Polyurethane compounds comprising perfluorinated groups, hydrolysable silane groups and (meth)acryloyl groups

Abstract

Described herein is a compound having the following formula (I). Also described are mixtures of compounds, reaction products comprising: i) a polyurethane compound comprising a perfluorooxyalkyl moiety and at least two (meth)acryloyl groups; and ii) a silane compound comprising a hydrolysable group and a group selected from an amine or a mercapto group; wherein i) and ii) are reacted in an equivalent ratio of excess of compound i) such that the (meth)acryloyl groups remain unreacted. Also described are methods and articles.

Description

SUMMARY

[0001] While various compounds have been described, industry will find that fluorinated compounds can advantageously improve adhesion to surfaces containing metal oxides.

[0002] In one embodiment, a compound having the formula:

[0003] [R f -QXC(O)HN] m -R i -[NHC(O)OQ(XC(O)C(R 4 )=CH2) p

[0004] (XC(O)CH2CH2R 1 R 2 Si(Y) b (R 3 ) 3-b ) a ] n

[0005] (Formula 1)

[0006] R i is a residue of a polyisocyanate;

[0007] R f is a monovalent perfluoro oxyalkyl group;

[0008] Q is independently an organic linking group of valence at least 2 or a covalent bond;

[0009] X is O, S, or NR, where R is H or an alkyl group having 1 to 4 carbons;

[0010] R 4 is H or CH3;

[0011] R 1 is -S- or -N(R 5 )-, where R 5 is C1-C4 alkyl or -R 2 Si(Y) b (R 3 ) 3-b ;

[0012] R 2 is a divalent alkylene group optionally containing one or more catenary oxygen atoms;

[0013] Y is a hydrolysable group;

[0014] R 3 is a non-hydrolysable group;

[0015] b is 1, 2, or 3;

[0016] m is at least 1;

[0017] n is at least 1;

[0018] for each n, p + a is no greater than 6, provided that

[0019] for at least one n, a is at least 1; and

[0020] for at least one n, and p is at least 1.

[0021] In another embodiment, a mixture of compounds is described comprising the reaction product of i) a polyurethane compound comprising a perfluorooxyalkyl moiety and at least two (meth)acryloyl groups; and ii) a silane compound comprising a hydrolysable group and a group selected from an amine or a mercapto group; wherein i) and ii) are reacted in an equivalent ratio of excess of compound i) such that the (meth)acryloyl groups remain unreacted.

[0022] In another embodiment, a method of making a cured composition is described comprising providing a polymerizable composition comprising a compound or mixture of compounds as described herein; and curing the (meth)acryloyl groups.

[0023] In other embodiments, an article is described comprising a film or film layer comprising the polymerizable composition comprising a compound or mixture of compounds as described herein. The polymerizable composition can further comprise other non-fluorinated or fluorinated free-radically polymerizable monomers, oligomers, or combinations thereof. In some embodiments, the film layer is disposed on a surface of a substrate, such as a (e.g., nanostructured) patterned surface. In some embodiments, the surface of the substrate comprises a metal oxide. BRIEF DESCRIPTION OF DRAWINGS

[0024] FIG. 1N - FIG. 1V is a side view of an illustrative process;

[0025] FIG. 2P - FIG. 2S is a side view of another illustrative process. DETAILED DESCRIPTION

[0026] A polyurethane compound according to Formula 1 comprising a perfluorinated group, a hydrolysable silane group, and a (meth)acryloyl group is presently described.

[0027] As used herein, the term "in-chain" refers to a carbon atom of a carbon chain that is substituted with a substituent (e.g., O or N). Thus, a pendant substituent (e.g., -OH) bonded to a carbon atom is not an in-chain oxygen atom.

[0028] The compounds described herein can be prepared by any suitable method.

[0029] In some embodiments, mixtures of compounds are described comprising the Michael addition reaction product of i) a polyurethane compound comprising a perfluorooxyalkyl moiety and at least two (meth)acryloyl groups; and ii) a silane compound comprising a hydrolysable group and a group selected from an amine or a mercapto group. As used herein, "(meth)acryloyl" means (meth)acrylate, (meth)acrylthio, or (meth)acrylamide. In some embodiments, acryloyl is preferred, i.e., acrylate, acrylthio, and acrylamide.

[0030] Compounds i) and ii) are reacted in equivalent ratios such that there is an excess of (meth)acryloyl groups relative to the number of active hydrogens of the amine or mercapto group. Mercapto groups have one active hydrogen. However, amines can have one or two active hydrogens. For example, primary amines contain two active hydrogens and can Michael add to both possible acryloyl groups. Secondary amines have only one active hydrogen and can Michael add to only one acryloyl group. In some embodiments, the equivalent ratio of i) to ii) is at least 1.1 : 1, 1.2: 1, 1.3: 1, 1.4: 1, 1.5: 1, 1.6: 1, 1.7: 1, 1.8: 1, 1.9: 1, or 2: 1. In some embodiments, the equivalent ratio of i) to ii) is in the range of 2: 1 to 99: 1. In some embodiments, the equivalent ratio of i) to ii) is at least 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, or 9: 1.

[0031] An exemplary synthesis is depicted as follows:

[0032]

[0033] i) a polyurethane compound comprising a perfluorooxyalkyl moiety and at least two (meth)acryloyl groups; and ii) a silane compound comprising a hydrolysable group and a group selected from an amine or a mercapto group are combined in a suitable solvent. A catalyst is optionally added when a homogeneous mixture or solution is obtained, and the reaction mixture is heated at a temperature and for a time sufficient to allow the reaction to proceed. The progress of the reaction can be monitored by using 1 The progress of the reaction can be monitored by using H Fourier Transform Nuclear Magnetic Resonance (FT-NMR) to monitor olefin concentration.

[0034] In typical embodiments, the solvent is non-fluorinated, such as in the case of ketones, such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, methyl amyl ketone, and N-methyl pyrrolidone (NMP); ethers, such as tetrahydrofuran, 2-methyl tetrahydrofuran, and methyl tetrahydrofurfuryl ether; esters, such as methyl acetate, ethyl acetate, and butyl acetate; cyclic esters, such as δ-valerolactone and γ-valerolactone.

[0035] The preparation of polyurethane compounds comprising a perfluorooxyalkyl moiety and at least two (meth)acryloyl groups is known. See, for example, WO 2006 / 102383; incorporated herein by reference.

[0036] Generally, compound i) is prepared by first reacting a polyisocyanate with a perfluorooxyalkyl-containing alcohol, thiol, or amine, and then with a hydroxy-functional (meth)acrylate, the above reactions typically being carried out in a non-hydroxylic solvent and in the presence of a catalyst, such as an organotin compound. Alternatively, compound i) is prepared by first reacting a polyisocyanate with a hydroxy-functional (meth)acrylate, and then with a perfluorooxyalkyl-containing alcohol, thiol, or amine, the above reactions typically being carried out in a non-hydroxylic solvent and in the presence of a catalyst, such as an organotin compound. Additionally, compound i) can be prepared by reacting all three components simultaneously, the reaction typically being carried out in a non-hydroxylic solvent and in the presence of a catalyst, such as an organotin compound.

[0037] Exemplary hydroxy-functional poly(meth)acrylates include, for example, 1,3- glycerol dimethacrylate and pentaerythritol triacrylate. When the isocyanate comprises at least three isocyanate groups, a hydroxy-functional mono(meth)acrylate can be used. Various hydroxy-functional mono(meth)acrylates are known, including, for example, hydroxyethyl (meth)acrylate and polycaprolactone. In some embodiments, a mixture of a hydroxy-functional poly(meth)acrylate and a hydroxy-functional mono(meth)acrylate can be utilized.

[0038] In some embodiments, the polyurethane compound comprising a perfluorooxyalkyl moiety and at least two (meth)acryloyl groups can have formula 2A:

[0039] R i -(NHC(O)XQR f ) m2 ,-(NHC(O)OQ(A) p2 ) n2 (Formula 2A)

[0040] wherein R i is a residue of a polyisocyanate; X is O, S, or NR, wherein R is H or lower alkyl of 1 to 4 carbon atoms; Q is a covalent bond or an organic linking group; Rf is a monovalent perfluorooxyalkyl group; and A is a (meth)acryloyl functional group -XC(O)C(R2)=CH2, where R2is H or methyl; m2is at least 1; n2is at least 1; p2is 2 to 6; and m2+n2is 2 to 10. Both units (i.e., m2and n2) are bonded to the residue of a polyisocyanate. Thus, when R i is a residue of a diisocyanate, Formula 2A can also be represented by the following Formula 2B:

[0041] [R f QXC(O)HN)] m2 -R i -[NHC(O)OQ(XC(O)C(R 4 )=CH2) p2 ] n2 (Formula 2B)

[0042] Q of Formulas 1 and 2A-2B can be a linear or branched or cyclic-containing linking group. Q can comprise covalent bonds, alkylene, arylene, aralkylene, or alkarylene groups. Q can optionally include heteroatoms, such as O, N, and S, and combinations thereof. Q can also optionally include functional groups containing heteroatoms, such as carbonyl or sulfonyl groups, and combinations thereof.

[0043] In some embodiments, the monovalent perfluorooxyalkyl group (R f of Formulas 1 and 2A-2B) comprises a moiety of 1 to 6 (e.g., linear or branched) perfluorinated carbon atoms and a single oxygen atom, such as CF3CF2CF2O-. In some embodiments, the number of perfluorinated carbon atoms is at least 2 or 3. In some embodiments, the number of perfluorinated carbon atoms is no greater than 5 or 4.

[0044] In typical embodiments, the monovalent perfluorooxyalkyl group includes a perfluorinated poly(oxyalkylene) group having divalent perfluorooxyalkylene group repeat units having the general structure -[C m F 2m O] s - where, for each s, m is independently in the range of 1 to 6. In some embodiments, m is at least 2 or 3. In some embodiments, m is no greater than 5 or 4. In one embodiment, Rfis “HFPO-”. When n is 1 and R f is a monovalent perfluorooxyalkyl group, HFPO- refers to the end group CF3CF2CF2O-[CF(CF3)CF2O] s-CF(CF3)-, wherein s is an integer from 2 to 25. In some embodiments, s is at least 3, 4, 5, 6, 7, 8, 9, or 10. In some embodiments, s is no greater than 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, or 10. HFPO- is typically present as a distribution or mixture of molecules having a range of values for s. Thus, s can be expressed as an average. Such average is typically not an integer.

[0045] Surface tension can be determined by dissolving the compound or mixture of compounds in a solvent and taking an image of a pendant drop supported by a needle (1.8 mm outer diameter) using a Kruess DSA 100 drop shape analyzer, using the Young-Laplace shape fitting feature of the Kruess Drop Shape Analysis Software version 1.9.2 and entering the density of the solvent (e.g., 1-methoxy-2-propanol having a density of 0.92 g / ml). In some embodiments, the compound i) has a surface tension that is less than that of 1-methoxy-2-propanol, which is 27.7 mN / m for a concentration ranging from 0.005 wt% to 10 wt% dissolved in 1-methoxy-2-propanol. The surface tension of the solution decreases with increasing concentration. The surface tension of the compound i) is typically no greater than 20 mN / m at a concentration of 0.5 wt% or 1 wt% dissolved in 1-methoxy-2-propanol. In some embodiments, the surface tension of the compound i) is no greater than 16.8 at a concentration of 6.7 wt% dissolved in 1-methoxy-2-propanol. Since the silane unit is typically a small weight fraction of the total molecular weight of the HFPO-functional urethanes compound comprising a perfluorooxyalkyl moiety and at least two (meth)acryloyl groups, it is expected that (e.g., Michael) addition of unit n to one or more silane groups will substantially increase the surface tension. Thus, the compounds described herein that also comprise one or more silane groups also have a surface tension within the range just described. A low surface tension facilitates the formation of a continuous coating on a (e.g., nano)structured surface free of defects such as air bubbles.

[0046] Many aliphatic or aromatic polyisocyanates can be used to make one or more fluorinated (meth)acryloyl silane urethane compounds as described. Such polyisocyanates can be diisocyanates having two NCO groups or polyisocyanates having three NCO groups. Non-limiting examples of polyisocyanate materials are commercially available such as Desmodur TM 3300, Desmodur TM TPLS 2294, and Desmodur TMN 3600, available from Bayer Polymers LLC of Pittsburgh, Pennsylvania. In some embodiments, the polyisocyanate used is based on hexamethylene diisocyanate (“HDI”). One commercially available HDI derivative is Desmodur TM N 100, available from Bayer Polymers LLC of Pittsburgh, Pennsylvania, is depicted below:

[0047]

[0048] The residue of the isocyanate has the same formula with the NCO group omitted. Thus, Desmodur TM The residue of N 100 is depicted below:

[0049]

[0050] One representative (meth)acryloyl-functional perfluorinated urethane compound prepared from Desmodur TM N 100 and HFPO oligomer amine, two equivalents of pentaerythritol triacrylate is depicted below:

[0051]

[0052] In some embodiments, the polyisocyanate can include a single polyisocyanate compound, such as a diisocyanate compound or a triisocyanate compound, or mixtures thereof. It should be understood that the polyisocyanate, especially the diisocyanate, can also include oligomers. Thus, R i The residue of the diisocyanate oligomer product can be included.

[0053] Some representative hexamethylene diisocyanate (“HDI”) oligomers are depicted below:

[0054]

[0055] The concentration of such oligomers is typically less than 40 wt%, 35 wt%, 30 wt%, 25 wt%, 20 wt%, 15 wt%, 10 wt%, or 5 wt%. Given the inclusion of oligomers, the number of isocyanate (-NCO) groups is typically an average. Thus, when a polyisocyanate is characterized as a triisocyanate, the majority of the compounds are triisocyanates. However, the average -NCO functionality is typically a non-integer greater than 3. For example, Desmodur TM 3300 is described as having a functionality of >3.2.

[0056] Thus, the reaction product comprises a mixture of compounds in which at least one amino silane or mercaptosilane has reacted with at least one of the (meth)acryl groups of the polyurethane compound comprising perfluorooxyalkyl moieties and at least two (meth)acryl groups.

[0057] In some embodiments of Formula 1, R i is a residue of a diisocyanate, m+n is on average 2, and a and p are each on average at least 1.

[0058] In other embodiments of Formula 1, R i is a residue of a triisocyanate, m+n is on average 3, n is on average 2, and for each n, a and p are each on average at least 1. Alternatively, wherein R i is a residue of a triisocyanate, m+n is on average 3, n is on average 2, wherein for a first n, a is on average 0 and p is on average 1; and for a second n, a is on average 1 and p is on average zero.

[0059] In other embodiments of Formula 1, R i is a residue of a polyisocyanate such that m+n is on average at least 4, 5, 6, 7, 8, 9, or 10; n is on average at least 3, 4, 5, 6, 7, 8, 9, or 10, wherein for at least one n, a is on average 0 and p is on average 1; and for at least one n, a is on average 1 and p is on average zero.

[0060] In mixtures also containing compounds of Formulae 2A-2C, the mole fraction of compounds according to Formula 1 that are unreacted with the amino or thiosilane is at least 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.15, 0.20, 0.25, 0.30, or 0.35 mole fraction. In mixtures also containing compounds of Formulae 2A-2C, the mole fraction of compounds according to Formula 1 that are unreacted with the amino or thiosilane is typically no more than 0.80, 0.70, 0.60, 0.50, or 0.40 mole fraction.

[0061] The silane compound is typically of the formula R 22 R 25 Si(Y) p (R 26 ) 3-p as defined in Formula 1 above. In typical embodiments, Y is a C1-C4 alkoxy group, and most typically a C1-C2 alkoxy group. R 26 is typically a C1-C6 alkyl group, an aromatic group such as phenyl, or hydrogen.

[0062] Examples of silane compounds comprising a hydrolysable group and an amine group include 3-aminopropyltrimethoxysilane (SILQUEST A-1110), 3-aminopropyltriethoxysilane (SILQUEST A-1100), N-methyl-3-aminopropyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane (DYNASYLAN 1189), bis(3-trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)n-methylamine, 3-(2-aminoethyl)aminopropyltrimethoxysilane (SILQUEST A-1120), SILQUEST A-1130, (aminoethylaminomethyl)-phenethyltrimethoxysilane, (aminoethylaminomethyl)-phenethyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane (SILQUEST A-2120), bis-(y-triethoxysilylpropyl)amine (SILQUEST A-1170), N-(2-aminoethyl)-3-aminopropyltributoxysilane, 6-(aminohexylaminopropyl)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-aminopropyl dimethyl methoxysilane, and 3-aminopropyl dimethyl ethoxysilane.

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

[0064] When the compound ii) comprises two silane groups, such as in the case of bis(3-trimethoxysilylpropyl)amine or bis(3-triethoxysilylpropyl)amine, for at least one n, R 5 is -R 2 Si(Y) b (R 3 ) 3-b .

[0065] Various other silane compounds comprising hydrolysable groups and amine or mercaptan groups are described in the literature.

[0066] Since the perfluorooxyalkyl groups of the starting polyurethane compound comprising at least two (meth)acryloyl groups comprise a mixture of perfluorooxyalkyl groups of various chain lengths, the resulting fluorinated silane compound also comprises a mixture of perfluorooxyalkyl groups of various chain lengths. The (e.g., number average) molecular weight of the compound (e.g., according to Formula 1) is typically no greater than 5000 g / mol, 4000 g / mol, 3000 g / mol, 2500 g / mol, 2000 g / mol, 1500 g / mol, 1000 g / mol, or 500 g / mol. In some embodiments, the (e.g., number average) molecular weight is at least 500 g / mol, 1000 g / mol, or 1500 g / mol. During synthesis of the compound, the molecular weight can be calculated from the equivalents of the reactants. Alternatively, the molecular weight of the coupling agent can be determined by nuclear magnetic resonance (NMR), liquid chromatography optionally followed by NMR, and / or mass spectrometry.

[0067] In some embodiments, the compound (e.g., according to Formulas 1 and 2) has an average fluorine weight % of at least 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, or 30 wt%. During synthesis of the compound, the fluorine weight % can be calculated from the reactants. Alternatively, the fluorine weight % can be calculated with combustion ion chromatography (CIC) as described in WO 2017 / 172390. In some embodiments, the compound has an average fluorine weight % of no greater than 50 wt%, 45 wt%, or 40 wt%.

[0068] Also described is a method of making a cured composition, the method comprising providing a (e.g., photo) polymerizable composition comprising a fluorinated (meth)acryloyl silane polyurethane compound as described herein; and curing the polymerizable composition.

[0069] In some embodiments, the polymerizable composition further comprises other non-fluorinated or fluorinated free-radically polymerizable monomers, oligomers, or combinations thereof.

[0070] In some embodiments, the fluorinated free-radically polymerizable oligomer is compound i) as previously described.

[0071] Useful non-fluorinated poly(meth)acrylate monomers and oligomers include:

[0072] (a) monomers containing di(meth)acryl groups, such as 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate (SR 238), 1,6-hexanediol monoacrylate monomethacrylate, ethylene glycol diacrylate, alkoxylated aliphatic diacrylates, alkoxylated cyclohexane dimethanol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycol diacrylate, caprolactone modified neopentyl glycol hydroxypivalate diacrylate, caprolactone modified neopentyl glycol hydroxypivalate diacrylate, cyclohexane dimethanol 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 glycol diacrylate, tricyclodecane dimethanol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate;

[0073] (b) monomers containing tri(meth)acryl groups, such as glyceryl triacrylate, trimethylolpropane triacrylate, ethoxylated triacrylates (e.g., ethoxylated trimethylolpropane triacrylate), propoxylated triacrylates (e.g., propoxylated glyceryl triacrylate, propoxylated trimethylolpropane triacrylate), trimethylolpropane triacrylate, tris(2-hydroxyethyl)-isocyanurate triacrylate;

[0074] (c) monomers containing higher functionality (meth)acryl groups, such as ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol tetraacrylate, and caprolactone modified dipentaerythritol hexaacrylate.

[0075] In some embodiments, the polymerizable composition comprises a monomer containing di(meth)acryl groups, such as 1,6-hexanediol diacrylate (SR 238), in an amount of at least 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt%.

[0076] Oligomeric (meth)acryl monomers, such as, for example, urethane acrylates, polyester acrylates, and epoxy acrylates, can also be employed.

[0077] In some embodiments, the polymerizable composition comprises an aliphatic polyurethane acrylate oligomer available under the trade designation PHOTOMER 6210 having a tensile strength of less than 10,000 kPa; an elongation of 30-50%; a modulus ranging from 50,000 kPa to 10,000 kPa; and a glass transition temperature ranging from 25°C to 50°C. The amount of oligo(meth)acryl monomer can be at least 50, 55, 60, 65, 70, or 75 weight percent.

[0078] Such (meth)acrylate monomers are widely available from suppliers such as, for example, Sartomer Company of Exton, Pennsylvania; Cytec Industries of Woodland Park, NJ; and Aldrich Chemical Company of Milwaukee, Wisconsin.

[0079] In typical embodiments, the (e.g., photo) polymerizable composition comprises one or more fluorinated (meth)acrylsilane polyurethane compounds as described herein in an amount of at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 weight percent solids. The amount of one or more fluorinated (meth)acrylsilane polyurethane compounds as described herein is typically no greater than 50 weight percent solids of the total polymerizable composition. The one or more fluorinated (meth)acrylsilane polyurethane compounds as described herein can be a single compound or a mixture of compounds as described herein.

[0080] The (meth)acryl groups are subjected to free radical curing by exposure to ultraviolet radiation (UV), electron beam (e-beam), ionizing radiation (gamma rays), plasma radiation, and thermal polymerization. In some embodiments, the method further comprises coating the polymerizable composition onto a substrate prior to curing. In some embodiments, upon radiation curing, the cured polymerizable composition forms a film or film layer, such as a film layer on a patterned surface of a tool.

[0081] In some embodiments, radiation curing comprises exposing the (e.g., coated) composition to wavelengths of ultraviolet light (UV) and visible light.

[0082] UV light sources can be of various types. Low intensity sources such as black light lamps typically provide in the range of 0.1 mW / cm2to 1 mW / cm2of UV light. Higher intensity sources such as mercury arc lamps typically provide in the range of 1 mW / cm2to 100 mW / cm2of UV light. 2 or 0.5 mW / cm2of UV light. 2(milliwatts per square centimeter) to 10 mW / cm 2 High intensity light sources typically provide intensities greater than 10 mW / cm 2 , 15 mW / cm 2 or 20 mW / cm 2 , up to 450 mW / cm 2 or more. In some embodiments, high intensity light sources provide intensities up to 500 mW / cm 2 , 600 mW / cm 2 , 700 mW / cm 2 , 800 mW / cm 2 , 900 mW / cm 2 or 1000 mW / cm 2 . UV light can be provided by a variety of light sources such as light emitting diodes (LEDs), fluorescent black lights, arc lamps such as xenon arc lamps, and medium and low pressure mercury lamps including germicidal lamps, microwave driven lamps, lasers, and the like or combinations thereof. The composition can also be polymerized with higher intensity light sources available from Fusion UV Systems Inc. Lamps that emit ultraviolet or blue light are generally preferred. The UV exposure time for polymerization and curing can vary depending on the intensity of the light source used. For example, curing with low intensity light sources can be accomplished in exposure times ranging from about 30 seconds to 300 seconds; whereas, curing with high intensity light sources can be accomplished in shorter exposure times ranging from about 1 second to 20 seconds.

[0083] In other embodiments, an article is described that includes a film or film layer comprising a cured polymerizable composition comprising one or more fluorinated (meth)acryloyl silane urethane compounds described herein. As previously described, the polymerizable composition further comprises one or more non-fluorinated or fluorinated free radically polymerizable monomers, oligomers, or combinations thereof.

[0084] In some embodiments, the film layer is disposed on a surface of a substrate. In some embodiments, the film layer is disposed on a (e.g., nanostructured) patterned surface. The surface of the substrate can include a metal oxide.

[0085] In some embodiments, the cured polymerizable composition can be cured by exposure to UV light having an intensity in the range of from about 0.1 mW / cm FIG. 1N - FIG. 1Vand as a mask layer (1150) in the method of forming an etched nanoscale pattern as described in FIGS. 11N-11V of WO 2020 / 095258 (incorporated herein by reference).

[0086] Referring to FIG. 1N - FIG. 1V In other exemplary embodiments, a method of forming an etched nanoscale pattern generally includes: (n) providing a substrate (1116) having a patterned surface (1118) including one or more recessed features (1124), each recessed feature adjoining at least one plateau structure (1122) extending away from the recessed feature; providing a first substrate (1110) having a first etch resist layer (1114), (o) superposing the first etch resist layer (1114) with a transfer layer (1160), (p) superposing the transfer layer (1160) with a second etch resist (1114'), optionally superposing an anti-stick coating (1145) on the patterned surface (1118), (q) optionally superposing an adhesion promotion layer (1132) on the second etch resist (1114'), superposing a mask layer (1150) on the patterned surface (1118) with the optional anti-stick coating (1145); (r) superposing the mask layer (1150) with the second etch resist (1114'); (s) removing the patterned surface of the first substrate (1110) from the second etch resist material (1114'); (t) etching the patterned surface to expose the second etch resist layer (1114'), and (u) selectively etching the patterned surface of the second etch resist layer (1114') to remove at least a portion of the second etch resistant material, optionally etching to the transfer layer (1160), optionally etching to the surface of the first etch resist layer (1114), thereby forming an etched nanoscale pattern (1120). In some embodiments, the etched nanoscale pattern includes a plurality of nanoscale features. In some embodiments, the etched nanoscale pattern can then be filled with a high refractive index material (1126) as shown in FIG. 1V In certain such embodiments, each nanoscale feature exhibits at least one dimension of 1 nm to 900 nm. In certain exemplary embodiments, at least one of the first substrate and the second substrate is flexible.

[0087] A polymerizable composition as described herein can be used as the etch resist-adhered mask layer (1150), the polymerizable composition comprising one or more fluorinated (meth)acryloyl silane polyurethane compounds.

[0088] Materials for the etch resist (e.g., etch block) layer 1114 or 1114' can be, but are not limited to, Si x C y H z (x = 1, y = 1-4, z = 1-4), or Si x Cy N z H n (x = 1, y = 1-4, z = 0-1, n = 1-4), Si x N y (x = 1, y = 0-1), SiO x (x = 1-2), Si x O y N z (x = 1, y = 1-2, z = 0-1), SiH x (x = 1-4), etc.

[0089] Thus, the polymerizable compositions as described herein exhibit good adhesion to siliceous (i.e., silicon-containing) materials and are proven to exhibit good adhesion to other metal oxides and inorganic materials such as zirconia, alumina, and titania materials, and combinations of such materials, comprising one or more fluorinated (meth)acryloyl silane polyurethane compounds. When the polymerizable compositions are used as a mask layer, they release from (e.g., nanostructured) patterned surfaces such as release-treated stencil films (1116, 1118, and 1145).

[0090] The following examples are provided to further illustrate the presently described invention.

[0091] The following examples are provided to further illustrate the presently described invention.

[0092] Table 1. Materials

[0093]

[0094]

[0095] Preparation of perfluoropolyether polyurethane acrylate from Michael addition of silane to perfluoropolyether polyurethane acrylate Silane

[0096] The approximate acrylate equivalent weight of Des N100 / 0.90 PET3A / 0.15 HFPO was calculated. One preparation of this material used the following equivalent weights of materials. Desmodur N100, 191 EW (equivalent weight), approximately trifunctional.

[0097] Pentaerythritol triacrylate (SR444C), EW 500. HFPO amine (HFPO-C(O)NHCH2CH2OH), EW 1371.

[0098] The reaction product of all three reactants comprises a compound having the following structure:

[0099]

[0100] The calculated MW of this structure is 3*191 + 1371 + 2*500 = 2944 g / mole. This structure has 6 acrylate esters, so its acrylate ester EW is 2922 / 6 = 490.66 g / mole.

[0101] The reaction product of Des N100 and PET3A contains a compound having the following structure:

[0102]

[0103] Its MW is 3*191 + 3*500 = 2073. This structure has 9 acrylate esters, so its acrylate ester EW is 2073 / 9 = 230.33.

[0104] Since the mixture of compounds contains 15% of material with HFPO amine and 85% of material without HFPO amine (0.05 equivalents of PET3A is not accounted for), the average acrylate ester EW of the mixture of compounds is: 0.15*490.66 + 0.85*230.33 = 269.38 or about 270 acrylate ester EW.

[0105] Des Formulation A (1900) of N100 / 0.90 PET 3A / 0.15 HFPO + 0.11 mole fraction of acrylate functionality reacted with N-methyl-3-aminopropyltrimethoxysilane (N-Me-APTMS) Des

[0106] A 5.5 mL vial equipped with a stir bar was charged with 1 g of a 65% solids solution of Des N100 / 0.90 PET3A / 0.15 HFPO (0.00240 acrylate equivalents) in acetone (dried over 4A molecular sieves) and 0.0503 g (0.00026 equivalents) of N-methyl-3-aminopropyltrimethoxysilane (N-Me-APTMS). The reaction was stirred at room temperature for 1 to 1.25 hours. About 0.25 g of the reaction product was weighed into a vial along with 0.4 g of deuterium-acetone and 1 H FTNMR showed the reaction was complete.

[0107] Formulation B (1901) of N100 / 0.90 PET 3A / 0.15 HFPO + 0.32 mole fraction of acrylate functionality reacted with bis-(propyltrimethoxysilyl)amine (B-PTMS) Des Formulation C (1902) of N100 / 0.90 PET 3A / 0.15 HFPO + 0.32 mole fraction of acrylate functionality reacted with bis-(propyltrimethoxysilyl)amine (B-PTMS)

[0108] Formulation B was performed according to the procedure of Formulation A with 1 g of a 65% solids solution of Des N100 / 0.90 PET3A / 0.15 HFPO (0.00240 acrylate equivalents) in acetone (dried over 4A molecular sieves) and 0.151 g (0.00078 equivalents) of N-methyl-3-aminopropyltrimethoxysilane (N-Me-APTMS). 1 H FTNMR analysis showed the reaction was complete.

[0109] DesFormulation D of N100 / 0.90 PET 3A / 0.15 HFPO + 0.11 mole fraction of acrylate functionality reacted with (3-mercaptopropyl)trimethoxysilane (MPTMS) Table 2. Solvent-based coating solutions

[0110] Formulation C was performed according to the procedure of Formulation A using 1 g of Des N100 / 0.90 PET 3A / 0.15 HFPO (0.00240 acrylic equivalents) in acetone (dried over 4A molecular sieves) at 65% solids and 0.2664 g (0.00078 equivalents) of bis-(propyltrimethoxysilyl)amine (B-PTMS), where 1 H FT NMR analysis showed the reaction to be about 25-30% complete.

[0111] FIG. 2P - FIG. 2S FIG. 1N - FIG. 1V FIG. 2P - FIG. 2S

[0112] Formulation D can be performed according to the procedure of Formulation A using 1 g of Des N100 / 0.90 PET 3A / 0.15 HFPO (0.00240 acrylic equivalents) in acetone (dried over 4A molecular sieves) at 65% solids and 0.0510 g (0.00026 equivalents) of (3-mercaptopropyl)trimethoxysilane (MPTMS) and 0.0026 g (5 wt% relative to MPTMS) of diisopropylethylamine (Hunig’s base).

[0113] Formulations A and B were combined with a polymerizable resin comprising 75 wt% Photomer 6210, 25 wt% SR238, and 0.5% TPO, solvents (MEK and PGME), and compound i) in the amounts described below in Table 2.

[0114] FIG. 1R

[0115]

[0116] The coating solutions of Table 2 were used as mask layers (1150) in a method of forming etched nanoscale patterns according to FIG. 1S .

[0117] In typical embodiments, the method will include a first etch resist (1114) and a transfer layer (1160) as described in WO 2020 / 095258 and above Table 3. Replicated results using controls (100% HFPO . However, in this particular experimental set, the first etch resist (1114) and transfer layer (1160) were omitted, such that adhesion failures between the mask layer (1150) and the second etch resist (1114’) were isolated from adhesion failures between other layers.

[0118] Reference is made to UA) and different levels of Formulations A and B, the base (1110) is a PET film (Melinex ST505 by Du Pont Teijin Films, Chester, VA, United States) coated via plasma enhanced chemical deposition (PECVD) to form a silicon-containing etch resist (1114’) having a composition (SiC x O y ) of 50 / 50 / 0. The roll-to-roll PECVD process is described in WO 2020 / 095258, Example 6, step 3, modified in that the base pressure is 0.9 mT (0.1 Pa), the oxygen flow rate is 2000 seem for the first treatment and 1000 seem for the second treatment.

[0119] Nanofeature template films (1116 and 1118) were prepared by die coating a polymerizable resin (comprising PHOTOMER 6210, SR238, SR351, and TPO in a weight ratio of 60 / 20 / 20 / 0.5) onto a 125-micrometer thick polycarbonate film (1116). The coated film was pressed against a nanostructured nickel surface attached to a steel roller controlled at a speed of 15.2 meters / minute using a rubber-covered roller at 60 °C. The nanostructured nickel tool consisted of twelve 6 mm x 6 mm patterned areas with features ranging in size between 75 nm and 500 nm. The patterned areas consisted of a multi-pitch pattern with pitches of 150 nm, 200 nm, and 250 nm and a width of the features that was half of the pitch (75 nm, 100 nm, 125 nm).

[0120] The features were arranged in a square grid such that the pitch varied in two axes, resulting in nine unit repeat cells of rectangles with all combinations of the above widths. In this repeat cell, the 150 nm pitch portion had 27 features, the 200 nm pitch portion had 20 features, and the 250 nm pitch portion had 16 features. The features were about 200 nm tall and had a sidewall angle of about 4 degrees.

[0121] The coating thickness of the polymerizable resin on the film was sufficient to completely wet the nickel surface and form a rolling bead of resin upon pressing the coated film against the nanostructured nickel surface. The film was exposed to radiation from two Fusion UV lamp systems (available under the trade designation "F600" from Fusion UV Systems, Gaithersburg, MD) fitted with D bulbs, both operating at 142 W / cm, while in contact with the nanostructured nickel surface. After the film was peeled away from the nanostructured nickel surface, the nanostructured side of the film was again exposed to radiation from the Fusion UV lamp systems.

[0122] The release layer (1145) was deposited on the nano-feature template film by plasma enhanced chemical vapor deposition (PECVD) with a release composition as described in WO 2020 / 095258. The PECVD process is described in Example 3, Step 2 of WO 2020 / 095258, modified in that the base pressure was 0.9 mT (0.1 Pa), the oxygen flow rate was 2000 seem for the first treatment and 1000 seem for the 2nd treatment.

[0123] Referring to FIG. 11Q, the release treated template film (1116, 1118, and 1145) was coated with the acrylate solution of Table 2 at 0.05 meters / second slot die to form a mask layer 1150. The solution was coated 10.16 cm wide and pumped at a rate of 1.2 seem with a Harvard syringe pump. The coating was partially cured 1.5 meters from the solution application using a 405 nm UV-LED system powered at 0.25 amperes at 40 volts. The coating was subjected to approximately 0.01 W / cm 2 to 0.005 W / cm 2 irradiance.

[0124] The film was then dried under ambient conditions for 3 minutes prior to entering the nip. At the nip, the release treated nanostructured template film was introduced from an auxiliary feed and laminated with the etch resist (1114') placed on the base (1110). The nip consisted of a rubber roll with a hardness of 90 and a steel roll set at 54 °C. The nip was engaged by two Bimba air cylinders set at 0.28 MPa pressure.

[0125] The solution was cured using a Fusion D bulb and the cured acrylate mixture mask layer (1150) was separated from the release treated template film that remained on the 3 layer film in the entire 6 mm x 6 mm patterned area. The web tension was set to approximately 0.0057 N / m.

[0126] As Coating solution name and Composition of release layerAs depicted in the middle, the mask layer (1150) is bonded with the etch resist material (1114') and released from the release treated template film (1116, 1118, and 1145). The pattern of the etch resist material (1114') is evaluated to determine the pattern transfer quality according to the following ranking:

[0127] 0 - No pattern transfer to the substrate

[0128] 1 - Large pattern transfer failure (> 50% pattern transfer failure)

[0129] 2 - Small pattern transfer failure (slight failure or tearing of the pattern around the edges)

[0130] 3 - Complete pattern transfer

[0131] Ranking AA

[0132] 100% HFPO polyurethane acrylate BB 50% Formulation A 50% HFPO polyurethane acrylate CC 100% Formulation A 1 DD 50% Formulation B 50% HFPO polyurethane acrylate 2 EE 100% Formulation B 3 ​ ​ 2 ​ ​ 3

Claims

1. A compound comprising a perfluorinated group and a hydrolysable silane group, the compound having the formula: wherein: Q is independently an organic linking group of valence at least 2; X is O, S, or NR, wherein R is H or an alkyl group having 1 to 4 carbons; Y is a hydrolysable C1-C2 alkoxy group; b is 1, 2, or 3; m is at least 1; n is at least 1; for each n, p + a is no greater than 6, provided that for at least one n, a is at least 1; and for at least one n, p is at least 1. R i is a residue of a polyisocyanate; R f is a monovalent perfluorooxyalkyl group having the formula CF3CF2CF2O-[CF(CF3)CF2O] s -CF(CF3)-, wherein s is an integer from 2 to 25; 4. The compound of claim 1, wherein m + n is on average 2 to 10.

9. A mixture of compounds comprising a Michael addition reaction product of: i) a polyurethane compound comprising a perfluorooxyalkyl moiety and at least two (meth)acryloyl groups; and ii) a silane compound comprising a hydrolysable group and a group selected from an amine or a mercapto group; wherein i) and ii) are reacted in an equivalent ratio of compound i) in excess such that the (meth)acryloyl groups remain unreacted, wherein the Michael addition reaction product comprises a compound according to any one of claims 1 to 8. R 4 is H or CH3; R 1 is -S- or -N(R 5 )-, wherein R 5 is C1-C4 alkyl or -R 2 Si(Y) b (R 3 ) 3-b ; R 2 is a divalent alkylene radical optionally containing carbon atoms of the carbon chain substituted with one or more oxygen atoms; 10. The mixture of compounds of claim 9, wherein the equivalent ratio of i) to ii) is in the range of 2: 1 to 10:

1. R 3 is a non-hydrolysable group; 11. The mixture of compounds of claim 9, wherein the mixture comprises one or more compounds according to claim 1.

12. The mixture of compounds of claim 9, wherein the mixture of compounds further comprises unreacted compound i).

13. The mixture of compounds of claim 9, wherein compound i) has the formula:

15. A method of making a cured composition, the method comprising: providing a polymerizable composition comprising a compound according to any one of claims 1 to 8 or a mixture of compounds according to any one of claims 9 to 14 in an amount no greater than 50 weight percent solids of the total polymerizable composition; curing the (meth)acryloyl groups of the polymerizable composition.

16. The method of claim 15, wherein the polymerizable composition further comprises one or more non-fluorinated or fluorinated free-radically polymerizable monomers, one or more non-fluorinated or fluorinated free-radically polymerizable oligomers, or a combination thereof.

17. The method of claim 15, wherein the curing comprises radiation curing.

2. The compound according to claim 1, wherein R i is a residue of a polyisocyanate selected from diisocyanate compounds and triisocyanate compounds.

3. The compound of claim 1, wherein R i including residues of diisocyanate oligomerization products.

18. The method of claim 15, wherein the cured polymerizable composition forms a film layer on a patterned surface.

5. The compound of claim 1, wherein R i is a residue of a diisocyanate, m + n is on average 2, and a and p are both on average at least 1.

6. The compound of claim 1, wherein R i is the residue of a triisocyanate, m + n is on average 3, n is on average 2, and a and p are on average at least 1 for each n.

7. The compound of claim 1, wherein R i is the residue of a triisocyanate, m+n is on average 3, n is on average 2, wherein for the first n, a is 0 and p is on average 1; and for the second n, a is on average 1 and p is on average zero.

8. The compound of claim 1, wherein R i is a residue of a polyisocyanate such that m + n is on average at least 4, 5, 6, 7, 8, 9, or 10; n is on average at least 3, 4, 5, 6, 7, 8, or 9, wherein for at least one n, a is on average 0 and p is on average 1; and for at least one n, a is on average 1 and p is on average zero.

19. The method of claim 18, wherein the film layer is a mask layer.

20. The method of claim 19, wherein the pattern comprises a nanostructure.

21. An article comprising: a film or film layer comprising a cured polymerizable composition comprising a compound according to any one of claims 1 to 8 or a mixture of compounds according to any one of claims 9 to 14. ​ ​ ​ ​ ​ ​ [R f QXC(O)HN)] m2 -R i -[NHC(O)OQ(XC(O)C(R 4 )=CH2) p2 ] n2 wherein the symbols have the same meaning as in claim 1 and p2 is 1-6 and n2 is at least 1, with the proviso that if p2 is 1, n2 is at least 2, and m2 + n2 is on average 2 to 10.

14. A mixture of compounds according to claim 9, wherein the compound ii) comprises two silane groups and for at least one n, R 5 is -R 2 Si(Y) b (R 3 ) 3-b wherein the symbols have the same meaning as in claim 1. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ 22. The article of claim 21, wherein the polymerizable composition further comprises one or more non-fluorinated or fluorinated free-radically polymerizable monomers, one or more non-fluorinated or fluorinated free-radically polymerizable oligomers, or a combination thereof.

23. The article of claim 21, wherein the film layer is disposed on a surface of a substrate.

24. The article of claim 21, wherein the film layer is disposed on a patterned surface.

25. The article of claim 24, wherein the pattern comprises nanostructures.

26. The article of claim 23, wherein the surface of the substrate comprises a metal oxide.

Images