and n are independently integers greater than or equal to 1; Each Z is independently [ka] (In the formula, R 2 is -S- or N(R 6 )- and R 6 is H, a C1-C4 alkyl group, or -R 3 Si(L) b (R 4 ) 3-b and; R 3 is a divalent alkylene group optionally substituted with one or more catenary oxygen atoms; R 4 is a monovalent non-hydrolyzable group; R 5 is H or methyl; each L is independently a monovalent hydrolyzable group; each b is independently 1, 2, or 3; a and p are independently integers greater than or equal to 0, and 1≦(a+p)≦6; a=1 for at least one Z; and p=1 for at least one Z. represents] The present invention provides a free radical polymerizable compound represented by the formula:

[0006] In another aspect, the present disclosure provides a method for producing a pharmaceutical composition comprising: i) a urethane compound comprising a poly(dialkylsiloxane) segment and at least two (meth)acrylic groups; ii) an organosilane compound containing a hydrolyzable group and a group selected from an amino group or a mercapto group; A free radical polymerizable reaction product of components comprising: A reaction product is provided in which the equivalent ratio of components i) to ii) is greater than 1, such that the (meth)acrylic groups remain unreacted.

[0007] In another aspect, the present disclosure provides a compound of the formula: [ka] wherein each Z independently represents: [ka] (In the formula, R 5 is H or methyl; and for at least one Z, p is at least 2).

[0008] In another aspect, the present disclosure provides a method for producing a pharmaceutical composition comprising: i) a compound containing at least two isocyanate groups; ii) a compound comprising a poly(dialkylsiloxane) segment and an isocyanate-reactive group; iii) a compound comprising an isocyanate-reactive group and at least two (meth)acrylate groups; and (b) providing a free radically polymerizable reaction product of components comprising:

[0009] In yet another aspect, the present disclosure provides a method of making a polymerized composition, comprising: providing a polymerizable composition comprising at least one free-radically polymerizable compound according to the present disclosure; free-radical polymerizing the polymerizable composition to provide a polymerized composition; The present invention provides a method comprising:

[0010] In yet another aspect, the present disclosure provides a method of making an article, comprising: a) placing a layer of a free radically polymerizable composition according to the present disclosure onto a mold surface of a first substrate, the mold surface having a pattern comprising nanostructures; b) contacting a layer of a free-radically polymerizable composition with a metal oxide surface of a second substrate; c) free-radically polymerizing at least a portion of the free-radically polymerizable composition to provide a polymerized composition; d) separating the polymerized composition from the mold surface; The present invention provides a method comprising:

[0011] In yet another aspect, the present disclosure provides an article comprising a polymerized reaction product disposed on a surface of a substrate produced according to the present method.

[0012] As used herein, The term "actinic radiation" refers to electromagnetic radiation in the wavelength range of 200-720 nm that is absorbed by molecules, thereby directly or indirectly forming free radicals.

[0013] The term "catenary" in reference to an atom means positioned within the longest continuous chain of atoms of a group or molecule.

[0014] Chemical group abbreviations "C f ~C g " means containing f to g carbon atoms.

[0015] The term "effective amount of actinic radiation" refers to sufficient actinic radiation to effect free radical polymerization.

[0016] The prefix "(meth)acrylic" refers to "acrylic" and / or "methacrylic".

[0017] The term "residue of a polyisocyanate" refers to the polyvalent portion of a polyisocyanate remaining after removal of its -N=C=O groups.

[0018] The term "urethane compound" refers to formula [ka] refers to any organic compound containing at least one divalent group represented by

[0019] The features and advantages of the present disclosure will be further understood by consideration of the detailed description and the appended claims. [Brief explanation of the drawings]

[0020] [Figure 1] 1 is a schematic side view of an exemplary article 100 according to one embodiment of the present disclosure.

[0021] It is to be understood that numerous other modifications and embodiments can be devised by those skilled in the art which fall within the scope and spirit of the principles of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0022] Described herein are free-radically polymerizable compounds that include at least one polysiloxane group, at least one silyl group having a hydrolyzable substituent, and at least one (meth)acrylic group.

[0023] In many embodiments, the free radically polymerizable compound can be represented by Formula I: [ka]

[0024] R i is C1 to C with a valence of m+n 60In some embodiments, R i has 1 to 50 carbon atoms, 1 to 40 carbon atoms, 1 to 30 carbon atoms, 1 to 20 carbon atoms, or 1 to 10 carbon atoms. One convenient method for preparing a free-radically polymerizable compound from the respective polyisocyanate is to prepare a free-radically polymerizable compound from R i often corresponds to the residue of a polyisocyanate. In many embodiments, R i is optionally composed of C, H, and N, O, and / or S atoms, while R i There are no additional restrictions on the structure or composition of (although this is not a requirement). i The groups may be residues of polyisocyanates, including diisocyanates, triisocyanates, and diisocyanate oligomerization products.

[0025] For example, Desmodur N100 has the nominal structure: [ka] and therefore its nominal residue is: is. [ka]

[0026] Numerous aliphatic or aromatic polyisocyanates can be used in preparing polymerizable compositions according to the present disclosure. Suitable polyisocyanates include diisocyanates having two -NCO groups and polyisocyanates having three or more -NCO groups. Polyisocyanates can be produced by known methods and / or obtained from commercial sources. Exemplary commercially available polyisocyanates include Desmodur 3300, Desmodur TPLS 2294, Desmodur N 3600, and Desmodur N 100 (all available from Covestro, Leverkusen, Germany). Available as (manufactured by) AG; 2,4- and 2,6-tolylene diisocyanate; methylene diisocyanate; ethylene diisocyanate; propylene diisocyanate; butylene diisocyanate; hexamethylene diisocyanate; octamethylene diisocyanate; decamethylene diisocyanate; cyclohexylene diisocyanate; o-, m-, and p-methylene diphenyl diisocyanate; naphthalene diisocyanate; polymethylene bis(phenyl isocyanate); 3,5,3',5'-bixylylene-4,4'-diisocyanate bis(2-isocyanatoethyl) ether; bis(2-isocyanatoethyl) ether of ethylene glycol; o-, m-, and p-phenylene diisocyanate; 3,3'-bitrylene-4,4'-diisocyanate; diphenyl ether 4,4'-diisocyanate; 3,5,5',5'-bixylylene-4,4'-diisocyanate; diphenylmethane-4,4'-diisocyanate; biphenylene diisocyanate; and 3,3'-dimethoxybiphenylene-4,4'-diisocyanate, and naphthalene diisocyanate.

[0027] Oligomers are often present in commercially available polyisocyanates depending on the method used to make them. For example, some representative hexamethylene diisocyanate (HDI) oligomers are shown below: [ka] and [ka]

[0028] When present, the concentration of such oligomers is often less than 40 weight percent, less than 35 weight percent, less than 30 weight percent, less than 25 weight percent, less than 20 weight percent, less than 15 weight percent, less than 10 weight percent, or even less than 5 weight percent. Taking into account the inclusion of oligomers, the number of isocyanato (—NCO) groups is often reported as an average value, particularly for commercially available polyisocyanates. For example, when a polyisocyanate is characterized as a triisocyanate, the average —NCO functionality is often a non-integer greater than 3, even though the majority of polyisocyanate bulk composition materials are triisocyanates. For example, Desmodur 3300 is described as having a functionality of >3.2.

[0029] Referring again to Formula I, each PDMS independently represents a monovalent group having a poly(dialkylsiloxane) segment.

[0030] In many embodiments, useful PDMS groups have the formula: [ka] [In the formula, Each R 7 represents a hydrocarbyl group having 1 to 8 carbon atoms (e.g., methyl, ethyl, propyl, butyl, phenyl, hexyl, octyl); Each w represents an integer of 5 or greater (e.g., 5 to 20, 5 to 50, or 5 to 100). It can be described by:

[0031] The PDMS group (e.g., segment) may have a molecular weight (Mn) of at least 500, 750, or 1000 g / mol. The PDMS group typically has a molecular weight (Mn) of 10,000 or 5,000 g / mol or less. In some embodiments, the PDMS group has a molecular weight (Mn) of less than 5000, 4500, or 3000 g / mol. For example, when a 0.35 equivalent compound prepared from PDMS with a molecular weight of 5000 or 4700 g / mol is used in the absence of an aminosilane compound, the wettability and transferability may be insufficient. However, compounds with insufficient wettability and transferability are expected to be suitable for other applications, such as release layers for adhesive tapes.

[0032] Referring again to Formula I, each Q is independently a covalent bond or an organic linking group having a valence of at least 2 (e.g., at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, or even at least 10).

[0033] Q can be a straight or branched chain and / or ring-containing linking group. In some embodiments, Q can be an alkylene, arylene, aralkylene, or alkarylene. Q can optionally contain one or more heteroatoms (e.g., catenary heteroatoms) such as O, N, S, and combinations thereof. Q can also optionally contain one or more heteroatom-containing divalent functional groups such as, for example, carbonyl, sulfonyl, or combinations thereof. In many embodiments, Q has 0 to 20 carbon atoms (often 2 to 12 carbon atoms or 2 to 6 carbon atoms), although this is not a requirement. Exemplary Q groups include a covalent bond, methylene, ethane-1,2-diyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, cyclohexane-1,4-diyl, octane-1,8-diyl, dodecane-1,12-diyl, hexadecane-1,16-diyl, eicosane-1,20-diyl, -CHC(=O)CH-, -CHCHOCHCH-, and -OCHCHOCHCHOCHCH-.

[0034] Referring again to Formula I, each X is independently O, S, or NR 1 and each R 1 are independently H or a C1-C4 alkyl group. Examples of C1-C4 alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, and isobutyl.

[0035] In some embodiments, each Q adjacent to the PDMS is propane-1,3-diyl and the X to which the Q is attached is NH. In some embodiments, proceeding from left to right in Formula I, each Q adjacent to the PDMS is -CHCHCHOCHCH- and the X to which the Q is attached is O.

[0036] The subscripts m and n are independently integers greater than or equal to 1 (i.e., at least 1). In many embodiments, the total number of (m+n) is 10 or less, and in some embodiments, (m+n) is 6 or less, although this is not a requirement. Examples of m include 1, 2, 3, 4, 5, 6, 7, 8, and 9. Of these, m=1, 2, 3, 4, or 5 is often used, with m=1, 2, or 3 often being preferred. Examples of n include 1, 2, 3, 4, 5, 6, 7, 8, and 9. Of these, n=1, 2, 3, 4, or 5 is often used, with n=1, 2, or 3 often being preferred.

[0037] In some embodiments, 2≦(m+n)≦10, although (m+n) can be greater than 10. In some embodiments, 2≦(m+n)≦6 or 2≦(m+n)≦3. In some embodiments, m=1, n=1, and the average value of a and p per Z group is each at least 1. In some embodiments, m=1, n=2, and the average value of a and p per Z group is each at least 1. In some embodiments, m=1, n=2, and a=0 and p=1 for at least one Z, and a=1 and p=0 for at least one other Z. In some embodiments, 4≦(m+n)≦10, 3≦n≦9, and a=0 and p=1 for at least one Z, and a=1 and p=0 for at least one other Z.

[0038] Referring again to Formula 1, in some embodiments, each Z is independently: [ka]

[0039] Each R 2 are independently -S- or -N(R 6 )

[0040] Each R 3 are independently divalent alkylene groups optionally substituted with one or more catenary oxygen atoms.3 R may have 1 to 4, 1 to 6, 1 to 8, 1 to 12, or 1 to 20 carbon atoms, although this is not a requirement. 3 Examples of R include methylene, ethane-1,2-diyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, cyclohexane-1,4-diyl, octane-1,8-diyl, dodecane-1,12-diyl, hexadecane-1,16-diyl, eicosane-1,20-diyl, -CHC(=O)CH-, -CHCHOCHCH-, and -OCHCHOCHCHOCHCH-. 3 is often -CH2CH2-, -CH2CH2CH2-, or -CH2CH2CH2CH2-.

[0041] Each R 4 are independently monovalent non-hydrolyzable groups. Generally, any group attached to a silicon atom by a C—Si bond is not a hydrolyzable group.

[0042] Each R 5 is independently H or methyl.

[0043] Each R 6 are independently H, a C1-C4 alkyl group (e.g., methyl, ethyl, propyl, or butyl), or -R 3 Si(L) b (R 4 ) 3-b is.

[0044] Each L is independently a monovalent hydrolyzable group. Generally, any monovalent group attached to a silicon atom by a bond to a heteroatom (e.g., O, N, S, Cl, Br) is a hydrolyzable group. Exemplary hydrolyzable groups include C1-C6 alkoxy groups (e.g., methoxy, ethoxy, propoxy, or butoxy) and C1-C6 alkylcarbonyloxy groups (e.g., acetoxy or CH3CH2C(=O)O-). Methoxy and ethoxy are often preferred.

[0045] Each b is independently 1, 2, or 3. Often, b is 3.

[0046] Each a and p is independently an integer greater than or equal to 0. The total number of (a+p) is greater than or equal to 1 and less than or equal to 6. For at least one Z (e.g., Z'), a=1. Also, for at least one Z (which may be the same as or different from Z'), p=1.

[0047] Referring again to Formula 1, in other embodiments, each Z is independently: [ka] [In the formula, R 5 is H or methyl; For at least one Z, p is at least 2.

[0048] In this embodiment, the compound may include at least two Z groups. In some embodiments, p is 6, 5, 4, or 3 or less.

[0049] The compounds described herein can be prepared, for example, by the addition of substituents (e.g., alcohols, primary or secondary amines, and / or thiols) to polyisocyanates, following overall synthesis methods known in the art. In some cases, a catalyst, such as dibutyltin dilaurate or 1,4-diazabicyclo[2.2.2]octane (DABCO), may facilitate the addition reaction. Generally, the reactants can be mixed, optionally with a solvent. When a homogeneous mixture or solution is obtained, a catalyst is optionally added, and the reaction mixture is heated at a temperature for a time sufficient for the reaction to occur.

[0050] For example, the polyisocyanates described above may have reactive end groups (e.g., —OH, —NH(R 6Such polysiloxanes can be produced by known methods, and many are commercially available. Examples include monocarbinol-terminated polydimethylsiloxanes available under the tradenames MCR-C12, MCR-C18, and MCR-C22, and monoaminopropyl-terminated polydimethylsiloxanes available under the tradenames MCR-A11 and MCR-A12, all from Gelest Inc. (Morrisville, Pennsylvania); monohydroxy-terminated polydimethylsiloxanes X-22-170BX and X-22-170DX, having an average Mn of about 2800 and about 4670 g / mol, respectively, from Shin-Etsu (Akron, Ohio); monohydroxy-terminated silicone fluid VE-208 from Guangzhou VanEyck New Material Co., Ltd. (Guangzhou, China); and Andisil MOH 100, Andisil MOH 10000, and Andisil MOH 10000 from AB Specialty Silicones (Waukegan, Illinois). Examples include monofunctional silanol polymers available under the tradename MOH 50000.

[0051] Similarly, a hydroxy-functional (meth)acrylate compound (generally a monohydroxy-functional (meth)acrylate compound) can be reacted with the remaining isocyanate group to produce a free-radically polymerizable intermediate compound containing PDMS segments and (meth)acrylic functionality, but without silyl groups with hydrolyzable substituents.

[0052] Exemplary hydroxy-functional multi(meth)acrylates include glycerol di(meth)acrylate (all isomers), pentaerythritol tri(meth)acrylate, trimethylolethane dimethacrylate, trimethylolethane diacrylate, and (meth)acrylic acid adducts with glycidyl (meth)acrylate.

[0053] When n≧3, hydroxy-functional mono(meth)acrylates can be used as well. Examples include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate (all isomers), hydroxybutyl (meth)acrylate (all isomers), poly(ε-caprolactone) mono[2-methacryloxyethyl]ester, glycerol dimethacrylate, 1-(acryloxy)-3-(methacryloxy)-2-propanol, 2-hydroxy-3-phenyloxypropyl methacrylate, 2-hydroxyalkyl methacryloyl phosphate, 4-hydroxycyclohexyl methacrylate, trime Examples of suitable methacrylates include ethylolpropane dimethacrylate, trimethylolethane dimethacrylate, 1,4-butanediol monomethacrylate, neopentyl glycol monomethacrylate, 1,6-hexanediol monomethacrylate, 3-chloro-2-hydroxypropyl methacrylate, 2-hydroxy-3-alkyloxy methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, ethylene oxide-modified phthalic acid methacrylate, and 4-hydroxycyclohexyl methacrylate.

[0054] In some embodiments, a mixture of a hydroxy-functional multi(meth)acrylate and a hydroxy-functional mono(meth)acrylate may be utilized.

[0055] Among the hydroxy-functional (meth)acrylates, some acrylate functionality is typically required.

[0056] Addition to an isocyanato group on an intermediate compound can be carried out, for example, using a suitable catalyst (eg, a tin catalyst such as dibutyltin dilaurate) with heating as described above.

[0057] Thus, a free-radically polymerizable compound comprising at least one (e.g., terminal) poly(dialkylsiloxane) segment and at least two (meth)acrylic groups is: i) a compound containing at least two isocyanate groups; ii) a compound comprising a poly(dialkylsiloxane) segment and an isocyanate-reactive group; iii) a compound comprising an isocyanate-reactive group and at least two (meth)acrylate groups; It can be prepared by reacting components comprising:

[0058] In some embodiments, the equivalent ratio of component ii) to component i) ranges from 0.05 to 0.60.

[0059] In some embodiments, the equivalent ratio of component iii) to component i) ranges from 0.45 to 1.00.

[0060] The resulting compound contains a terminal PDMS segment and at least two (meth)acrylate groups, which can provide good wetting of the release-treated nanostructured film and good adhesion to oxide-coated substrates. Such compounds can also be used as intermediate compounds.

[0061] To provide Z groups further comprising organosilanes, intermediate compounds that are polyfunctional with respect to the (meth)acryl groups can subsequently be reacted by Michael addition with corresponding organosilanes bearing, for example, amino, alkylamino, or mercapto groups.

[0062] Suitable organosilanes include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, bis(3-trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, methylbis(3-trimethoxysilylpropyl)amine, 3-(2-aminoethyl)aminopropyltrimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, (aminoethylaminomethyl)phenethyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)amine, N-(2-aminoethyl)-3-aminopropyltributoxysilane, 6-(aminohexylaminopropyl)aminopropyl )trimethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, p-(2-aminoethyl)phenyltrimethoxysilane, 3-aminopropyltris(methoxyethoxyethoxy)silane, 3-aminopropylmethyldiethoxysilane, 3-(N-methylamino)propyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, and 3-aminopropyldimethylethoxysilane.

[0063] Examples of silane compounds containing a hydrolyzable group and a mercapto group include, for example, 3-mercaptopropyltriethoxysilane; 3-mercaptopropyl-trimethoxysilane; 11-mercaptoundecyltrimethoxysilane; s-(octanoyl)mercaptopropyltriethoxysilane; (mercaptomethyl)methyldiethoxysilane; and 3-mercaptopropylmethyldimethoxysilane.

[0064] Of course, different synthetic methodologies may be used, further description of which can be found in the Examples included below.

[0065] Similarly, a free-radically polymerizable compound comprising at least one poly(dialkylsiloxane) segment, at least one (meth)acrylic group, and at least one hydrolyzable silyl group, may in some embodiments be according to Formula I, and may be prepared by reacting ingredients comprising: i) a urethane compound comprising a poly(dialkylsiloxane) segment and at least two (e.g., at least two, at least three, at least four, at least five, or at least six) (meth)acrylic groups; ii) an organosilane compound containing a hydrolyzable group and a group selected from an amino group or a mercapto group, wherein the equivalent ratio of components i) to ii) is greater than 1 so that the (meth)acrylic groups remain unreacted;

[0066] In some embodiments, the ratio of equivalents of components i) to ii) is from 2:1 to 10:1 or from 2:1 to 6:1.

[0067] The synthesis reaction (eg, between components i) and ii) or other addition / condensation reactions can be carried out in a solvent.

[0068] Exemplary solvents include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, methyl amyl ketone, and N-methylpyrrolidone (NMP); ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, and methyl tetrahydrofurfuryl ether; esters such as methyl acetate, ethyl acetate, and butyl acetate; and cyclic esters such as delta-valerolactone and gamma-valerolactone.

[0069] However, the claimed compounds of the present disclosure are prepared, and they are often accompanied by various other compounds (e.g., addition products, other by-products, or impurities formed in statistical amounts). For example, combining equal equivalents of an amine and a diisocyanate (or di(meth)acrylate) can result in a mixture of unreacted diisocyanate (or di(meth)acrylate), a 1:1 adduct, and a 2:1 adduct (i.e., both isocyanato or (meth)acrylic groups have reacted), for example, in a statistical relative ratio of approximately 1:2:1.

[0070] Accordingly, the present disclosure also provides free-radically polymerizable compositions comprising one or more compounds according to the present disclosure.

[0071] In many embodiments, the free-radically polymerizable composition further comprises at least one additional free-radically polymerizable compound (i.e., other than a free-radically polymerizable compound according to the present disclosure). In many embodiments, the at least one additional free-radically polymerizable compound comprises one or more free-radically polymerizable (meth)acrylic group-containing monomers and / or oligomers.Examples include 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol monoacrylate monomethacrylate, ethylene glycol diacrylate, alkoxylated aliphatic diacrylates, alkoxylated cyclohexanedimethanol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycol diacrylate, caprolactone-modified neopentyl glycol hydroxypivalate diacrylate, caprolactone-modified neopentyl glycol hydroxypivalate diacrylate, cyclohexanedimethanol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, hydroxypivalaldehyde-modified trimethylolpropane diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, tetraethylene ... di(meth)acrylic-containing monomers such as ethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, triethylene glycol diacrylate, and tripropylene glycol diacrylate; tri(meth)acrylic-containing monomers such as glycerol triacrylate, trimethylolpropane triacrylate, ethoxylated triacrylates (e.g., ethoxylated trimethylolpropane triacrylate), propoxylated triacrylates (e.g., propoxylated glyceryl triacrylate and propoxylated trimethylolpropane triacrylate), trimethylolpropane triacrylate, and tris(2-hydroxyethyl)isocyanurate triacrylate; and higher-functionality (meth)acrylic-containing monomers such as ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, and caprolactone-modified dipentaerythritol hexaacrylate.

[0072] Oligomeric (meth)acrylic monomers such as, for example, urethane acrylates, polyester acrylates, and epoxy acrylates can also be used. In some embodiments, the polymerizable composition comprises an aliphatic urethane acrylate oligomer available under the trade name PHOTOMER 6210, which has a tensile strength of less than 10,000 kPa, an elongation of 30-50%, a modulus of elasticity in the range of 50,000-10,000 kPa, and a glass transition temperature in the range of 25-50°C.

[0073] In some embodiments, the free radically polymerizable composition comprises di(meth)acrylic group-containing monomers in an amount of at least 25, at least 30, at least 35, at least 40, at least 45, or even at least 50 weight percent of the free radically polymerizable composition.

[0074] In a typical embodiment, the free-radically polymerizable composition comprises one or more free-radically polymerizable compounds (e.g., those of Formula I) comprising at least one poly(dialkylsiloxane) segment, at least one (meth)acrylic group, and optionally at least one hydrolyzable silyl group, as described herein, in an amount of at least 1, at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, or even at least 10 weight percent based on the nonvolatile solids content of the free-radically polymerizable composition. The amount of such free-radically polymerizable compounds is typically 50 weight percent or less based on the total nonvolatile solids content of the free-radically polymerizable composition. Preferred concentrations can vary depending on the desired properties and the particular compounds utilized.

[0075] In many cases, such compositions can include, for example, an effective amount of an initiator for free radical polymerization (also known as a free radical initiator). Free radical initiators can be thermally activated (e.g., peroxides and certain azo compounds) and / or photoactivated (e.g., Norrish Type I and Type II photoinitiators). Such photoinitiators are activated by exposure to actinic radiation (e.g., ultraviolet and / or visible electromagnetic radiation).

[0076] Free radical polymerization can be achieved, for example, by heating or exposure to actinic radiation (e.g., ultraviolet and / or visible light, gamma radiation, or electron beam), depending on the presence and / or selection of a free radical initiator, of which exposure to actinic radiation is often preferred due to ease of implementation.

[0077] When present, the amount of photoinitiator is typically an effective amount. In some embodiments, the effective amount of free radical initiator comprises less than 10 weight percent, more typically less than 7 weight percent, and more typically less than 3 weight percent of the total adhesive layer. It will be recognized that curing may be complete even if polymerizable (meth)acrylate groups remain.

[0078] Exemplary photoinitiators include α-cleavage photoinitiators such as benzoin and its derivatives, e.g., α-methylbenzoin; α-phenylbenzoin; α-allylbenzoin; α-benzylbenzoin; benzoin ethers, e.g., benzil dimethyl ketal (available as OMNIRAD 651 from iGM Resins USA, Charlotte, North Carolina, USA), benzoin methyl ether, benzoin ethyl ether, benzoin n-butyl ether; acetophenone and its derivatives, e.g., 2-hydroxy-2-methyl-1-phenyl-1-propanone (available as DAROCUR 1173 from BASF, Florham Park, New Jersey, USA) and 1-hydroxycyclohexyl phenyl ketone (available as OMNIRAD 184 from iGM Resins); 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone (available as OMNIRAD 184 from iGM Resins USA), and the like. 907); 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone (available from iGM Resins USA as OMNIRAD 369); titanium complexes such as bis(η5-2,4-cyclopentadien-1-yl)bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium (available from iGM Resins USA as OMNIRAD 784); and monoacylphosphines and bisacylphosphines (available from iGM Resins as OMNIRAD 1700 or from BASF as IRGACURE 1800, IRGACURE 1850, and DAROCUR 4265). One useful photoinitiator, a bifunctional alpha hydroxyketone, is available from iGM Resins USA as ESACURE ONE.

[0079] Preferably, when an acylphosphine or acylphosphine oxide photoinitiator is utilized, the photoinitiator is combined with a photoinitiator having a high extinction coefficient at one or more wavelengths of actinic radiation (e.g., 2-hydroxy-2-methyl-1-phenyl-1-propanone). Such a combination typically promotes surface cure while maintaining low levels of often expensive photoinitiators.

[0080] Other useful photoinitiators include anthraquinones (e.g., anthraquinone, 2-ethylanthraquinone, 1-chloroanthraquinone, 1,4-dimethylanthraquinone, 1-methoxyanthraquinone) and benzophenone and its derivatives (e.g., phenoxybenzophenone, phenylbenzophenone).

[0081] Free-radically polymerizable compositions according to the present disclosure may contain optional additional components, such as organic solvents (e.g., as described above), stabilizers, colorants, photosensitizers, fillers, wetting agents, and leveling agents.

[0082] Examples of suitable actinic radiation sources include, for example, lasers, arc lamps (e.g., medium pressure mercury arc lamps), LED lamps, xenon flash lamps, microwave-driven lamps (e.g., with H-type or D-type bulbs), and actinic radiation. The selection of appropriate exposure conditions is within the ability of one skilled in the art.

[0083] Generally, the free-radically polymerizable compositions can be prepared by conventional mixing procedures.

[0084] Free-radically polymerizable compounds according to the present disclosure and compositions comprising them are useful. For example, the free-radically polymerizable composition can be disposed on the surface of a substrate (e.g., as a continuous or discontinuous, optionally patterned film) and then polymerized (e.g., by exposure to an effective amount of actinic radiation).

[0085] In some embodiments, the cured polymerizable composition may be utilized as a masking layer in methods for forming etched nanoscale patterns, such as those described in WO 2020 / 095258 (Van Lengerich et al.), the disclosure of which is incorporated herein by reference.

[0086] 1, an exemplary article 100 includes a layer 120 of a free-radically polymerized composition disposed on a surface 105 of a substrate 110 that includes a metal oxide layer 140. Layer 120 includes patterned nanostructures 130 that form a metasurface.

[0087] Exemplary substrates include sheets, plates, and films comprising any of glass, metal, organic polymers (e.g., polyethylene terephthalate (PET), polycarbonate (PC), polyethylene terephthalate glycol modified (PETG), polyethylene, polyimide, polystyrene, or polyurethane), inorganic metal oxides, and combinations thereof. In some embodiments, the surface has a pattern comprising nanostructures. In some embodiments, the surface comprises a metal oxide (e.g., an oxide of titanium, zirconium, hafnium, niobium, or cerium).

[0088] Objects and advantages of the present disclosure are further illustrated by the following non-limiting examples, but the specific materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit the present disclosure. [Example]

[0089] Unless otherwise stated, all parts, percentages, ratios, etc. in the examples and elsewhere in this specification are by weight. Table 1 (below) lists the materials used in the examples and their sources. [Table 1]

[0090] Preparation examples PE-1~PE-6 Preparative Examples PE-1 to PE-6 were synthesized using the following general procedure and the component amounts reported in Table 2. A 250 mL round-bottom flask equipped with a magnetic stir bar was charged with a given amount of DES N 100 and approximately 25 grams (g) of tetrahydrofuran (THF). A given amount of PDMS-2000 or PDMS-1000 was then added at room temperature via a pressure-equalizing dropping funnel over 70 minutes (min) under a dry air atmosphere, at which point the funnel was rinsed with 5 g of THF. A given amount of BHT and a given amount of a 10 wt% solution of XK-672 in THF were added to the reaction mixture. A given amount of PET3A was added in one go, along with approximately 15 g of THF. After 1 hour (h) 20 minutes, the flask was placed in a 55°C oil bath and a condenser was attached to the top. After an additional 4 hours and 15 minutes, the reaction was adjusted to 30 wt% solids by adding THF (such that the amount of THF was 2.33 times the combined amount of the given amounts of DES N100, PDMS-2000, PDMS-1000, and PET3A) and bottled. [Table 2]

[0091] Calculation of acrylate equivalent weight for PE1 to PE-6 and PE11 to PE-20 A representative procedure for calculating the approximate acrylate equivalent weight (grams of material / moles of acrylate moiety) of PE-3 is shown below: A similar procedure was used to calculate the approximate acrylate equivalent weight (EW) of PE-1, PE-2, PE-4, PE-5, and PE-6, as well as PE-11 through PE-20.

[0092] DES N100 has an isocyanate equivalent weight of 191 g / mol and an isocyanate functionality of approximately 3. DES N100 has a molecular weight of approximately 573 g / mol. PET3A has an alcohol equivalent weight and molecular weight of 480.3 g / mol.

[0093] PDMS-2000 has an alcohol equivalent weight and molecular weight of approximately 2000 g / mol.

[0094] The molecule obtained by adding 1 equivalent of PDMS-2000 and 2 equivalents of PET3A to DES N100 has the ideal structure shown below: [ka]

[0095] "PDMS" in the above structure is -(Si(CH3)2O) n represents Si(C4H9)(CH3)2, where n is approximately 24.7. (In the given preparation example, when PDMS-1000 is used, n is approximately 11.2.) The approximate molecular weight of the molecule shown above is 573 + 2000 + 2 480.3 = 3533.6 g / mol. Because this structure has six acrylates, its acrylate EW is 3533.6 / 6 = 588.9 g / eq.

[0096] The molecule obtained by adding three equivalents of PET3A to DES N100 has the idealized structure shown below: [ka]

[0097] The approximate molecular weight of the molecule shown above is 573 + 3 480.3 = 2013.9 (in g / mol). Since this structure has 9 acrylates, its acrylate EW is 2013.9 / 9 = 223.8 g / eq.

[0098] The resulting material, PE-3, ideally contains a mixture of the two molecules shown above. The ratio of the two molecules in the mixture is determined by the molar equivalents of PDMS-2000 (or PDMS-1000) and PET3A added (note that a 0.05 equivalent excess of PET3A is added but ignored in the calculation). For PE-3, 0.35 molar equivalents of PDMS-2000 (relative to the isocyanate equivalent weight of DES N100) were added, resulting in a mixture that was 35% of the first structure (acrylate equivalent weight 588.9) and 65% of the second structure (acrylate equivalent weight 223.8). Therefore, the average acrylate equivalent weight of the PE-3 mixture is 0.35 * 588.93 + 0.65 * 223.8 = 351.6 g / eq. The final PE-3 material is provided as a 30 wt % solution in THF, so the acrylate equivalent weight of the solution is 351.6 / 0.3=1172.0 g / eq.

[0099] Preparation Example 7 DES Nl00 / 0.35 PDMS-2000 / 0.30 APTMS / 0.4 PET3A A 250 mL round-bottom flask equipped with a magnetic stir bar was charged with 2.86 g of DES N100 and 28.57 g of THF and placed in a 55 °C oil bath. Then, 10.47 g of PDMS-2000 was added via a pressure-equalizing dropping funnel over 1.5 hours under a dry air atmosphere, at which point the funnel was rinsed with 5 g of THF. After 10 minutes, 0.80 g of APTMS was added all at once to the reaction. After 2 hours, 0.009 g of BHT, 0.085 g of a 10 wt% solution of XK-672 in THF, and 2.87 g of PET3A were added to the reaction. The reaction was carried out at 55 °C for an additional 6 hours and then allowed to cool overnight. The reaction was adjusted to contain a total of 33.52 g of THF. It was then diluted with 6.13 g of isopropanol (IPA) to 30 wt % solids, bottled, and stored in a -30°C freezer.

[0100] Preparation Example 8 DES Nl00 / 0.35 PDMS-1000 / 0.30 APTMS / 0.4 PET3A A 250 mL round-bottom flask equipped with a magnetic stir bar was charged with 3.50 g of DES N100 and 26.00 g of THF and placed in a 55 °C oil bath. Then, 6.41 g of PDMS-1000 was added via a pressure-equalizing dropping funnel over 1.5 h under a dry air atmosphere, at which point the funnel was rinsed with 5 g of THF. After 10 min, 0.99 g of APTMS was charged to the reaction in one portion. After 2 h, 0.007 g of BHT, 0.07 g of a 10 wt% solution of XK-672 in THF, and 3.52 g of PET3A were added to the reaction. The reaction was carried out at 55 °C for an additional 6 h and then allowed to cool overnight. It was then diluted to 30% (wt) solids with 7.60 g of isopropanol (IPA), bottled, and stored in a -30 °C freezer.

[0101] Preparation Example 9 DES Nl00 / 0.15 HFPO Amidoll / 0.9 PET3A / 0.33 N-Me-APTMS A 20 mL vial equipped with a stir bar was charged with 5 g of HFPO UA (0.012 acrylate equivalents; acrylate equivalent weight 415.4 g / mol) and 0.754 g of N-Me-APTMS (0.0039 equivalents). The reaction was stirred at room temperature for 1.25 hours and then stored at -30°C. The resulting material was 69.6 wt% solids.

[0102] Preparation example PE-10 Photopolymerizable resin solution A standard polymerizable resin was prepared in a glass container consisting of 9.7 parts by weight of PHOTOMER 6210, 3.2 parts by weight of SR238, 0.06 parts by weight of TPO, 43.5 parts by weight of methyl ethyl ketone (MEK) and 43.5 parts by weight of PGME.

[0103] Examples EX-1 to EX-18 A given amount of a given example solution (the 30 weight percent solution shown above, shown in the "Starting Materials" column of Table 3) was added to a 20 mL glass vial equipped with a magnetic stir bar. A given amount of N-Me-APTMS was then added to the vial. The resulting mixture was stirred at room temperature for at least 1 hour and then stored at -30°C until use. [Table 3]

[0104] Examples EX-19 to EX-30 and Comparative Examples CE-1 to CE-11 Examples EX-19 through EX-30, along with Comparative Examples CE-1 through CE-11, were prepared by combining the given amounts of the ingredients in Table 4 in a glass vial and stirring to mix. Note that the "Excipient Identity" column refers to some example materials provided as a solution of the active ingredient in a solvent according to the respective synthesis details above. [Table 4]

[0105] After preparing the above solutions, nanoreplication experiments were performed to test their performance in terms of both 1) wet-out to release-treated substrates and 2) bonding to metal oxide-coated PET substrates during the nanoreplication process.

[0106] Fabrication of patterned template films Tooling films were fabricated via UV replication on a nickel master. The nickel master was a nanostructured tool with a 65 mm x 65 mm square packed hole array of 310 nm deep holes with a 200 nm diameter, 400 nm pitch, and a 6.3° draft angle. The resin was prepared by combining and mixing PHOTOMER 6210, SR238, SR351, and TPO in a 60 / 20 / 20 / 0.5 weight ratio. The resin was coated onto a 125 μm thick polycarbonate film, and when the coated polycarbonate film was pressed against the nanostructured nickel surface, it was sufficient to wet the nickel surface and form a rolling bead of resin.

[0107] The film, while in contact with the nanostructured nickel surface, was exposed to radiation from two Fusion UV lamp systems (obtained from Fusion UV Systems under the designation "F600"), both fitted with D bulbs operating at 142 W / cm. After peeling the film from the nanostructured nickel surface, the nanostructured side of the film was then exposed to radiation from a Fusion UV lamp system (obtained from Fusion UV Systems under the designation "F600"), both fitted with D bulbs operating at 142 W / cm. It was again exposed to radiation from a UV lamp system. Following UV radiation contact with the surface and subsequent fusion exposure, the resin solidified into a square-packed array of posts, the opposite generation from the nickel tool.

[0108] The patterned template film was then peeled with HMDSO to create a peelable surface suitable for nanoreplication, using the peeling method described in WO 2020 / 095258 (Van Lengerich et al.) at page 60, line 19 to page 61, line 11. The peeling was necessary to allow the acrylate resin to cleanly separate from the template film after UV replication, enabling transfer to the oxide-coated substrate. The oxide-coated PET film (Melinex ST504 DuPont Teijin Films, Chester, Virginia, United States) was generally coated with a silicon-containing etch resist (25 nm SiAl ) as described in WO 2017 / 003870 (Rowe et al.) at page 22, line 28 to page 29, line 11. x O y ) was prepared by sputter coating.

[0109] Roland transcription process The coating solutions of Examples EX19-EX-30 and Comparative Examples CE-1-CE-11 were used in a coating and curing process known as Rowland transfer, described below. A benchtop Rowland transfer process was performed to test for wet-out of the solution onto a tooling film and transfer of the pattern to an oxide coating on a PET substrate. First, approximately 1 mL of a given coating solution was dispensed onto a HMSDO-treated template film using a pipette. Next, a wire-wound No. 4 rod (delivering a wet film thickness of 0.4 thousandths of an inch (mil), or approximately 10 micrometers (μm)) was drawn down to spread the coating over the structured section of the template film. The film was then left at ambient conditions for 120 seconds (s) to allow the solvent to evaporate. Any wetting removal of the film was observed throughout the evaporation process, both inside and outside the patterned areas.

[0110] After a dwell time of 120 seconds, the solvent was evaporated and the film dried to a coating thickness of approximately 1.3 microns. This film was laminated onto an oxide-coated polyethylene terephthalate substrate using a 1-inch (2.5 cm) wide hand roll laminator. After lamination, the film stack was exposed to a 385 nm UV-LED curing source for approximately 20 seconds, sufficient to solidify the coating. The films were then separated and inspected for replication and transfer quality. The results of these tests are reported in Table 5.

[0111] In Table 5, the wettability of the coating solutions on the release-treated HMDSO surface was evaluated according to the following ranking scale: Insufficient: The coating solution wetted off or broke into small beads on either the patterned and / or unpatterned areas of the template film. Good The coating solution remained wetted out in a continuous layer on the template film.

[0112] In Table 5, the pattern transfer of nanostructures on oxide surfaces was evaluated to determine the pattern transfer quality according to the following ranking scale: 0 Pattern cannot be transferred to the substrate 1. The majority of cases are pattern transfer failures (>50% are pattern transfer failures) 2 Minor pattern transfer failure (slight pattern failure or break around edge). 3 Complete pattern transfer [Table 5]

[0113] Examples EX-31 to EX-34 and Comparative Examples CE-12 to CE-15 Preparation of coating solution The coating solutions of Examples EX-31 to EX-34, along with Comparative Examples CE-1 to CE-9, were made by combining the given amounts of the ingredients in Table 6 in a glass vial and stirring to mix. Note that the "Excipient Identity" column refers to some example materials provided as a solution of the active ingredient in a solvent according to the respective synthesis details above. [Table 6]

[0114] Roll-to-roll pattern transfer The pattern was transferred from the template film to the oxide-coated PET in the following roll-to-roll process. Portions of the release-treated template film used in Examples EX-19-EX-30 and Comparative Examples CE-1-CE-11 were slot-die coated with a different one of the coating solutions from Examples EX-31-EX-34 and Comparative Examples CE-12-CE-15, each at a speed of 0.0508 meters / second. In each case, the solution was coated over a 10.2 cm width and pumped at a rate of 1.20 mL / min using a Harvard syringe pump. The coating was allowed to dry at ambient conditions and then partially cured 10 meters downstream from the solution application using a nitrogen-inerted 385 nm UV-LED system powered at 40 volts and 0.25 amps. The coated film was then coated with the SiAl x O yThe coated film was laminated with the film. The nip consisted of a 90 Duro rubber roll and a steel roll set at 54°C. The nip was coupled to two air cylinders pressed at 0.28 MPa. The overall web tension was set at approximately 0.0057 N / m. The solution was cured using a Fusion UV Systems microwave-driven lamp equipped with a D-shaped bulb (Heraeus, Hanau, Germany), which separated the dried coating solution into oxide-coated films from the release-treated template film with fidelity that varied depending on the solution composition. The results are shown in Table 7 (below) and use the same wetting and transfer evaluation scheme used in Table 5. [Table 7]

[0115] Preparation Examples: Synthesis of PE-11 to PE-16 Preparative Examples PE-11 to PE-16 were synthesized using the same general procedure as PE-1 to PE-6, except that for PE-11, PE12, PE14, PE15, and PE16, PDMS carbinol was used, and XK-672 was charged with DES N100 and THF. The component amounts are reported in Tables 8 and 9. [Table 8] [Table 9]

[0116] Examples EX-35 to EX-40 The following examples were prepared in a similar manner to Examples EX-1 to EX-18.

[0117] A given amount of a given example solution (30 weight percent solution shown above, shown in the "Starting Materials" column of Table 10) was added to a 20 mL glass vial equipped with a magnetic stir bar. A given amount of coupling agent was then added to the vial. The resulting mixture was stirred at room temperature for at least 1 hour and then stored at -30°C until use. [Table 10]

[0118] Examples EX-41 to EX-55 and Comparative Example CE-16 Examples EX-41 through EX-55, along with Comparative Example CE-16, were prepared by combining the given amounts of the ingredients in Table 11 in a glass vial and stirring to mix. Note that the "Excipient Identity" column refers to some example materials provided as a solution of the active ingredient in a solvent according to the respective synthesis details above. [Table 11]

[0119] The coating solutions of Comparative Example CE-16 and Examples EX-41 through EX-55 were used in a coating and curing process known as Rowland transfer as described above for Examples EX19 through EX-30 and Comparative Examples CE-1 through CE-11. The results are shown in Table 12, using the same wetting and transfer evaluation scheme used in Table 5. [Table 12]

[0120] Examples EX-56 to EX-61 The following examples were prepared in a similar manner to Examples EX-1 to EX-18.

[0121] A given amount of a given example solution (30 weight percent solution shown above, shown in the "Starting Materials" column of Table 13) was added to a 20 mL glass vial equipped with a magnetic stir bar. A given amount of coupling agent was then added to the vial. The resulting mixture was stirred at room temperature for at least 1 hour and then stored at -30°C until use. [Table 13]

[0122] Examples EX-62 to EX-78 and Comparative Example CE-17 Examples EX-66 through EX-72, along with Comparative Example CE-17, were prepared by combining the given amounts of the ingredients in Table 14 in a glass vial and stirring to mix. Note that the "Excipient Identity" column refers to some example materials provided as a solution of the active ingredient in a solvent, according to the respective synthesis details above. Results are presented in Table 15, using the same wettability and transfer evaluation scheme used in Table 5. [Table 14] [Table 15]

[0123] All references, patents, and patent applications cited in this application that are incorporated by reference are incorporated in a consistent manner. In the event of a conflict or inconsistency between any portion of an incorporated reference and this application, the information in this application shall prevail. The foregoing description is intended to enable one skilled in the art to practice the disclosure as set forth in the claims, and should not be construed as limiting the scope of the disclosure, which is defined by the claims and all equivalents thereof. The present invention includes the following aspects. (1) Formula: [ka] [In the formula, R i is C1 to C with a valence of m+n 60 is an organic group; Each PDMS independently represents a monovalent group having a poly(dialkylsiloxane) segment; each Q is independently a covalent bond or an organic linking group having a valence of at least two; Each X is independently O, S, or NR 1 and each R 1 are independently H or a C1-C4 alkyl group; m and n are independently integers greater than or equal to 1; Each Z is independently [ka] (In the formula, R 2 is -S- or N(R 6 )- and R 6 is H, a C1-C4 alkyl group, or -R 3 Si(L) b (R 4 ) 3-b and; R 3 is a divalent alkylene group optionally substituted with one or more catenary oxygen atoms; R 4 is a monovalent non-hydrolyzable group; R 5 is H or methyl; each L is independently a monovalent hydrolyzable group; each b is independently 1, 2, or 3; a and p are independently integers greater than or equal to 0, and 1≦(a+p)≦6; a=1 for at least one Z; and p=1 for at least one Z. represents] A free radical polymerizable compound represented by the formula: (2)R i is a residue of a polyisocyanate selected from diisocyanates and triisocyanates. (3)Ri comprises residues of diisocyanate oligomerization products. (4) The free radical polymerizable compound according to any one of items 1 to 3, wherein 2≦(m+n)≦10. (5) The free radical polymerizable compound according to any one of items 1 to 4, wherein m=1, n=1, and the average values of a and p per Z group are each at least 1. (6) The free radical polymerizable compound according to any one of items 1 to 4, wherein m=1, n=2, and the average values of a and p per Z group are each at least 1. (7) m=1, n=2, a=0 and p=1 for at least one Z, and a=1 and p=0 for at least one other Z. The free radical polymerizable compound according to item 1. (8) 4≦(m+n)≦10, 3≦n≦9, a=0 and p=1 for at least one Z, and a=1 and p=0 for at least one other Z. The free radical polymerizable compound according to item 1. (9) A free radical polymerizable composition comprising a plurality of different free radical polymerizable compounds according to any one of items 1 to 8. (10) The free radical polymerizable composition according to item 9, further comprising at least one additional free radical polymerizable compound. 11. The free radical polymerizable composition according to claim 9 or 10, wherein the polymerizable composition further comprises at least one free radical photoinitiator, and the method further comprises exposing the polymerizable composition to an effective amount of actinic radiation. (12) i) a urethane compound comprising a poly(dialkylsiloxane) segment and at least two (meth)acrylic groups; ii) an organosilane compound containing a hydrolyzable group and a group selected from an amino group or a mercapto group; A reaction product of components comprising: A reaction product wherein the equivalent ratio of components i) to ii) is greater than 1, such that (meth)acrylic groups remain unreacted. (13) The reaction product according to item 12, wherein the equivalent ratio of components i) to ii) is 2:1 to 10:1. (14) The reaction product according to item 12 or 13, wherein the reaction product contains unreacted component i). (15) A method for making a polymerized composition, comprising: Preparing a polymerizable composition comprising at least one free-radically polymerizable compound according to any one of items 1 to 8; free-radical polymerizing the polymerizable composition to provide the polymerized composition; A method comprising: 16. The method of claim 15, wherein the polymerizable composition further comprises at least one additional free-radically polymerizable compound. 17. The method of claim 15, wherein the polymerizable composition further comprises at least one free radical photoinitiator, and the method further comprises exposing the polymerizable composition to an effective amount of actinic radiation. (18) A method of manufacturing an article, comprising: a) disposing a layer of the free radically polymerizable composition according to any one of items 9 to 11 onto a mold surface of a first substrate, wherein the mold surface has a pattern comprising nanostructures; b) contacting a layer of said free-radically polymerizable composition with a metal oxide surface of a second substrate; c) free-radically polymerizing at least a portion of said free-radically polymerizable composition to provide a polymerized composition; d) separating the polymerized composition from the mold surface; A method comprising: 19. The method of claim 18, wherein the free radical polymerization in step c) comprises exposing the free radical polymerizable composition to actinic radiation. (20) An article manufactured according to the method described in Item 18 or 19. Equation (21): [ka] [In the formula, R iis C1 to C with a valence of m+n 60 is an organic group; Each PDMS independently represents a monovalent group having a poly(dialkylsiloxane) segment; each Q is independently a covalent bond or an organic linking group having a valence of at least two; Each X is independently O, S, or NR 1 and each R 1 are independently H or a C1-C4 alkyl group; m and n are independently integers greater than or equal to 1; Each Z is independently [ka] (In the formula, R 5 is H or methyl; For at least one Z, p is at least 2. represents] A free radical polymerizable compound represented by the formula: (22) The free radical polymerizable compound according to item 21, further characterized by any one of items 2 to 6. (23) i) a compound containing at least two isocyanate groups; and ii) a compound comprising a poly(dialkylsiloxane) segment and an isocyanate-reactive group; iii) a compound comprising an isocyanate-reactive group and at least two (meth)acrylate groups; A reaction product of components including: (24) A method for producing a polymerized composition, comprising: Preparing a polymerizable composition containing at least one free-radically polymerizable compound according to any one of items 21 to 23; free-radical polymerizing the polymerizable composition to provide the polymerized composition; A method comprising: (25) The method according to item 24, further characterized by item 16 or 17. (26) A method of manufacturing an article, comprising: a) disposing a layer of the free radically polymerizable composition according to any one of items 21 to 24 onto a mold surface of a first substrate, wherein the mold surface has a pattern comprising nanostructures; b) contacting a layer of said free-radically polymerizable composition with a metal oxide surface of a second substrate; c) free-radically polymerizing at least a portion of said free-radically polymerizable composition to provide a polymerized composition; d) separating the polymerized composition from the mold surface; A method comprising:

Claims

1. formula: 【Chemical 1】 [In the formula, R ｉ is C with a valence of m+n １ ~C ６０ is an organic group; Each PDMS independently represents a monovalent group having a poly(dialkylsiloxane) segment; each Q is independently a covalent bond or an organic linking group having a valence of at least two; Each X is independently O, S, or NR １ and each R １ are independently H or C １ ~C ４ is an alkyl group; m and n are independently integers greater than or equal to 1; Each Z is independently 【Chemistry 2】 (In the formula, R ２ is -S- or N(R ６ )- and R ６ is H, C １ ~C ４ alkyl group or -R ３ Si(L) ｂ (R ４ ) ３－ｂ and R ３ is a divalent alkylene group optionally substituted with one or more catenary oxygen atoms; R ４ is a monovalent non-hydrolyzable group; R ５ is H or methyl; each L is independently a monovalent hydrolyzable group; each b is independently 1, 2, or 3; a and p are independently integers of 0 or greater, with 1≦(a+p)≦6; a=1 for at least one Z; and p=1 for at least one Z. represents and I) m=1, n=1, and the average values of a and p per Z group are each at least 1; II) m=1, n=2, and the average values of a and p per Z group are each at least 1; III) m=1, n=2, and for at least one Z, a=0 and p=1, and for at least one other Z, a=1 and p=0; and IV) 4≦(m+n)≦10, 3≦n≦9, a=0 and p=1 for at least one Z, and a=1 and p=0 for at least one other Z; A free radical polymerizable compound that falls into one of the above categories.

2. A free-radically polymerizable composition comprising a plurality of different free-radically polymerizable compounds according to claim 1.

3. 3. The free-radically polymerizable composition of claim 2, further comprising at least one additional free-radically polymerizable compound.

4. 3. The free radical polymerizable composition of claim 2, wherein the polymerizable composition further comprises at least one free radical photoinitiator.

5. i) a urethane compound comprising a poly(dialkylsiloxane) segment and at least two (meth)acrylic groups; ii) an organosilane compound containing a hydrolyzable group and a group selected from an amino group or a mercapto group; A reaction product of components comprising: A reaction product wherein the equivalent ratio of components i) to ii) is greater than 1, such that (meth)acrylic groups remain unreacted.

6. 6. The reaction product of claim 5, wherein the equivalent ratio of components i) to ii) is from 2:1 to 10:

1.

7. 6. The reaction product of claim 5, wherein the reaction product comprises unreacted component i).

8. 1. A method of making a polymerized composition, comprising: Providing a polymerizable composition comprising at least one free-radically polymerizable compound of claim 1; free-radical polymerizing the polymerizable composition to provide the polymerized composition; A method comprising:

9. The method of claim 8 , wherein the polymerizable composition further comprises at least one additional free-radically polymerizable compound.

10. 10. The method of claim 8, wherein the polymerizable composition further comprises at least one free radical photoinitiator, and the method further comprises exposing the polymerizable composition to an effective amount of actinic radiation.

11. 1. A method of manufacturing an article, comprising: a) disposing a layer of a free radically polymerizable composition onto a mold surface of a first substrate, the mold surface having a pattern comprising nanostructures; b) contacting a layer of said free-radically polymerizable composition with a metal oxide surface of a second substrate; c) free-radically polymerizing at least a portion of said free-radically polymerizable composition to provide a polymerized composition; d) separating the polymerized composition from the mold surface; Including, The free radically polymerizable composition may comprise a plurality of different free radically polymerizable compounds of the formula: 【Chemistry 3】 [In the formula, R ｉ is C with a valence of m+n １ ~C ６０ is an organic group; Each PDMS independently represents a monovalent group having a poly(dialkylsiloxane) segment; each Q is independently a covalent bond or an organic linking group having a valence of at least two; Each X is independently O, S, or NR １ and each R １ are independently H or C １ ~C ４ is an alkyl group; m and n are independently integers greater than or equal to 1; Each Z is independently 【Chemistry 4】 (In the formula, R ２ is -S- or N(R ６ )- and R ６ is H, C １ ~C ４ alkyl group or -R ３ Si(L) ｂ (R ４ ) ３－ｂ and R ３ is a divalent alkylene group optionally substituted with one or more catenary oxygen atoms; R ４ is a monovalent non-hydrolyzable group; R ５ is H or methyl; each L is independently a monovalent hydrolyzable group; each b is independently 1, 2, or 3; a and p are independently integers of 0 or greater, with 1≦(a+p)≦6; a=1 for at least one Z; and p=1 for at least one Z. represents The method of claim 1, further comprising the step of:

12. 12. The method of claim 11, wherein the free radical polymerization in step c) comprises exposing the free radically polymerizable composition to actinic radiation.

13. 12. An article made according to the method of claim 11.

14. 1. A method of manufacturing an article, comprising: a) disposing a layer of a free radically polymerizable composition onto a mold surface of a first substrate, the mold surface having a pattern comprising nanostructures; b) contacting a layer of said free-radically polymerizable composition with a metal oxide surface of a second substrate; c) free-radically polymerizing at least a portion of said free-radically polymerizable composition to provide a polymerized composition; d) separating the polymerized composition from the mold surface; Including, The free radical polymerizable composition comprises i) a compound containing at least two isocyanate groups; ii) a compound comprising a poly(dialkylsiloxane) segment and an isocyanate-reactive group; iii) a compound comprising an isocyanate-reactive group and at least two (meth)acrylate groups; a free radically polymerizable compound that is the reaction product of components comprising:

15. 1. A method of manufacturing an article, comprising: a) disposing a layer of a free radically polymerizable composition onto a mold surface of a first substrate, the mold surface having a pattern comprising nanostructures; b) contacting a layer of said free-radically polymerizable composition with a metal oxide surface of a second substrate; c) free-radically polymerizing at least a portion of said free-radically polymerizable composition to provide a polymerized composition; d) separating the polymerized composition from the mold surface; Including, The free radically polymerizable composition has the formula: 【Chemistry 5】 [In the formula, R ｉ is C with a valence of m+n １ ~C ６０ is an organic group; Each PDMS independently represents a monovalent group having a poly(dialkylsiloxane) segment; each Q is independently a covalent bond or an organic linking group having a valence of at least two; Each X is independently O, S, or NR １ and each R １ are independently H or C １ ~C ４ is an alkyl group; m and n are independently integers greater than or equal to 1; Each Z is independently 【Chemistry 6】 (In the formula, R ２ is -S- or N(R ６ )- and R ６ is H, C １ ~C ４ alkyl group or -R ３ Si(L) ｂ (R ４ ) ３－ｂ and R ３ is a divalent alkylene group optionally substituted with one or more catenary oxygen atoms; R ４ is a monovalent non-hydrolyzable group; R ５ is H or methyl; each L is independently a monovalent hydrolyzable group; each b is independently 1, 2, or 3; a and p are independently integers of 0 or greater, with 1≦(a+p)≦6; a=1 for at least one Z; and p=1 for at least one Z. represents The method of claim 1, further comprising the step of:

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