WO2015142562A1

WO2015142562A1 - Method of preparing non-aqueous emulsion, non-aqueous emulsion prepared thereby, and methods of preparing surface-treated articles

Info

Publication number: WO2015142562A1
Application number: PCT/US2015/019566
Authority: WO
Inventors: Michael L. Bradford; William James Schulz, Jr.
Original assignee: Dow Corning Corporation
Priority date: 2014-03-17
Filing date: 2015-03-10
Publication date: 2015-09-24
Also published as: TW201600571A

Abstract

A method of preparing a non-aqueous emulsion comprises combining an organic vehicle and an additive compound to form an organic mixture. The method further comprises combining the organic mixture and a polyfluoropolyether silane, thereby preparing the non-aqueous emulsion. The non-aqueous emulsion comprises a continuous organic phase comprising the organic vehicle. The non-aqueous emulsion further comprises a discontinuous phase comprising the polyfluoropolyether silane. Methods of preparing surface treated articles therewith are also disclosed.

Description

METHOD OF PREPARING NON-AQUEOUS EMULSION, NON-AQUEOUS

EMULSION PREPARED THEREBY, AND METHODS OF PREPARING

SURFACE-TREATED ARTICLES

FIELD OF THE INVENTION

[0001] The invention generally relates to a method of preparing a non-aqueous emulsion and, more specifically, to a method of preparing a non-aqueous emulsion for treating a surface, the non-aqueous emulsion formed thereby, and methods of preparing surface treated articles with the non-aqueous emulsion.

DESCRIPTION OF THE RELATED ART

[0002] An "emulsion" generally is a fluid colloidal system in which liquid droplets and/or liquid crystals are dispersed in a liquid. The majority of known emulsions are aqueous emulsions. "Colloidal" generally refers to a state of subdivision, wherein (macromolecular) molecules or polymolecular particles are dispersed in a medium and wherein the molecules or particles have, at least in one direction, a dimension roughly between 1 nanometer (nm) and 1 micrometer (μηι). A "colloidal dispersion" generally is a system in which particles of colloidal size of any nature (e.g. solid, liquid or gas) are dispersed in a continuous phase of a different composition (or state). A "dispersion" as used in polymer science generally is a material comprising finely divided phase domains and a continuous phase domain, where the finely divided phase domains are distributed throughout the continuous phase domain of the dispersion. The finely divided phase domains are often, but not always, in the colloidal size range. Thus, an emulsion is a subtype of a colloidal dispersion, and a colloidal dispersion is a subtype of a dispersion. Not all dispersions are colloidal dispersions and not all colloidal dispersions are emulsions.

[0003] The Tyndall effect is seen when light-scattering particulate-matter is dispersed in an otherwise-light-transmitting medium, when the cross-section of an individual particulate is the range of roughly between 40 nm and 900 nm, i.e., somewhat below or near the wavelength of visible light (400 nm to 750 nm). The effect may be observed as giving a blue tint to the medium. The particle size range of 40 nm to 900 nm giving the Tyndall effect is a subset of the particle size range of 1 nm to 1 ,000 nm giving emulsions. Thus, not all emulsions are able to exhibit the Tyndall effect. Further, of the emulsions that are able to exhibit the Tyndall effect, not all of those emulsions are able to exhibit the Tyndall effect for a period of time. In order to exhibit the Tyndall effect for a period of time, an emulsion must have a degree of stability so that an observer could have time to detect it. That is, the emulsion must not be transitory (i.e., lifetime < 1 second) and must not promptly collapse after being formed. An unstable emulsion, once formed, would promptly collapse and thus be unable to exhibit the Tyndall effect for a period of time.

[0004] Surfaces of electronic and optical devices/components are susceptible to staining and smudging, oftentimes due to oils from hands and fingers. For example, electronic devices including an interactive touch-screen display, e.g. smart phones, are generally smudged with fingerprints, skin oil, sweat, cosmetics, etc., when used. Once these stains and/or smudges adhere to the surfaces of these devices, the stains and/or smudges are not easily removed. Moreover, such stains and/or smudges decrease the usability of these devices.

[0005] In an attempt to minimize the appearance and prevalence of such stains and smudges, conventional surface treatment compositions have been applied on the surfaces of various devices/components to form conventional layers thereon. Such conventional surface treatment compositions typically consist of a fluorinated polymer and a solvent. However, the solvents utilized in such conventional surface treatment compositions are typically limited to halogenated (e.g. fluorinated) solvents to properly solubilize the fluorinated polymer, and such halogenated solvents are comparatively expensive. Moreover, these halogenated solvents may have undesirable environmental profiles. Alternative solvents, such as organic solvents, are generally incapable of solubilizing fluorinated polymers. When the fluorinated polymers are not properly dispersed or homogeneous within conventional treating surface treatment, resulting physical properties of the conventional layers formed therefrom suffer.

SUMMARY OF THE INVENTION AND ADVANTAGES

[0006] The invention provides a method of preparing a non-aqueous emulsion. The method comprises combining an organic vehicle and an additive compound to form an organic mixture. The method further comprises combining the organic mixture and a polyfluoropolyether silane, thereby preparing the non-aqueous emulsion. The non-aqueous emulsion comprises a continuous organic phase comprising the organic vehicle. The nonaqueous emulsion further comprises a discontinuous phase comprising the polyfluoropolyether silane.

[0007] The invention also provides a non-aqueous emulsion formed by the method.

[0008] Further, the invention provides methods of preparing a surface-treated article. In a first method, the non-aqueous emulsion is applied to a surface of an untreated article to form a wet layer thereof on the surface of the untreated article. The first method further comprises removing the organic vehicle from the wet layer to form a layer on the surface of the untreated article and give the surface-treated article. In a second method, the non-aqueous emulsion and a pellet are combined to form an impregnated pellet. The second method further comprises removing the organic vehicle from the impregnated pellet to form a neat pellet. The second method also comprises forming a layer on a surface of an untreated article with the neat pellet via a deposition apparatus.

[0009] The non-aqueous emulsion forms layers that are easy to clean and which have excellent physical properties, including stain and smudge resistance. Further, the layers formed from the non-aqueous emulsion may be formed at a fraction of the cost of conventional surface treatment compositions while still providing excellent and desirable physical properties.

DETAILED DESCRIPTION OF THE INVENTION

[0010] The invention provides a method of preparing a non-aqueous emulsion, the nonaqueous emulsion formed thereby, and methods of preparing surface-treated articles with the non-aqueous emulsion. The non-aqueous emulsion forms layers that are easy to clean and which have excellent physical properties, including smudge and stain resistance. Further, the layers formed from the non-aqueous emulsion have a significantly reduced cost and more favorable toxicological and environmental profiles as compared to conventional layers formed from conventional compositions including fluorinated polymers and halogenated solvents. In addition, the inventive method of preparing the non-aqueous emulsions allows for incorporation of additive compounds in the non-aqueous emulsions while maintaining excellent stability.

[0011] The method of preparing the non-aqueous emulsion comprises combining an organic vehicle and an additive compound to form an organic mixture. The organic mixture is referred to as such in view of the organic vehicle therein, although the additive compound need not be organic itself, as described below. The organic vehicle constitutes a continuous phase of the non-aqueous emulsion once formed. As described below, the non-aqueous emulsion includes a discontinuous phase comprising a polyfluoropolyether silane. By "non-aqueous," it is meant that water does not constitute either the continuous or the discontinuous phase of the non-aqueous emulsion. It has been surprisingly found that the method by which the components are combined to prepare the non-aqueous emulsion impacts significantly the physical properties thereof. In fact, merely combining the components, even in the presence of a shear force, e.g. a vortex, generally will not prepare the non-aqueous emulsion absent the steps of the inventive method. For example, merely combining the components may result in a heterogeneous mixture prone to settling and instability, rather than the nonaqueous emulsion.

[0012] The organic vehicle and the additive compound may be combined via various techniques. For example, the additive compound may be disposed in the organic vehicle, the organic vehicle may be disposed in the additive compound, both the additive compound and the organic vehicle may be simultaneously disposed in a vessel, etc. If desired, the organic vehicle and the additive compound may be mixed, e.g. by vortex or other techniques, to disperse the additive compound in the organic vehicle to give the organic mixture. Typically, as described below, the polyfluoropolyether silane is combined with a fluorinated vehicle to pre-form a fluorinated composition prior to combining the organic mixture and the polyfluoropolyether silane. In these embodiments, combining the organic mixture and the polyfluoropolyether silane comprises combining the organic mixture and the fluorinated composition. The organic mixture and the fluorinated composition may be combined in any manner, such as those described above with reference to the additive compound and the organic vehicle.

[0013] The organic vehicle of the continuous phase may be any organic vehicle capable of emulsifying the polyfluoropolyether silane. The organic vehicle is generally referred to as an organic vehicle as opposed to an organic solvent because the organic vehicle need only disperse or emulsify the discontinuous phase (and any other components of the continuous phase, if present), but not solubilize the discontinuous phase (or the continuous phase). The organic vehicle may alternatively be referred to as an organic solvent when the components of the continuous phase solubilize therein, which is desirable.

[0014] In certain embodiments, the organic vehicle is selected such that the non-aqueous emulsion exhibits the Tyndall effect for a period of time. That is, the organic vehicle is a substance that enables the non-aqueous emulsion to exhibit the Tyndall effect for a period of time. The Tyndall effect, which is also referred to as Tyndall scattering, is understood in the art to refer to light scattering by particles in a certain size range in a colloid or emulsion. More specifically, under the Tyndall effect, shorter-wavelength light is reflected via scattering, whereas longer-wavelength light is transmitted. In the non-aqueous emulsion, the light scattering is generally attributable to the discontinuous phase, which is present in the form of dispersed particles in the continuous phase. In particular, the organic vehicle of the continuous phase is generally a light-transmitting medium, whereas the polyfluoropolyether silane of the discontinuous phase is generally a light-scattering medium. Techniques for easily screening organic vehicles to determine suitability thereof and whether a particular organic vehicle will result in a non-aqueous emulsion exhibiting the Tyndall effect for a period of time are described below.

[0015] Various classes of organic vehicles are suitable for the continuous phase of the nonaqueous emulsion. For example, the organic vehicle may be aliphatic, aromatic, cyclic, alicyclic, etc. Although the organic vehicle is generally derived from a hydrocarbon, the organic vehicle may include ethylenic unsaturation and may be substituted or unsubstituted. By "substituted," it is meant that one or more hydrogen atoms of the organic vehicle may be replaced with atoms other than hydrogen (e.g. a halogen atom, such as chlorine, fluorine, bromine, etc.) or substituents other than hydrogen (e.g. a carbonyl group, an amine group, etc.), or a carbon atom within the organic vehicle may be replaced with an atom other than carbon, i.e., the organic vehicle may include one or more heteroatoms, such as oxygen, sulfur, nitrogen, etc.

[0016] In certain embodiments, the organic vehicle comprises an ester. Specific examples of esters suitable for the purposes of the organic vehicle include n-butyl acetate, t-butyl acetate, methyl 10-undecenoate, t-butyl acetoacetate, isoamyl acetate, dimethyl fumarate, diethyl fumarate, propylene glycol monomethyl ether acetate, and combinations thereof. In other embodiments, the organic vehicle comprises a ketone. Specific examples of ketones suitable for the purposes of the organic vehicle include acetone, t-butyl acetoacetate (which constitutes both an ester and a ketone), methyl isobutyl ketone, 2-pentanone, 2-butanone, acetylacetone, and combinations thereof. The continuous phase of the non-aqueous emulsion may comprise combinations of esters, combinations of ketones, combinations of esters and ketones, or a ketone and/or an ester in combination with another organic vehicle and/or solvent.

[0017] The organic vehicle is not limited to esters or ketones. For example, in various embodiments, the organic vehicle is selected from the group consisting of t-butyl acetate, acetone, tetrahydrofuran, n-butyl acetate, dimethyl sulfoxide, methylene chloride, diglyme, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl 10-undecenoate, dimethylformamide, t-butyl acetoacetate, methyl isobutyl ketone, 2-pentanone, 2-butanone, acetylacetone, limonene, xylene, propylene carbonate, isopropanol, 1 -methoxy-2-propanol, propylene glycol monomethyl ether acetate, isoamyl acetate, diethyl fumarate, t-butanol, 1 - butanol, t-butyl methyl ether, toluene, ethylene glycol, and combinations thereof. [0018] In specific embodiments, the organic vehicle is selected from the group consisting of acetone, dimethyl sulfoxide, methylene chloride, xylene, n-butyl acetate, propylene carbonate, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl isobutyl ketone, isoamyl acetate, diethyl fumarate, t-butanol, 2-butanone, tetrahydrofuran, t- butyl acetate, and combinations thereof. In other specific embodiments, the organic vehicle is selected from the group consisting of acetone, n-butyl acetate, triethylene glycol dimethyl ether, methyl isobutyl ketone, 2-pentanone, 2-butanone, tetrahydrofuran, t-butyl acetate, and combinations thereof.

[0019] The additive compound is different from the organic vehicle and the polyfluoropolyether silane. Further, the additive compound is also different from the fluorinated vehicle, which may optionally be present in the discontinuous phase of the nonaqueous emulsion, as introduced above.

[0020] The additive compound is generally selected to modify at least one physical property of the non-aqueous emulsion and/or the layers formed from the non-aqueous emulsions. The additive compound may vary based on the desired physical property to be modified.

[0021] Specific examples of the additive compound include siloxane polymers, drying agents, reactive silanes, and combinations thereof. A suitable, non-limiting example of a typical siloxane polymer is trialkoxysilyl endblocked polydimethylsiloxane, and a suitable, non-limiting example of a reactive silane is dimethyldimethoxysilane.

[0022] In certain embodiments, the additive compound comprises a siloxane polymer. The siloxane polymer comprises repeating R2S1O2/2 units, where each R is an independently selected C-1 -C22 hydrocarbyl group. R may be linear, branched, or cyclic. In addition, R may include heteroatoms within the hydrocarbyl group, such as oxygen, nitrogen, sulfur, etc., and may be substituted or unsubstituted. For example, R may be substituted with one or more halogen atoms (e.g. independently CI, F, Br, etc.). Typically, R is C-1 -C4 alkyl group.

[0023] Because the siloxane polymer comprises repeating R2S1O2/2 units, the siloxane polymer has a linear portion or moiety. However, the siloxane polymer may optionally be branched and/or may include a resinous portion having a three-dimensional networked structure. In such embodiments, the siloxane polymer further comprises includes RS1O3/2 units and/or S1O4/2 units. R2S1O2/2 units are generally referred to as D units, RS1O3/2 units are generally referred to as T units, and S1O4/2 units are generally referred to as Q units. Branching of the siloxane polymer itself, or the resinous portion of the siloxane polymer, if present, is attributable to the presence of T and/or Q units.

[0024] The siloxane polymer may consist of siloxane bonds (Si-O-Si) within the backbone of the siloxane polymer. Alternatively, the siloxane polymer may include siloxane bonds separated by one or more bivalent groups, e.g. a CH2 linking group, where CH2 may be repeated up to, for example, 10 times. The presence of absence of such bivalent groups is generally attributable to the reaction mechanism by which the siloxane polymer is formed, with siloxane polymers consisting of siloxane bonds being formed from condensation and siloxane polymers including one or more bivalent groups being formed from hydrosilylation.

[0025] In addition to groups represented by R, the siloxane polymer may include additional substituents or functional groups at any terminal or pendant position. For example, the siloxane polymer may include silicon-bonded alkenyl groups, silicon-bonded hydroxyl groups, silicon-bonded alkoxy groups, etc. Such groups or atoms may be present in the repeating D units (described below) or in terminal M units (which generally have the formula R3S1O-1 /3, unless one or more of R is replaced by one of these additional substituents or functional groups). In various embodiments including such functional groups, the functional groups may be terminal, pendant, or both. Typically, the functional groups are terminal. For example, the siloxane polymer may be dimethylvinyl endblocked, divinylmethyl endblocked, dimethylhydroxyl endblocked, dihydroxylmethyl endblocked, etc. In certain embodiments, the siloxane polymer includes a terminal group selected from a hydrolysable group, an alkenyl group, of combinations thereof. Generally, physical properties of the layers formed from the non-aqueous emulsions are improved when the siloxane polymer includes such a terminal group.

[0026] In various embodiments in which the siloxane polymer is linear, the siloxane polymer has the following general formula (A):

(X)3-a(R)a-Si-(CH₂)b-(0)^

0)_k-SiR₂)|-(0)_m-(CH2)n-Si-(X)3-p(R)_p;

wherein X is an independently selected hydrolysable group; R is defined above; a and p are each integers independently selected from 0 to 3; b, f, i, and n are each integers independently selected from 0 to 10; c and m are each independently 0 or 1 ; d, g, and k are each integers independently selected from 0 or from 1 to 2,000 with the proviso that d, g, and k are not simultaneously 0; e, h, and I are each integers independently selected from 0 and 1 with the proviso that e, h, and I are not simultaneously 0; and j is an integer selected from 0 to 5; provided that when subscript d is 0, subscript e is also 0; when subscript d is greater than 0, subscript e is 1 ; when subscript g is 0, subscripts h, i, and j are also 0; when subscript g is greater than 1 , subscript h is 1 and subscript j is at least 1 ; when subscript k is 0, subscript I is also 0; and when subscript k is greater than 0, subscript I is 1 .

[0027] The hydrolysable groups represented by X in general formula (A) are independently selected from H, a halide, -OR¹ , -NHR¹ , -NR¹ R², -OOC-R¹ , 0-N=CR¹ R², 0-C(=CR¹ R²)R³, and -NR¹ COR², wherein R¹ , R² and R³ are each independently selected from H and a C1 -C22 hydrocarbon group, and wherein R¹ and R², together with the nitrogen atom to which they are both bonded in -NR¹ R², optionally can form a cyclic amino group..

[0028] In general formula (A) above, subscripts d, g, and k represent the repeating R2S1O2/2 units of the siloxane polymer.

[0029] In various embodiments, subscripts c and m are 0 and subscripts b, d, e, f, g, h, i, j, k, I, and n are each integers of 1 or more. When subscript j is 1 , the resulting siloxane polymer includes three segments of repeating siloxane bonds each separated by a bivalent linking group, which such bivalent linking groups being represented by subscripts b, f, i, and n, respectively. In these embodiments, the siloxane polymer is typically formed from hydrosilylation and may be represented by the following general formula:

(X)3-a(R)a-Si-(CH2)b-((SiR2-0)_d-SiR2)e-(CH2)f-[((SiR2-0)g-SiR2)_h-(CH₂)i]j-((SiR2-0)_k-

SiR2)|-(CH₂)n-Si-(X)3-p(R)p.

Typically, when subscripts d, g, and k are 1 or more, subscript j is 1 (and as defined above, because subscripts d is greater than 0, subscript e is 1 , and because subscript g is greater than 0, subscript h is 1 . In these embodiments, the siloxane polymer has the following general formula:

(X)3-a(R)a-Si-(CH₂)b-(SiR2-0)_d-SiR₂ -(CH2)f-(SiR2-0)g-SiR2-(CH₂)i-(SiR2-0)_k-SiR2- (CH₂)n-Si-(X)₃-p(R)p.

Most typically, subscripts d and k are each 1 and subscript g is an integer greater than 1 such that the block represented by subscript g provides the repeating R2S1O2/2 units in the siloxane polymer. In these embodiments, the siloxane polymer has the following general formula: (X)3._a(R)_a-Si-(CH2)b-SiR2-0-SiR2-(CH2)f-(SiR2-0)g-SiR2-(CH2)i-SiR2-0-SiR2-(CH₂)n-Si- (X)3-p(R)p-

[0030] In certain embodiments introduced above, subscripts a and p are each 0 such that the siloxane polymer is endblocked with three silicon-bonded hydrolysable groups (represented by X) at each end. However, as noted above, the siloxane polymer need not have any silicon-bonded hydrolysable groups as subscripts a and p may each be 3. In embodiments in which subscripts a and p are each 0, the siloxane polymer has the following general formula:

(X)3-Si-(CH2)b-SiR2-0-SiR2-(CH2)f-(SiR2-0)g-SiR2-(CH2)i-SiR2-0-SiR2-(CH2)_n-Si-(X)3. In these embodiments, subscripts b, f, i, and n are each 2. Accordingly, when the hydrolysable groups represented by X are each alkoxy groups, e.g. methoxy groups, the siloxane polymer has the following general formula:

(OCH3)3-Si-CH2CH2-SiR2-0-SiR2-CH2CH2-(SiR2-0)g-SiR2-CH₂CH2-SiR2-0-SiR2- CH₂CH2-Si-(OCH₃)3.

Specific species of the siloxane polymer within the general formula immediately above are set forth below for illustrative purposes only, where each R is independently methyl or CH₂CH₂CF₃:

As noted above, R is independently selected such that even within the repeating block represented by subscript g there may be different substituents represented by R in different blocks. For example, in the first structure above, R may independently vary between methyl and CH₂CH₂CF₃ [0031] In other embodiments, subscripts c and m are 1 and subscripts b, f, i, and n are each 0. In these embodiments, the siloxane polymer is typically formed from condensation and may be represented by the following general formula:

(X)3-a(¾-Si-0-((SiR₂-0)_d-SiR₂)_e-W

Because R is independently selected and may vary in different R2S1O2/2 units, the general formula above may be rewritten to exclude any of the blocks represented by subscripts e, h, j, and I, so long as not all of these subscripts are simultaneously 0. For example, the general formula above may be rewritten while only including the R2S1O2/2 units within the block represented by subscript d, subscript h, subscript j, and/or subscript I, as each of these formulas would be duplicative with one another, save for potential differences in molecular weight in embodiments in which the siloxane polymer includes greater than 200 repeating R2S1O2/2 units. As but one example, the general formula introduced above is rewritten below where subscripts d, e, k, and I are 0, subscript g is an integer greater than 1 , and subscripts h and j are 1 :

(X)3-a(R)a-Si-0-(SiR2-0)g-SiR₂-0-Si-(X)3.p(R)p.

Further, because R is independently selected, the general formula introduced immediately above may be further condensed as follows:

(X)3-a(R)a-Si-0-(SiR₂-0)g-Si-(X)₃.p(R)p.

Subscripts a and p may each independently be from 0 to 3 such that the siloxane polymer of these embodiments need not have any silicon-bonded hydrolysable groups. Specific species of the siloxane polymer within the general formula immediately above are set forth below for illustrative purposes only:

In each of these examples, subscript g represents the repeating R2S1O2/2 units, and g is selected based on the desired molecular weight and viscosity of the siloxane polymer.

[0032] Further examples of the siloxane polymer when the siloxane polymer includes hydrolysable groups are set forth below for illustrative purposes only:

In each of these examples, subscript g represents the repeating R2S1O2/2 units, and g is selected based on the desired molecular weight and viscosity of the siloxane polymer. Subscript b represents an optionally repeating CH2 group and is defined above.

[0033] A single species of the siloxane polymer may be utilized or various combinations of different species of the siloxane polymer may be utilized in concert with one another in the non-aqueous emulsion as the additive compound. For example, two different types of siloxane polymers may be utilized in combination with one another, or a siloxane polymer may be utilized in combination with a silicone resin, e.g. an MQ resin. The siloxane polymer may be obtained or formed combined with the organic vehicle as a discrete component, or the siloxane polymer may be disposed in a carrier solvent or vehicle prior to combining the siloxane polymer and the organic vehicle.

[0034] The carrier vehicle for the silicone polymer may be any vehicle capable of solubilizing, partially solubilizing, or otherwise dispersing the siloxane polymer. The carrier vehicle may, in certain embodiments, be referred to as a solvent when capable of solubilizing the siloxane polymer. The vehicle is generally referred to as a vehicle as opposed to a solvent because the vehicle need only disperse the siloxane polymer, but not solubilize the siloxane polymer, although solublization is typical. For example, in certain embodiments, the carrier vehicle comprises a siloxane fluid. Specific examples of siloxane fluids suitable for the purposes of the carrier vehicle of the composition include volatile methylsiloxane fluids, such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, octamethyltetracyclosiloxane, and combinations thereof. Volatile methylsiloxane fluids are commercially available, such as OS-10, OS-20, or OS-30, from Dow Corning® Corporation of Midland, Ml. In other embodiments, the carrier vehicle of the siloxane polymer is a non- polar hydrocarbon carrier, which may be aromatic, aliphatic, cyclic, alicyclic, etc. Specific examples of aliphatic hydrocarbon vehicles suitable for the carrier vehicle include hexane, heptane, octane, etc. Specific examples of aromatic hydrocarbon vehicles suitable for the carrier vehicle include toluene, xylene, trimethylbenzene, etc. Generally, however, the carrier vehicle is the siloxane fluid, which has improved miscibility with the vehicle generally utilized to solubilize the polyfluoropolyether silane, as described below.

[0035] The molecular weight or viscosity of the siloxane polymer is generally not limited when the non-aqueous emulsion is utilized in wet coating methods. In these embodiments, the viscosity of the siloxane polymer is typically such that the non-aqueous emulsion including the siloxane polymer is flowable. However, when the non-aqueous emulsion is utilized in other methods, e.g. physical vapor deposition, the molecular weight or viscosity of the siloxane polymer is typically selected such that the siloxane polymer volatilizes. In these embodiments, the siloxane polymer typically has a viscosity of from 50 to 500,000, alternatively from 100 to 300,000, alternatively from 300 to 100,000, cSt at 25 °C.

[0036] When the additive compound comprises the siloxane polymer, the amount of the siloxane polymer utilized in the non-aqueous emulsion may vary dependent upon the desired physical properties of the layer formed from the non-aqueous emulsion as well as the method by which the layer is formed. For example, when the non-aqueous emulsion is utilized in wet coating applications, the siloxane polymer is typically present in the nonaqueous emulsion in an amount of from 0.01 to 0.5, alternatively from 0.05 to 0.35, alternatively from 0.10 to 0.30, percent by weight based on the total weight of the nonaqueous emulsion. The amount of the siloxane polymer present in the non-aqueous emulsion may vary from the ranges set forth immediately above contingent on the absence or presence of various optional components employed in the non-aqueous emulsion.

[0037] When the additive compound comprises the siloxane polymer, the siloxane polymer and the polyfluoropolyether silane may be utilized in various weight ratios from 0.1 /99.9 to 99.9/0.1 . The relative amounts of the siloxane polymer and the polyfluoropolyether silane are typically selected based on the desired physical properties of the layer formed from the nonaqueous emulsion. For example, as the amount of the siloxane polymer increases in the non-aqueous emulsion relative to the amount of the polyfluoropolyether silane in the nonaqueous emulsion, the layer formed from the composition generally has a lesser coefficient of friction (kinetic), which is desirable in certain applications. Conversely, as the amount of the siloxane polymer decreases in the non-aqueous emulsion relative to the amount of the polyfluoropolyether silane in the non-aqueous emulsion, the layer formed from the nonaqueous emulsion generally has a greater durability (as determined based on a water contact angle after abrasion, as described below), which is also desirable in certain applications. Accordingly, the ratio of the siloxane polymer and the polyfluoropolyether silane in the non-aqueous emulsion may be selectively chosen based on whether a lesser coefficient of friction or a greater durability of the layer is more desirable based on the particular application in which the layer is utilized.

[0038] In these or other embodiments, the additive compound may comprise the drying agent. The drying agent may be, for example, (i) water- reactive or (ii) a desiccant. The drying agent may comprise combinations of different water- reactive drying agents and/or different desiccant drying agents.

[0039] "Water-reactive," with reference to the water-reactive drying agent, means a drying agent that reacts chemically with water if present in the non-aqueous emulsion. For example, the water-reactive drying agent may react with water to form a by-product or reaction product other than water, such as an acid, a base, an alcohol, etc. The water-reactive drying agent and water may react to form a single type of compound as the by-product other than water, or the water-reactive drying agent and water may react to form combinations of different byproducts other than water.

[0040] The water- reactive drying agent may comprise any suitable compound that reacts chemically with water. The water-reactive drying agent may be a solid, a liquid, a gas, or combinations thereof. The water-reactive drying agent is typically not pyrophoric. Said differently, the water-reactive drying agent generally does not combust or ignite spontaneously, e.g. while in the presence of atmospheric moisture. Thus, the water-reactive drying agent is generally not selected from known pyrophoric water-reactive compounds, such as Alkali metals, metal hydrides, etc.

[0041] In certain embodiments, the water-reactive drying agent is a monomeric compound having a water-reactive functional group. By monomeric compound it is meant that the water- reactive drying agent includes three or fewer repeating units such that the water-reactive drying agent is distinguished from an oligomer and a polymer. One exemplary water-reactive functional group is a hydrolysable group. Suitable hydrolysable groups are set forth above with reference to the silicone polymer and include, for example, H, a halogen atom, an alkoxy group, an alkylamino group, a carboxy group, an alkyliminoxy group, an alkenyloxy group, or an N-alkylamido group.

[0042] In these or other embodiments, the water-reactive drying agent is silicon-based. By silicon-based, it is meant that the water-reactive drying agent includes at least one silicon atom, e.g. one silicon atom or two silicon atoms. The functional group bonded directly to the silicon atom is water reactive. If two or more silicon atoms are present in the water-reactive drying agent, the silicon atoms may be bonded to one another via a covalent bond, or may be linked via a bivalent linking group, which may be organic or non-organic. Examples of organic bivalent linking groups include hydrocarbylene, heterohydrocarbylene, and organoheterylene linking groups. Specific examples of non-organic bivalent linking groups include NH and O.

[0043] Alternatively, the water-reactive drying agent may be free from silicon atoms. Specific examples of the water-reactive drying agent in these embodiments include trialkyl orthoformate (e.g. trimethyl orthoformate), phosphorus pentoxide, and combinations thereof.

[0044] Specific examples of such water-reactive drying agents suitable for the non-aqueous emulsion include alkyltrialkoxysilane, disilazane, alkyltrioximosilane, alkyltri(carboxylic acid ester)silane, trialkylhalosilane, and combinations thereof.

[0045] Alkyltrialkoxysilanes have the general formula: R⁴(OR5)3Si, where R⁴ and R^ are each independently selected alkyl groups having from 1 to 10, alternatively from 1 to 6, alternatively from 1 to 4, alternatively from 1 to 2, carbon atoms. Specific examples of alkyltrialkoxysilanes include methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, methyldimethoxyethoxysilane, etc.

[0046] The disilizanes may have the general formula R^SiNHSiR^ where each R^ is an independently selected alkyl group, alkenyl group, aryl group, alkaryl group, or aralkyl group. Specific examples of disilazanes include tetraalkyldialkenyldisilazane, hexaalkyldisilazane, diaryltetraalkyldisilazane, tetraalkyldialkaryldisilazane, tetraalkyldiaralkyldisilazane, etc.

[0047] Tetraalkyldialkenyldisilazanes have the general formula: R^R^SiNHSiRSR^, where each R⁷ is an independently selected alkyl group as defined above for R⁴ and R^ and each

R8 is an independently selected alkenyl group having from 2 to 10, alternatively from 2 to 6, alternatively from 2 to 4, alternatively 2, carbon atoms. Specific examples of tetraalkyldialkenyldisilazanes include tetramethyldivinyldisilazane, tetraethyldivinyldisilazane, tetramethyldiallyldisilazane, dimethyldiethyldivinyldisilazane, etc.

[0048] Hexaalkyldisilazanes have the general formula: R^SiNHSiR^, where each R§ is an independently selected alkyl group as defined above for R⁴ and R5. Specific examples of hexaalkyldisilazanes include hexamethyldisilazane, diethyltetramethyldisilazane, etc.

[0049] Diaryltetraalkyldisilazanes have the general formula: R^{1 (}½R^{1 1} SiNHSiR^{1 0}R¹ , where each R¹ ^ is an independently selected alkyl group as defined above for R⁴ and R^ and each R^{1 1} is an independently selected aryl group having from 3 to 12, alternatively from 3 to 8, alternatively from 3 to 6, alternatively 6, carbon atoms. Although not required, each

R^{1 1} may independently also contain from one or more heteroatoms (e.g. O, N, S, and P).

Specific examples of R^{1 1} include phenyl, naphthyl, thienyl, and indolyl groups. A specific example of diaryltetraalkyldisilazanes includes diphenyltetramethyldisilazane.

[0050] In certain embodiments, the disilazanes are selected from the group of tetraalkyldialkenyldisilazanes, hexaalkyldisilazanes, diaryltetraalkyldisilazanes, and combinations thereof.

[0051] In certain embodiments, the drying agent comprises the disilazane with the disilazane being selected from the group of hexaalkyldisilazane, tetraalkyldialkenylsilazane, and diaryltetraalkylsilazane.

[0052] Alkyltrioximosilanes have the general formula: R^Si(ON=CH2)3, where is an alkyl group as defined above for R⁴ and R^. Specific examples of alkyltrioximosilanes include methyltrioximosilane, ethyltrioximosilane, propyltrioximosilane, etc.

[0053] Alkyltri(carboxylic acid ester)silanes have the general formula: R¹3Si(OOCR¹⁴)3, where R¹ ^ and each R¹⁴ is an independently selected alkyl group as defined above for R⁴ and R5. Typically, each R^⁴ is methyl. In these embodiments, alkyltri(carboxylic acid ester)silanes may alternatively be referred to as alkyltriacetoxysilanes. Specific examples thereof include methyltriacetoxysilane, ethyltriacetoxysilane, propyltriacetoxysilane, etc.

[0054] Trialkylhalosilanes have the general formula: R^gSiX^ , where each j$ an independently selected alkyl group as defined above for R⁴ and R^ and X¹ is a halogen atom selected from F, CI, Br, and I. Specific examples of trialkylhalosilanes include trimethylchlorosilane, triethylchlorosilane, trimethylbromosilane, dimethylethylchlorosilane, etc.

[0055] In specific embodiments, the water-reactive drying agent comprises disilazane with the disilazane being selected from the group of hexaalkyldisilazane, tetraalkyldialkenylsilazane, and diaryltetraalkyldisilazane. Exemplary species thereof include hexamethyldisilazane, diphenyltetramethyldisilazane, and tetramethyldivinyldisilazane.

[0056] Alternatively, as introduced above, the drying agent may be a desiccant drying agent. The desiccant drying agent may be any hygroscopic material suitable for reducing or eliminating any water within or from the non-aqueous emulsion. The hygroscopic material of the desiccant drying agent generally absorbs or otherwise removes water from its vicinity. As contrasted from the water-reactive drying agent, the desiccant drying agent does not react with water, but instead absorbs or removes water. As with the water-reactive drying agent, the desiccant drying agent may be a solid, a liquid, a gas, or combinations thereof, although the desiccant drying agent is typically a solid. Generally, the desiccant drying agent absorbs water via physical techniques (i.e., the desiccant physically binds the water), as opposed to chemical reactivity, with chemical reactivity being within the scope of "water-reactive."

[0057] Specific examples of desiccant drying agents suitable for the non-aqueous emulsion include molecular sieves, sodium sulfate, calcium chloride, magnesium sulfate, calcium sulfate, magnesium chloride, lithium chloride, zeolites, aluminasilicates, and combinations thereof. The desiccant drying agent is typically anhydrous or nearly so.

[0058] When the additive compound comprises the drying agent, a concentration of the drying agent in the organic mixture (and non-aqueous emulsion) may vary based on, for example, a storage vessel in which the non-aqueous emulsion is disposed, relative humidity, initial water content, etc. For example, lesser concentrations may be utilized when the nonaqueous emulsion is also stored in a hermetically-sealed vessel. Conversely, greater concentrations may be utilized if the non-aqueous emulsion is exposed to atmospheric moisture. In addition, when the drying agent comprises the water-reactive drying agent, the concentration of the water- reactive drying agent is generally dynamic over time. For example, the concentration of the water-reactive drying agent may be continuously reduced as the water-reactive drying agent reacts with any water in the organic mixture and/or nonaqueous emulsion and is so consumed. In certain embodiments in which the additive compound comprises the drying agent, the drying agent is present in the non-aqueous emulsion in a molar ratio of at least 1 :1 ; alternatively at least 2:1 ; alternatively at least 5:1 ; alternatively at least 10:1 ; alternatively at least 25:1 ; alternatively at least 100:1 ; of the drying agent to the polyfluoropolyether silane. The upper limit may be, for example, 1 ,000:1 ; 5,000:1 ; or even 10,000:1 .

[0059] When the additive compound comprises the drying agent, the additive compound may serve to minimize or control a total water content of the non-aqueous emulsion. For example, in certain embodiments in which the additive compound comprises the drying agent, the total water content of the non-aqueous emulsion is controlled at from 0 to less than 1 weight percent based on the total weight of the non-aqueous emulsion. More typically, the total water content of the non-aqueous emulsion is controlled at from 0 to less than 0.9, alternatively from 0 to less than 0.8, alternatively from 0 to less than 0.7, alternatively from 0 to less than 0.6, alternatively from 0 to less than 0.5, alternatively from 0 to less than 0.4, alternatively from 0 to less than 0.3, 0 to less than 0.9, alternatively from 0 to less than 0.2, alternatively from 0 to less than 0.1 , weight percent based on the total weight of the nonaqueous emulsion.

[0060] Even more typically, the total water content of the non-aqueous emulsion is controlled at less than 500 parts per million (ppm) based on the total weight of the non-aqueous emulsion, e.g. from 0 to 500, alternatively from 0 to 250, alternatively from 0 to 100, alternatively from 0 to 50, alternatively from 0 to 25, alternatively from 0 to 10, alternatively 0, ppm based on the total weight of the non-aqueous emulsion.

[0061] Further description regarding control of the total water content of the non-aqueous emulsion, as well as options for storing the non-aqueous emulsion, are disclosed in copending U.S. Pat. Appln. Ser. No. 61/954099 (DC1 1818; H&H 071038.01445), entitled Non- Aqueous Emulsion and Methods of Preparing Surface-Treated Articles Therewith, which is incorporated by reference herein in its entirety.

[0062] The additive compound may comprise a combination of the silicone polymer and the drying agent, or may comprise the silicone polymer and/or the drying agent along with a different additive compound.

[0063] As introduced above, the organic mixture formed by combining the organic vehicle and the additive compound is combined with a polyfluoropolyether silane. For example, in certain embodiments, combining the organic mixture and the polyfluoropolyether silane forms a heterogeneous mixture. In these embodiments, the method further comprises applying a shear force to the heterogeneous mixture to prepare the non-aqueous emulsion. The shear force may be applied via any mechanism, e.g. stirring, shaking, a vortex, etc.

[0064] The polyfluoropolyether silane of the discontinuous phase of the non-aqueous emulsion may be any known perfluoropolyether silane, which are often utilized in conventional surface treatment compositions. The polyfluoropolyether silane may be monomeric, oligomeric, or polymeric. Alternatively, the polyfluoropolyether silane may comprise various combinations of different monomeric, oligomeric, and/or polymeric polyfluoropolyether silanes.

[0065] In various embodiments, the polyfluoropolyether silane has the following general formula (B): Y-Z_a1 -[(OC₃F₆)_b1 -(OCF(CF₃)CF₂)c1 -(OCF₂CF(CF₃))_{d 1} -(OC₂F₄)_ei -(CF(CF₃))_f -

(OCF₂)_gi ]-(CH₂)hl -B-(C_ni H_2r11 )-((SiR^{1 6} ₂-0)m1 "SIR^{1 6} ₂)i1 -(Cji H_{2j 1} )-Si-(X)₃._z1 (R^{1 7})_Z1 - [0066] While the polyfluoropolyether silane of the non-aqueous emulsion is not limited to that of general formula (B), specific aspects of general formula (B) are described in greater detail below. The groups indicated by subscripts b1 -g1 , i.e., the groups within the square brackets in formula (B), may be present in any order within the polyfluoropolyether silane, including a different order as that which is represented in general formula (B) above and throughout this disclosure. Moreover, these groups may be present in randomized or block form. In addition, the group represented by subscript b is typically linear, i.e., the group represented by subscript b1 may alternatively be written as (0-CF₂-CF₂-CF₂)_|-₎-_| . In the description below,

C-p" - Cq" (with p" and q" each being integers) regarding a hydrocarbyl or alkyl group means such group has from p" to q" carbon atoms. When the group indicated by subscript i1 is present, the polyfluoropolyether silane comprises a siloxane segment. Even in these embodiments, the polyfluoropolyether silane is generally referred to as a silane in view of the terminal silicon atom that is not present in any siloxane segment.

[0067] In general formula (B) above, Z is independently selected from -(CF₂)-, -

(CF(CF₃)CF₂0)-, -(CF₂CF(CF₃)0)-, -(CF(CF₃)0)-, -(CF(CF₃)-CF₂)-, -(CF₂-CF(CF₃))-, and

-(CF(CF₃))-. Z is typically selected such that the polyfluoropolyether silane does not include an oxygen-oxygen (O-O) bond within the backbone. In addition, in this general formula, a1 is an integer from 1 to 200; b1 , c1 , d1 , e1 , f 1 , and g1 are integers each independently selected from 0 or from 1 to 200; hi , n1 and j1 are integers each independently selected from 0 or from 1 to 20; i1 and ml are integers each independently selected from 0 or from 1 to 5; B is a divalent organic group or an oxygen atom; R¹ ^ is an independently selected C-| -C₂₂ hydrocarbyl group; z1 is an integer independently selected from 0 to 2; X is an independently selected hydrolysable group; R^{1 7} is an independently selected C-| -C₂₂ hydrocarbyl group which is free of aliphatic unsaturation; and Y is selected from H, F, and (R⁷)_z-| (X)₃__z-| Sie^ ^^-((SiR^O^ -SiRe^ -^ wherein X, B, z1 , R6, R7, jl , m 1 , i1 , n1 , and hi are as defined above.

[0068] R¹6, which is an independently selected C-| -C₂₂ hydrocarbyl group, may be linear, branched, or cyclic. In addition, R¹ ^ may include heteroatoms within the hydrocarbyl group, such as oxygen, nitrogen, sulfur, etc., and may be substituted or unsubstituted. Typically, R¹6 is C1 -C4 alkyl group. In addition, the groups indicated by subscripts n1 and j1 , i.e., groups (C_n-| H2n1 ) ^and (Cj-| H2j ), may also be independently linear or branched. For example, when n1 is 3, these groups may independently have the structure -CH2-CH2- CH₂- -CH(CH₃)-CH₂-, or -ΟΗ₂-ΟΗ(ΟΗ₃)-, wherein the latter two structures have pendant alkyl groups, i.e., these structures are branched and not linear.

[0069] With respect to the moieties represented by subscripts ml , i1 , and j1 : when subscript i1 is 0, subscript j1 is also 0; when subscript i1 is an integer greater than 0, subscript j1 is also an integer greater than 0; and when subscript i1 is an integer greater than 0, ml is also an integer greater than 0. Said differently, when the group represented by subscript i1 is present, the group represented by subscript j1 is also present. The inverse is also true, i.e., when the group represented by subscript i1 is not present, the group represented by subscript j1 is also not present. In addition, when i1 is an integer greater than 0, the group represented by subscript ml is present, and ml is also an integer greater than 0. In certain embodiments, subscripts ml and i1 are each 1 . Typically, the subscript i1 does not exceed 1 , although the subscript ml may be an integer greater than 1 such that siloxane bonds (i.e., Si-0 bonds) are present within the group represented by subscript i1 .

[0070] In certain embodiments, the polyfluoropolyether silane of the non-aqueous emulsion is subject to the proviso that when Y is F; Z is -(CF2)-; a1 is an integer from 1 to 3; and subscripts c1 , d1 , f1 , , ml , and j1 are each 0.

[0071] The hydrolysable group represented by X in general formula (B) may be selected from any of those described above with respect to the silicone polymer. In certain embodiments, the hydrolysable group represented by X in general formula (B) is independently selected from an alkoxy group and an alkylamino group.

[0072] Non-limiting, exemplary embodiments of particular species of the polyfluoropolyether silane of the non-aqueous emulsion are described in detail below. Typically in these embodiments, z1 is 0 such that polyfluoropolyether silane includes three hydrolysable groups represented by X. However, as described above, z can be an integer other than 0 (e.g. 1 or 2) such that these particular polyfluoropolyether silanes include fewer than three hydrolysable groups.

[0073] In certain embodiments, Y in general formula (B) is F. Typically, when Y in general formula (B) is F, subscripts c1 , d1 , and g1 in general formula (B) are each 0. As such, in these embodiments, when the groups indicated by subscripts c1 , d1 , and g1 are absent, the polyfluoropolyether silane has the general formula F-Z_a-| -[(OC3Fg)b-| -(OC₂F4)_e-| -

(CF(CF₃))_f ]-(CH₂)hl -B-(C_ni H_{2n 1} H(SiR ⁶ ₂-0)m1 "SiR^{1 6} ₂)i1 -(Cji H_{2j 1} )-Si-(X)₃._z1 (R^{1 7})_z1 .

[0074] In one embodiment of the non-aqueous emulsion in which Y in general formula (B) is F, as introduced above, Z in general formula (B) is -(CF₂)-, subscripts c1 , d1 , f1 , and g1 in general formula (B) are 0 and subscripts b1 , e1 , hi , and n1 in general formula (B) are each independently an integer greater than 0. As but one example of this embodiment, subscript a1 is 3, subscript b1 is at least 1 , subscript e1 is 1 , subscript hi is 1 , B is an oxygen atom, subscript n1 is 3, and subscripts ml , i1 , and j1 are each 0. In this one example, the polyfluoropolyether silane has the following general formula: CF3-CF₂-CF₂-(0-CF₂-CF₂-

CF₂)b-| -0-CF₂-CF₂-CH₂-0-CH₂-CH₂-CH₂-Si-(X)3._zi (R^{1 7})_zi . Thus, when the hydrolysable groups represented by X are all alkoxy groups, e.g. methoxy groups, this particular polyfluoropolyether silane has the following general formula: CF3-CF₂-CF₂-(0-CF₂-CF₂-

CF₂)_b1 -0-CF₂-CF₂-CH₂-0-CH₂-CH₂-CH₂-Si-(OCH₃)₃. Alternatively, when the hydrolysable groups represented by X are all alkylamino groups, e.g. N(CH3)₂ groups, this particular polyfluoropolyether silane has the following general formula: CF3-CF₂-CF₂-(0-

CF₂-CF₂-CF₂)b-| -0-CF₂-CF₂-CH₂-0-CH₂-CH₂-CH₂-Si-(N(CH₃)₂)₃. In these embodiments, subscript b1 is typically an integer from 17 to 25.

[0075] In another embodiment of the non-aqueous emulsion in which Y in general formula (B) is F and Z in general formula (B) is -(CF₂)-, as described above, subscripts c1 , d1 , f1 , and g1 in general formula (B) are 0 and subscripts b1 , e1 , hi , n1 , ml , , and j1 in general formula (B) are each independently an integer greater than 0. As but one example of this embodiment, subscript a1 is 3, subscript b1 is at least 1 , subscript e1 is 1 , subscript hi is 1 , B is an oxygen atom, subscript n1 is 3, subscripts ml and i1 are each 1 , and subscript j1 is 2. In this one example, the polyfluoropolyether silane has the following general formula: CF3-

CF₂-CF₂-(0-CF₂-CF₂-CF₂)_b1 -0-CF₂-CF₂-CH₂-0-CH₂-CH₂-CH₂-Si(CH₃)₂-0-Si(CH₃)₂-

CH₂-CH₂-Si-(X)3__Z-| (R^{1 7})_Z-| . Thus, when the hydrolysable groups represented by X are all alkoxy groups, e.g. methoxy groups, and z1 is 0, this particular polyfluoropolyether silane has the following general formula: CF₃-CF₂-CF₂-(0-CF₂-CF₂-CF₂)_b1 -0-CF₂-CF₂-CH₂-0-CH₂- CH2-CH2-Si(CH3)2-0-Si(CH3)2-CH2-CH2-Si(OCH₃)3. In these embodiments, subscript b1 is typically an integer from 17 to 25.

[0076] In another embodiment of the non-aqueous emulsion in which Y in general formula (B) is F, as introduced above, Z in general formula (B) is -(CF(CF3)CF20)-. In this embodiment, subscripts b1 , c1 , d1 , e1 , and g1 in general formula (B) are 0, and subscripts f1 , hi , and n1 in general formula (B) are each independently an integer greater than 0. As but one example of this embodiment, subscripts b1 , c1 , d1 , e1 , and g1 in general formula (B) are 0, subscript a1 is at least 1 , subscript f1 is 1 , subscript hi is 1 , B is an oxygen atom, subscript n1 is 3, and subscripts i1 , ml , and j1 are each 0. In this one example, the polyfluoropolyether silane has the following general formula: F-(CF(CF3)-CF2-0)_a-| -

CF(CF₃)-CH2-0-CH2-CH2-CH2-Si-(X)3._zi (R^{1 7})_zi . Thus, when the hydrolysable groups represented by X are all alkoxy groups, e.g. methoxy groups, and z1 is 0, this particular polyfluoropolyether silane has the following general formula: F-(CF(CF3)-CF2-0)_a-| -

CF(CF₃)-CH2-0-CH2-CH2-CH2-Si-(OCH₃)3. Alternatively, when the hydrolysable groups represented by X are all alkylamino groups, e.g. N(CH3)2 groups, this particular polyfluoropolyether silane has the following general formula: F-(CF(CF3)-CF2-0)_a-| - CF(CF₃)-CH2-0-CH2-CH2-CH2-Si-(N(CH₃)2)3. In these embodiments, subscript a1 is typically an integer from 14 to 20.

[0077] In another embodiment of the non-aqueous emulsion in which Y in general formula (B) is F and Z in general formula (B) is -(CF(CF3)CF20)-, as introduced immediately above, subscripts b1 , c1 , d1 , e1 , and g1 in general formula (B) are 0, subscript a1 is at least 1 , subscript f1 is 1 , subscript hi is 1 , B is an oxygen atom, subscript n1 is 3, subscripts ml and i1 are each 1 , and subscript j1 is 2. In this one example, the polyfluoropolyether silane has the following general formula: F-(CF(CF₃)CF20)_ai -CF(CF₃)-CH2-0-CH2-CH2-CH2-

Si(CH₃)2-0-Si(CH₃)2-CH2-CH2-Si-(X)3._zi (R^{1 7})_zi . Thus, when the hydrolysable groups represented by X are all alkoxy groups, e.g. methoxy groups, and z1 is 0, this particular polyfluoropolyether silane has the following general formula: F-(CF(CF3)CF20)_a-| -CF(CF3)-

CH2-0-CH2-CH2-CH2-Si(CH3)2-0-Si(CH3)2-CH2-CH2-Si(OCH₃)3. In these embodiments, subscript a1 is typically an integer from 14 to 20. [0078] In other embodiments, Y in general formula (B) is (R ⁷)_z-| (X)3-_Z1 Si-(Cj-| H₂ji )-

((SiR¹⁶2-0)_mi-SiR¹⁶2)ii-(C_n-|H2_ni)-B-(CH₂) i-- Typically, when Y in general formula (B) is (R¹⁷)z1 (X)3-z1 SKCj! H_2ji )-((SiRl 6₂-0)_m1 -SiRl ⁶ ₂)i1 -(C_nl H_2r11 )-B-(CH₂)_hl -, subscripts b1 , c1 , and f1 in general formula (B) are 0. As such, in these embodiments, when the groups indicated by subscripts b1, c1, and f1 are absent, the polyfluoropolyether silane has the following general formula: Y-Z_a1-[(OCF2CF(CF3))_d1-(OC2F4)_e-|-(OCF2)gi]-(CH₂) i-B-

(Cn1 H₂n1 )-((SiR¹⁶ ₂-0)_m1 -SiRl ⁶ ₂)_M -(Cj-, H_2j1 )-Si-(X)₃._z1 (R¹⁷)_z1.

[0079] In one embodiment in which Y in general formula (B) is (R¹⁷)z(^)3-z1 Si-(Cj-| H2ji )-

((SiR¹⁶ ₂-0)_m-|-SiR¹⁶ ₂)j-|-(C_n-|H_2ni)-B-(CH₂)[_r|-, as introduced immediately above, Z is -

(CF₂)-, B is an oxygen atom, subscripts b1, c1, d1, and f1 in general formula (B) are 0, and subscripts e1 and g1 in general formula (B) are each independently an integer greater than 0. As but one example of this embodiment, Z is -(CF₂)-, B is an oxygen atom, subscripts b1 , c1 , d1 , f1 , ml , , and j1 in general formula (B) are 0, subscript e1 is at least 1 , subscript g1 is at least 1, subscript hi is 1, B is an oxygen atom, and subscript n1 is 3. In this one example, the polyfluoropolyether silane has the following general formula: (R¹⁷)_zl(X)3-z"|Si-

CH₂-CH₂-CH₂-0-CH₂-CF₂-(OCF₂CF₂)_e1-(OCF₂)_g1-CH₂-0-CH₂-CH₂-CH₂-Si-(X)₃.

zl(R¹⁷)z1- Thus, when the hydrolysable groups represented by X are all alkoxy groups, e.g. methoxy groups, and z1 is 0, this particular polyfluoropolyether silane has the following general formula: (CH₃0)3Si-CH₂-CH₂-CH₂-0-CH₂-CF₂-(OCF₂CF₂)_e-|-(OCF₂)g-|-CH₂-0-

CH₂-CH₂-CH₂-Si-(OCH3)3. Alternatively, when the hydrolysable groups represented by X are all alkylamino groups, e.g. N(CH3)₂ groups, and z1 is 0, this particular polyfluoropolyether silane has the following general formula: ((CH3)₂N)3Si-CH₂-CH₂-CH₂-

0-CH₂-CF₂-(OCF₂CF₂)_e1-(OCF₂)_g1-CH₂-0-CH₂-CH₂-CH₂-Si-(N(CH₃)₂)3.

[0080] Alternatively, in another embodiment in which Y in general formula (B) is

(R¹⁷)z1 (X)3-z1 SKCj! H_2j1 )-((SiRl 6₂-0)_m1 -SiRl 6_2)j1._(Cn1 H_2n1 )-B-(CH₂)_h1 -, as introduced above, Z is -(CF₂)-, B is an oxygen atom, subscripts b1, c1, e1, and f1 in general formula (B) are 0, and subscripts d1 and g1 in general formula (B) are each independently an integer greater than 0. [0081] Notably, in the specific formulas provided above, which are representative of exemplary polyfluoropolyether silanes, one or more fluorine atoms of the polyfluoropolyether silane may be replaced with other atoms. For example, other halogen atoms (e.g. CI) may be present in the polyfluoropolyether silane, or the polyfluoropolyether silane may have lesser degree of fluorination. By lesser degree of fluorination, it is meant that one or more of the fluorine atoms of any of the general formulas above may be replaced with hydrogen atoms.

[0082] Methods of preparing polyfluoropolyether silanes are generally known in the art. For example, polyfluoropolyether silanes are typically prepared via a hydrosilylation reaction between an alkenyl-terminated polyfluoropolyether compound and a silane compound having a silicon-bonded hydrogen atom. The silane compound typically includes at least one hydrolysable group, such as a silicon-bonded halogen atom. The silicon-bonded halogen atom may be reacted and converted to other hydrolysable groups. For example, the silicon- bonded halogen atom may be reacted with an alcohol such that the resulting polyfluoropolyether silane compound includes alkoxy functionality attributable to the alcohol. The byproduct of such a reaction is hydrochloric acid. One of skill in the art understands how to modify the starting components to obtain the desired structure of the polyfluoropolyether silane. Specific examples of methods for preparing various polyfluoropolyether silanes are disclosed in U.S. Publ. Pat. Appln. No. US 2009/0208728 A1 , which is incorporated by reference herein in its entirety.

[0083] As introduced above, in certain embodiments, the polyfluoropolyether silane is combined with a fluorinated vehicle to pre-form a fluorinated composition prior to combining the organic mixture and the polyfluoropolyether silane.

[0084] The fluorinated vehicle is different from the polyfluoropolyether silane and may, in certain embodiments, be referred to as a fluorinated solvent. In these embodiments, the fluorinated vehicle may be any fluorinated vehicle capable of solubilizing the polyfluoropolyether silane and is typically selected such that the fluorinated vehicle is non- reactive with the polyfluoropolyether silane or any other components in the non-aqueous emulsion. The fluorinated vehicle generally has a lesser molecular weight and increased volatility as compared to the polyfluoropolyether silane. Specific examples of fluorinated vehicles suitable for the discontinuous phase of the non-aqueous emulsion include polyfluorinated hydrocarbons. Examples of polyfluorinated hydrocarbons include, but are not limited to, polyfluorinated aliphatic hydrocarbons such as decafluoropentane; perfluoroaliphatic hydrocarbons such as perfluoroaliphatic C5-C12 hydrocarbons such as perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1 ,3-dimethylcyclohexane; polyfluorinated aromatic hydrocarbons, such as bis(trifluoromethyl)benzene; hydrofluoroethers (HFEs), such as perfluorobutyl methyl ether (C4F9OCH3), ethyl nonafluorobutyl ether (C4F9OC2H5), ethyl nonafluoroisobutyl ether (C4F9OC2H5), and like

HFEs; perfluoropolyethers; perfluoroethers; nitrogen-containing polyfluorinated vehicles, such as nitrogen-containing perfluorinated vehicles; etc. Such fluorinated vehicles are known in the art and commercially available from various suppliers.

[0085] In various embodiments including the fluorinated vehicle in the discontinuous phase, the fluorinated vehicle comprises a perfluoropolyether vehicle. In these embodiments, the perfluoropolyether vehicle typically has a boiling point temperature of at least 40, alternatively at least 60, alternatively at least 80, alternatively at least 100, 'Ό at atmospheric pressure (i.e., 101 .325 kilopascals). In one specific embodiment, the perfluoropolyether vehicle has a boiling point temperature of from 125 to 145, alternatively from 130 to 140, 'Ό at atmospheric pressure. In another specific embodiment, the perfluoropolyether vehicle has a boiling point temperature of from 160 to 180, alternatively from 165 to 175, °C at atmospheric pressure. Typically, the boiling point temperature of the perfluoropolyether vehicle is from greater than 120 to 180, alternatively from greater than 125 to 180, alternatively from greater than 160 to 180, 'Ό at atmospheric pressure. However, the depending on the molecular weight of the perfluoropolyether vehicle, the boiling point temperature of the perfluoropolyether vehicle may be greater than the upper range of 180 °C, e.g. to 200, 230, or 270 °C.

[0086] In embodiments in which the fluorinated vehicle comprises the perfluoropolyether vehicle, the perfluoropolyether vehicle typically has the following general formula:

F,C- -O- -CF— CF; ^■O— CF₂- -O— CF₃

CF,

wherein a" is an integer greater than 1 and b" is 0 or greater Specifically, subscripts a" and b" of the general formula above are chosen so as to provide the desired boiling point temperature of the perfluoropolyether vehicle. In particular, the relationship between subscripts a" and b", the boiling point temperature, and the molecular weight of the perfluoropolyether vehicle is set forth below:

Boiling Point (^<€) Typical a" Typical b" Average MW (Da)

125-145 1 -3 1 -7 600-620 160-180 1 -4 1 -10 750-770

190-210 ≥ 1 ≥ 1 860-880

220-240 ≥ 1 ≥ 1 1010-1030

260-280 ≥ 1 ≥ 1 1540-1560

[0087] Alternatively, the fluorinated vehicle may comprise a nitrogen-containing polyfluorinated vehicle, such as a nitrogen-containing perfluorinated vehicle. In these embodiments, the nitrogen-containing perfluorinated or polyfluorinated vehicle is typically a tertiary amine in which the nitrogen atom is a center atom having three polyfluorinated substituents such as three perfluorinated substituents, optionally including heteroatoms, such as oxygen, nitrogen, and/or sulfur. Typically, each of the substituents bonded to the nitrogen atom are identical, although these substituents may differ in terms of the number of carbon atoms present, the presence or absence of heteroatoms, and/or fluorine content. These substituents generally independently include from 2 to 10 carbon atoms, and are typically perfluorinated. As but one example of such a nitrogen-containing perfluorinated vehicle, a structure representative of C-12F27 is set forth below for illustrative purposes only:

Typically, when the fluorinated vehicle comprises the nitrogen-containing perfluorinated or polyfluorinated vehicle, the fluorinated vehicle comprises a combination of different nitrogen- containing perfluorinated or polyfluorinated vehicles.

[0088] The discontinuous phase of the non-aqueous emulsion (or the fluorinated composition, which are generally one in the same) may utilize a single fluorinated vehicle or a combination of two or more fluorinated vehicles. Such fluorinated vehicles may be linear, branched, cyclic, alicyclic, aromatic, or may contain combinations thereof. In certain embodiments, the fluorinated vehicle is not perfluorinated. In these embodiments, the fluorinated vehicle is typically polyfluorinated and may be selected from polyfluorinated aromatic hydrocarbons, such as bis(trifluoromethyl)benzene; polyfluorinated aliphatic hydrocarbons; (HFEs), such as perfluorobutyl methyl ether, ethoxy-nonafluorobutane, and like HFEs, and combinations thereof. Typically, the fluorinated vehicle comprises an HFE.

[0089] When the discontinuous phase of the non-aqueous emulsion further comprises the fluorinated vehicle, the fluorinated vehicle and the polyfluoropolyether silane may be present in the discontinuous phase in various amounts or ratios as compared to one another. Generally, the polyfluoropolyether silane is combined with the fluorinated vehicle prior to forming the non-aqueous emulsion for obtaining better self-emulsification properties during preparation of the non-aqueous emulsion.

[0090] To this end, the discontinuous phase may comprise the polyfluoropolyether silane in an amount of 100 parts by weight based on 100 parts by weight of the discontinuous phase of the non-aqueous emulsion (when the discontinuous phase does not include the fluorinated vehicle). Alternatively, in embodiments including the fluorinated vehicle in the discontinuous phase, the polyfluoropolyether silane is typically present in the discontinuous phase in an amount of from greater than 0 to less than 100 based on 100 parts by weight of the discontinuous phase, with the actual value being chosen based on the desired physical properties of the non-aqueous emulsion. For example, repeatability of the non-aqueous emulsion generally decreases when the discontinuous phase comprises the polyfluoropolyether silane in an amount of greater than 50 parts by weight based on 100 parts by weight of the discontinuous phase. Accordingly, in certain embodiments, the discontinuous phase comprises the polyfluoropolyether silane in an amount of from 1 to 50, alternatively from 10-30, alternatively from 15-25, alternatively from 18-22, parts by weight based on 100 parts by weight of the discontinuous phase. The balance of the discontinuous phase is generally the fluorinated vehicle. Said differently, the discontinuous phase typically comprises the fluorinated vehicle in an amount of from 51 to 99, alternatively from 70 to 90, alternatively from 75-85, alternatively from 78-82, parts by weight based on 100 parts by weight of the discontinuous phase. In certain embodiments, the polyfluoropolyether silane and the fluorinated vehicle have similar densities such that the parts by weight described above may alternatively be referred to as parts by volume, i.e., these ranges also apply to the relative volumes of the polyfluoropolyether silane and the fluorinated vehicle in the discontinuous phase in these embodiments. [0091] The relative amount of the discontinuous phase present in the non-aqueous emulsion is generally contingent on whether the discontinuous phase further includes the fluorinated vehicle. For example, in embodiments excluding the fluorinated vehicle from the discontinuous phase, the discontinuous phase is typically present in the non-aqueous emulsion in an amount of from greater than 0 to 1 .0, alternatively from greater than 0 to 0.50, alternatively from 0.10 to 0.30, alternatively from 0.15 to 0.25, percent by weight based on the total weight of the non-aqueous emulsion. In these embodiments, the discontinuous phase consists essentially of, or consists of, the polyfluoropolyether silane. In these embodiments, the discontinuous phase is typically present in the non-aqueous emulsion in an amount of from greater than 0 to 0.56, alternatively from greater than 0 to 0.28, alternatively from 0.06 to 0.17, alternatively from 0.08 to 0.14, percent by volume based on the total volume of the non-aqueous emulsion.

[0092] Alternatively, in embodiments including the fluorinated vehicle in the discontinuous phase, the discontinuous phase is typically present in the non-aqueous emulsion in an amount of from greater than 0 to 10, alternatively from greater than 0 to 5, alternatively from .25 to 2.0, alternatively from 0.75 to 1 .25, percent by weight based on the total weight of the non-aqueous emulsion. In these embodiments, the discontinuous phase typically comprises the polyfluoropolyether silane and the fluorinated vehicle in the amounts set forth immediately above. In these embodiments, the discontinuous phase is typically present in the non-aqueous emulsion in an amount of from greater than 0 to 5.86, alternatively from greater than 0 to 2.86, alternatively from 0.14 to 1 .13, alternatively from 0.42 to 0.70, percent by volume based on the total volume of the non-aqueous emulsion.

[0093] Accordingly, in certain embodiments, the discontinuous phase comprises the polyfluoropolyether silane in a concentration of from 1 to 50, alternatively from 10-30, alternatively from 15-25, alternatively from 18-22, parts by weight based on 100 parts by weight of the discontinuous phase. The balance of the discontinuous phase is generally the fluorinated vehicle. Said differently, the discontinuous phase typically comprises the fluorinated vehicle in an amount of from 51 to 99, alternatively from 70 to 90, alternatively from 75-85, alternatively from 78-82, parts by weight based on 100 parts by weight of the discontinuous phase. In certain embodiments, the polyfluoropolyether silane and the fluorinated vehicle have similar densities such that the parts by weight described above may alternatively be referred to as parts by volume, i.e., these ranges also apply to the relative volumes of the polyfluoropolyether silane and the fluorinated vehicle in the discontinuous phase in these embodiments.

[0094] The concentrations of the polyfluoropolyether silane and the fluorinated vehicle in the discontinuous phase of the non-aqueous emulsion may vary from the ranges set forth immediately above contingent on the absence or presence of various optional components employed in the non-aqueous emulsion, as described in greater detail below.

[0095] As noted above, the organic vehicle is typically selected such that the non-aqueous emulsion exhibits the Tyndall effect for a period of time. The organic vehicle may be combined with the polyfluoropolyether silane (either singularly or via the fluorinated composition) to readily determine whether the resulting mixture exhibits the Tyndall effect for a period of time. This determination is generally made via visual or optical inspection. In particular, to determine whether a particular organic vehicle is suitable for the purpose of the non-aqueous emulsion, the polyfluoropolyether silane is combined with the fluorinated vehicle to pre-form the fluorinated composition, and the fluorinated composition is combined with the organic vehicle. The fluorinated composition generally self-disperses in the organic vehicle such that the fluorinated composition and the organic vehicle self-emulsify and exhibit the Tyndall effect for a period of time (in the case of certain organic vehicles) in the resulting non-aqueous emulsion. However, a shear force may be applied to emulsify the components, e.g. by shaking or subjecting to a vortex. Generally, if the resulting mixture exhibits the Tyndall effect for a period of time, the resulting mixture is a non-aqueous emulsion. Said differently, when the resulting mixture does not exhibit the Tyndall effect for a period of time, an emulsion generally does not form from the organic vehicle and the polyfluoropolyether silane. In these embodiments, i.e., when no Tyndall effect is exhibited, the resulting mixture typically settles and/or precipitates.

[0096] For example, to readily determine whether a particular organic vehicle is suitable for preparing a non-aqueous emulsion that exhibits the Tyndall effect for a period of time, 0.02 grams of the polyfluoropolyether silane may be combined with 0.08 grams of the fluorinated vehicle to form the fluorinated composition. The fluorinated composition, having a mass of 0.10 grams, may be disposed in 9.90 grams of the organic vehicle dropwise to form a mixture. The mixture can be shaken or stirred to determine whether the mixture emulsifies to prepare the non-aqueous emulsion that exhibits the Tyndall effect for a period of time. Although other amounts of the organic vehicle, the polyfluoropolyether silane, and/or the fluorinated vehicle may be utilized, this procedure allows for high throughput analysis of numerous organic vehicles at a reproducible and repeatable basis. Further, this procedure allows for a quick determination of whether the particular organic vehicle is suitable for preparing a non-aqueous emulsion that exhibits the Tyndall effect while requiring only minimal amounts of the organic vehicle, the polyfluoropolyether silane, and the fluorinated vehicle.

[0097] Generally, the greater the period of time during which the non-aqueous emulsion exhibits the Tyndall effect, the greater the shelf-life and stability of the non-aqueous emulsion. In various embodiments, the organic vehicle is selected such that the non-aqueous emulsion exhibits the Tyndall effect for a period of time of greater than 0 seconds, alternatively at least 5 seconds, alternatively at least 1 minute, alternatively at least 5 minutes, alternatively at least 1 hour, alternatively at least 8 hours, alternatively at least 1 day, alternatively at least 2 days, alternatively at least 1 week, alternatively at least 1 month, alternatively at least 1 year, alternatively up to 50 years. Generally, the non-aqueous emulsion no longer exhibits the Tyndall effect once the non-aqueous emulsion substantially settles. In these embodiments, the non-aqueous emulsion may typically be re-formed by applying a shear force to the heterogeneous mixture, such as by shaking or stirring. Said differently, the components, if settled, generally once again form the non-aqueous emulsion upon application of a shear force. In certain embodiments, the non-aqueous emulsion may exhibit the Tyndall effect perpetually, i.e., the non-aqueous emulsion may not settle and has excellent long term stability.

[0098] The continuous phase of the non-aqueous emulsion may consist essentially of, or consist of, the organic vehicle. Alternatively, the continuous phase of the non-aqueous emulsion may consist essentially of, or consist of, the organic vehicle and the additive compound. The continuous phase of the non-aqueous emulsion typically comprises the organic vehicle in an amount of at least 10, alternatively at least 20, alternatively at least 30, alternatively at least 40, alternatively at least 50, alternatively at least 60, alternatively at least 70, alternatively at least 80, alternatively at least 90, alternatively at least 95, alternatively at least 96, alternatively at least 97, alternatively at least 98, alternatively at least 99, percent by weight based on the total weight of the continuous phase. In these embodiments, the continuous phase of the non-aqueous emulsion typically comprises the organic vehicle in an amount of at least 16.56, alternatively at least 30.86, alternatively at least 43.35, alternatively at least 54.35, alternatively at least 64.10, alternatively at least 72.82, alternatively at least 80.65, alternatively at least 87.72, alternatively at least 94.14, alternatively at least 97.14, alternatively at least 97.72, alternatively at least 98.30, alternatively at least 98.87, alternatively at least 99.44, percent by volume based on the total volume of the continuous phase. For example, if desired, the non-aqueous emulsion may be a concentrate in which the continuous phase is minimized in the ranges set forth above and the discontinuous phase is maximized. Alternatively, to reduce overall cost of the non-aqueous emulsion, the continuous phase may be maximized in the ranges set forth above. The amount of the organic vehicle in the continuous phase may vary from the ranges set forth immediately above contingent on the absence or presence of various optional components employed in the non-aqueous emulsion, as described in greater detail below.

[0099] The amount of the continuous phase present in the non-aqueous emulsion is contingent on the amount of the discontinuous phase present in the non-aqueous emulsion, which is largely based on the presence or absence of the fluorinated vehicle.

[00100] For example, in embodiments excluding the fluorinated vehicle from the discontinuous phase, the continuous phase is typically present in the non-aqueous emulsion in an amount of from 99.0 to less than 100, alternatively from 99.5 to less than 100, alternatively from 99.7 to 99.9, percent by weight based on the total weight of the nonaqueous emulsion. In these embodiments, the continuous phase is typically present in the non-aqueous emulsion in an amount of from 99.44 to less than 100, alternatively from 99.72 to less than 100, alternatively from 99.83 to less than 100, alternatively from 99.9 to less than 100, percent by volume based on the total volume of the non-aqueous emulsion.

[00101]Alternatively, in embodiments including the fluorinated vehicle in the discontinuous phase, the continuous phase is typically present in the non-aqueous emulsion in an amount of from 70 to less than 100, alternatively from 80 to less than 100, alternatively from 90 to less than 100, alternatively from 95 to less than 100, alternatively from 98.0 to 99.75, alternatively from 98.75 to 99.25, percent by weight based on the total weight of the nonaqueous emulsion. In these embodiments, the continuous phase is typically present in the non-aqueous emulsion in an amount of from 80.65 to less than 100, alternatively from 87.72 to less than 100, alternatively from 94.14 to less than 100, alternatively from 97.14 to less than 100, alternatively from 98.87 to 99.86, alternatively from 99.3 to 99.58, percent by volume based on the total volume of the non-aqueous emulsion.

[00102] As understood in the art, the discontinuous phase typically has a greater density than the continuous phase. As such, based on a selection of the discontinuous phase and the continuous phase, the relative weights or masses and corresponding volumes of the discontinuous phase and the continuous phase may vary.

[00103]The discontinuous phase generally forms particles in the continuous phase of the non-aqueous emulsion. The particles are liquid and may alternatively be referred to as droplets. The size of the particles is typically contingent on, for example, whether the discontinuous phase also comprises the fluorinated vehicle, and the relative amounts of the polyfluoropolyether silane and the fluorinated vehicle in the discontinuous phase. In certain embodiments, the particles have an average particle size of from 0.01 to 2.0, alternatively from 0.05 to 1 .5, alternatively from 0.1 to 1 .0, alternatively from 0.15 to 0.5, alternatively from 0.20 to 0.40, micrometers, as measured via a dynamic light scattering technique. As understood in the art, the average particle size may vary dependent on the technique utilized to measure the average particle size, and techniques other than dynamic light scattering may be utilized herein.

[00104] The average particle size of the discontinuous phase of the non-aqueous emulsion may be selectively controlled. In particular, when the discontinuous phase comprises the fluorinated vehicle in combination with the polyfluoropolyether silane, increasing the concentration of the fluorinated vehicle (i.e., decreasing the concentration of the polyfluoropolyether silane) in the fluorinated concentration results in smaller particle sizes. As such, modifying the relative amounts of the fluorinated vehicle and the polyfluoropolyether silane in the fluorinated composition impacts particle size of the discontinuous phase of the non-aqueous emulsion.

[00105] In one specific embodiment, the non-aqueous emulsion comprises the organic vehicle in an amount of from 90 to 99.9, alternatively from 95 to 99.8, alternatively from 98 to 99.7, percent by weight based on the total weight of the non-aqueous emulsion. In this embodiment, the non-aqueous emulsion comprises the fluorinated vehicle in an amount of from greater than 0 to 5, alternatively from 0.15 to 2.5, alternatively from 0.30 to 2.0, percent by weight based on the total weight of the non-aqueous emulsion. Finally, in this embodiment, the non-aqueous emulsion comprises the polyfluoropolyether silane in an amount of from greater than 0 to 1 , alternatively from 0.05 to 0.5, alternatively from 0.1 to 0.3, percent by weight based on the total weight of the non-aqueous emulsion. In this specific embodiment, the non-aqueous emulsion comprises the organic vehicle in an amount of from 94.14 to 99.94, alternatively from 97.14 to 99.89, alternatively from 98.87 to 99.83, percent by volume based on the total volume of the non-aqueous emulsion. In this embodiment, the non-aqueous emulsion comprises the fluorinated vehicle in an amount of from greater than 0 to 2.86, alternatively from 0.08 to 1 .42, alternatively from 0.17 to 1 .13, percent by volume based on the total volume of the non-aqueous emulsion. Finally, in this embodiment, the non-aqueous emulsion comprises the polyfluoropolyether silane in an amount of from greater than 0 to 0.56, alternatively from 0.03 to 0.28, alternatively from 0.06 to 0.17, percent by volume based on the total volume of the non-aqueous emulsion.

[00106] In various embodiments, the non-aqueous emulsion further comprises a surfactant. The surfactant may be present in the continuous phase and/or the discontinuous phase (or at an interface thereof). The surfactant may be nonionic, anionic, cationic, amphoteric, or Zwitterionic. The surfactant may be, for example, monomeric, oligomeric, or polymeric in nature. While surfactants are generally required in conventional emulsion, because the instant non-aqueous emulsion is generally prepared via self-emulsification in the absence of significant shear, the instant non-aqueous emulsion may be prepared in the absence of any surfactants. If utilized, the surfactant may be present at an interface between the continuous and discontinuous phase, contingent on its ionicity and other physical properties. The surfactant may additionally or alternatively be present in the continuous and/or discontinuous phase of the non-aqueous emulsion. Further, if utilized, the surfactant is typically present in the non-aqueous emulsion in an amount of less than 1 , alternatively less than 0.1 , alternatively less than 0.01 , percent by weight based on the total weight of the non-aqueous emulsion. However, because the surfactant is not required to prepare the instant nonaqueous emulsion, in certain embodiments, the non-aqueous emulsion consists essentially of, or consists of, the organic vehicle in the continuous phase and the fluorinated vehicle and the polyfluoropolyether silane in the discontinuous phase. The surfactant may be utilized as the additive compound, but typically is distinguished therefrom.

[00107] The non-aqueous emulsion may additionally include any other suitable component(s), such as a coupling agent, an antistatic agent, an ultraviolet absorber, a plasticizer, a leveling agent, a pigment, a catalyst, and so on. Such components may be present in the continuous phase and/or the discontinuous phase of the non-aqueous emulsion. These components may be utilized as the additive compound, but typically are distinguished therefrom.

[00108] Catalysts may optionally be utilized to promote surface modification by the nonaqueous emulsion. These catalysts may promote the reaction between any hydrolysable groups of the polyfluoropolyether silane and the surface of the article. These catalysts can be used individually or as a combination of two or more in the non-aqueous emulsion. Examples of suitable catalytic compounds include acids, such as carboxylic acids, e.g. formic acid, acetic acid, propionic acid, butyric acid, and/or valeric acid; bases; metal salts of organic acids, such as dibutyl tin dioctoate, iron stearate, and/or lead octoate; titanate esters, such as tetraisopropyl titanate and/or tetrabutyl titanate; chelate compounds, such as acetyl acetonato titanium; aminopropyltriethoxysilane, and the like. If utilized, the catalysts are typically utilized in an amount of from greater than 0 to 5, alternatively 0.0001 to 1 , alternatively 0.001 to 0.1 , percent by weight, based on 100 parts by weight of the nonaqueous emulsion.

[00109] As set forth above, the invention further provides a surface-treated article and methods of preparing surface-treated articles, which are described collectively in greater detail below.

[00110] To prepare the surface-treated article, a layer is deposited on a surface of an untreated article. The untreated article is ready for surface treatment as described below. In certain embodiments, a silica (Si0₂) is pre-deposited on the surface of the untreated article prior to depositing the layer. As such, in these embodiments, the surface of the untreated article includes the pre-deposited silica. The layer is formed from the non-aqueous emulsion, which is applied on the surface of the untreated article to prepare the surface-treated article. For example, the method of preparing the surface-treated article comprises applying the nonaqueous emulsion on the surface of the untreated article to form a wet layer thereof on the surface of the untreated article. The method further comprising removing the organic vehicle from the wet layer to form a layer on the surface of the untreated article and give the surface- treated article. Although the article may be any article, because of the excellent physical properties obtained from the non-aqueous emulsion of the invention, the article is typically an electronic article, an optical article, consumer appliances and components, automotive bodies and components, etc. Most typically, the article is an article for which it is desirable to reduce stains and/or smudges resulting from fingerprints or skin oils.

[00111] Examples of electronic articles typically include those having electronic displays, such as LCD displays, LED displays, OLED displays, plasma displays, etc. These electronic displays are often utilized in various electronic devices, such as computer monitors, televisions, smart phones, GPS units, music players, remote controls, hand-held video games, portable readers, etc. Exemplary electronic articles include those having interactive touch-screen displays or other components which are often in contact with the skin and which oftentimes display stains and/or smudges.

[00112] As introduced above, the article may also be a metal article, such as consumer appliances and components. Exemplary articles are a dishwasher, a stove, a microwave, a refrigerator, a freezer, etc, typically those having a glossy metal appearance, such as stainless steel, brushed nickel, etc.

[00113] Alternatively, the article may be a vehicle body or component such as an automotive body or component. For example, the non-aqueous emulsion may be applied directly on a top coat of an automobile body to form the layer, which imparts the automobile body with a glossy appearance, which is aesthetically pleasing and resists stains, such as dirt, etc., as well as smudges from fingerprints.

[00114] Examples of suitable optical articles include inorganic materials, such as glass plates, glass plates comprising an inorganic layer, ceramics, and the like. Additional examples of suitable optical articles include organic materials, such as transparent plastic materials and transparent plastic materials comprising an inorganic layer, etc. Specific examples of optical articles include antireflective films, optical filters, optical lenses, eyeglass lenses, beam splitters, prisms, mirrors, etc.

[00115] Among organic materials, examples of transparent plastic materials include materials comprising various organic polymers. From the view point of transparency, refractive index, dispersability and like optical properties, and various other properties such as shock resistance, heat resistance and durability, materials used as optical members usually comprise polyolefins (polyethylene, polypropylene, etc.), polyesters (polyethylene terephthalate, polyethylene naphthalate, etc.), polyamides (nylon 6, nylon 66, etc.), polystyrene, polyvinyl chloride, polyimides, polyvinyl alcohol, ethylene vinyl alcohol, acrylics, celluloses (triacetylcellulose, diacetylcellulose, cellophane, etc.), or copolymers of such organic polymers. It is to be appreciated that these materials may be utilized in ophthalmic elements. Non-limiting examples of ophthalmic elements include corrective and non- corrective lenses, including single vision or multi-vision lenses like bifocal, trifocal and progressive lenses, which may be either segmented or non-segmented, as well as other elements used to correct, protect, or enhance vision, including without limitation contact lenses, intra-ocular lenses, magnifying lenses and protective lenses or visors. Preferred material for ophthalmic elements comprises one or more polymers selected from polycarbonates, polyamides, polyimides, polysulfones, polyethylene terephthalate and polycarbonate copolymers, polyolefins, especially polynorbornenes, diethylene glycol- bis(allyl carbonate) polymers - known as CR39 - and copolymers, (meth)acrylic polymers and copolymers, especially (meth)acrylic polymers and copolymers derived from bisphenol A, thio(meth)acrylic polymers and copolymers, urethane and thiourethane polymers and copolymers, epoxy polymers and copolymers, and episulfide polymers and copolymers.

[00116] In addition to the articles described above, the non-aqueous emulsion of the invention can be applied to form the layer on other articles, such as window members for automobiles or airplanes, thus providing advanced functionality. To further improve surface hardness, it is also possible to perform surface modification by a so-called sol-gel process using a combination of the non-aqueous emulsion and TEOS (tetraethoxysilane).

[00117] One particular substrate of interest on which the non-aqueous emulsion may be applied to form the layer is any generation of Gorilla^® Glass, commercially available from Corning Incorporated of Corning, New York. Another particular substrate of interest is Dragontrail^®glass, commercially available from Asahi Glass Company of Tokyo, Japan.

[00118] The method by which the non-aqueous emulsion is applied on the surface of the untreated article to prepare the surface-treated article may vary.

[00119] For example, in certain embodiments, the step of applying the non-aqueous emulsion on the surface of the untreated article to form the wet layer uses a wet coating application method. Specific examples of wet coating application methods suitable for the method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, sputtering, slot coating, inkjet printing, and combinations thereof. The organic vehicle may be removed from the wet layer via heating or other known methods.

[00120] In other embodiments, the step of applying the non-aqueous emulsion on the surface of the untreated article may comprise forming the layer on the surface of the untreated article with a deposition apparatus. For example, when the deposition apparatus is utilized, the deposition apparatus typically comprises a physical vapor deposition apparatus. In these embodiments, the deposition apparatus is typically selected from a sputtering apparatus, an atomic layer deposition apparatus, a vacuum apparatus, and a DC magnetron sputtering apparatus. The optimum operating parameters of each of these physical deposition vapor apparatuses are based upon the non-aqueous emulsion utilized, the article on which the layer is to be formed, etc. In certain embodiments, the deposition apparatus comprises a vacuum apparatus. [00121] For example, when the layer is formed via physical vapor deposition (PVD), the method comprises combining the non-aqueous emulsion and a pellet to impregnate the pellet with the non-aqueous emulsion, thereby forming an impregnated pellet. The pellet typically comprises a metal, alloy, or other robust material, such as iron, stainless steel, aluminum, carbon, copper, ceramic, etc. Typically, the pellet has a very high surface area to volume ratio for contacting the polyfluoropolyether silane of the non-aqueous emulsion. The surface area to volume ratio of the pellet may be attributable to porosity of the pellet, i.e., the pellet may be porous. Alternatively, pellet may comprise woven, unwoven, and/or randomized fibers, such as nanofibers, so as to provide the desired surface area to volume ratio. The pellet may comprise a material selected from, for example, S1O2, T1O2, r02, MgO, AI2O3, CaS04, Cu, Fe, Al, stainless steel, carbon, or combinations thereof. The material may be a plug within a casing, which comprises the metal, alloy, or other robust material. The non-aqueous emulsion may be introduced in or to the pellet in any manner so long as the material of the pellet and the polyfluoropolyether silane are combined or otherwise contacted. For example, the pellet may be submerged in the non-aqueous emulsion, or the non-aqueous emulsion may be disposed within the casing such that the porous material is impregnated with the non-aqueous emulsion. Alternatively, the pellet may be submerged in the organic vehicle, or the organic vehicle may be disposed within the casing such that the material of the pellet is impregnated with the organic vehicle, and then the polyfluoropolyether silane, or the fluorinated composition, is disposed in the organic vehicle within the casing such that the material of the pellet is impregnated with the nonaqueous emulsion, which is formed in situ in or on the pellet. In these embodiments, the method further comprises removing the organic vehicle (and the fluorinated vehicle, if present) from the impregnated pellet to form a neat pellet prior to deposition. For example, the organic vehicle (and the fluorinated vehicle, if present) may be flashed from the pellet via the application of heat. Alternatively, the organic vehicle (and the fluorinated vehicle, if present) may be removed from the pellet by drying at room temperature or a slightly elevated temperature, optionally in the presence of a vacuum or purging air. The neat pellet may be stored until utilized in the deposition apparatus. In various embodiments, the neat pellet is stored in a vacuum-sealed aluminum bag.

[00122] Once specific example of a vacuum apparatus suitable for forming the layer from the non-aqueous emulsion is an HVC-900DA vacuum apparatus, commercially available from Hanil Vacuum Machine Co., Ltd. of Incheon, South Korea. Another example of a deposition apparatus is an Edwards AUTO 306, commercially available from Edwards of Sanborn, NY.

[00123] The neat pellet is generally placed on a heating element in a chamber of the deposition apparatus along with the article to be coated and the polyfluoropolyether silane is volatilized via resistive heat evaporation, thereby forming the layer on the surface of the article.

[00124] Independent of the method by which the layer is formed, once the layer is formed on the surface of the article from the non-aqueous emulsion, the layer may further undergo heating, humidification, catalytic post treatment, photoirradiation, electron beam irradiation, etc. For example, when the non-aqueous emulsion is applied via the deposition apparatus, the layer formed therefrom is generally heated at an elevated temperature, e.g. 80-150 'Ό, for a period of time, e.g. 45-75 minutes. Alternatively, the layer formed from the non-aqueous emulsion may be allowed to stand at room temperature and ambient conditions for a period of time, e.g. 24 hours.

[00125] Typically, the thickness of the layer formed from the non-aqueous emulsion is from 1 -1 ,000, alternatively 1 -200, alternatively 1 -100, alternatively 5-75, alternatively 10-50, alternative, 1 -5, alternatively 2-3, nanometers (nm).

[00126] As noted above, layers formed from the non-aqueous emulsion may have an excellent (i.e., low) coefficient of friction and excellent (i.e., high) durability. This is true regardless of whether the non-aqueous emulsion is applied via a wet coating method or via the deposition apparatus. For example, sliding (kinetic) coefficient of friction may be measured by disposing an object having a determined surface area and mass onto a surface-treated article including a layer formed from the non-aqueous emulsion with a select material (e.g. a standard piece of legal paper) between the object and the layer. A force is then applied perpendicular to gravitational force to slide the object across the layer for a predetermined distance, which allows for a calculation of the sliding coefficient of friction of the layer. The sliding coefficient of friction may vary depending not only on the relative amounts of the discontinuous phase and the continuous phase in the non-aqueous emulsion, but also on the particular polyfluoropolyether silane utilized in the non-aqueous emulsion. Durability of the layers formed from the non-aqueous emulsion is generally measured via the water contact angles of the layers after subjecting the layers to an abrasion test. For example, for layers having a lesser durability, the water contact angle decreases after abrasion, which generally indicates that the layer has at least partially deteriorated. [00127] In certain embodiments, the layers formed from the non-aqueous emulsion have a water contact angle of from 75-120, alternatively from 80-120, alternatively from 90-120, alternatively 100-120 degrees (^°), before and after subjecting the layers to the abrasion test. Because the non-aqueous emulsions have increased stability due to the control of the total water content, the layers formed from the non-aqueous emulsions typically have such water contact angles even after the non-aqueous emulsion is aged, e.g. after 1 month, after 2 months, after 3 months, etc. In certain embodiments, the layers formed from the nonaqueous emulsions have such water contact angles after aging the non-aqueous emulsions for up to 1 year, alternatively up to 2 years, alternatively up to 3 years. Aging refers to the non-aqueous emulsion itself, rather than the layer. For example, the non-aqueous emulsion may be stored, optionally in the dry sealed container or other vessel (e.g. a hermetically sealed container), while still being capable of forming layers having excellent physical properties. Without being held to any particular theory, it is believed that this contact angle performance is exhibited when the total water content of the non-aqueous emulsion is from 0 to less than 100, alternatively from 0 to 75, or alternatively from 0 to 50, parts per million (ppm) based on the total weight of the non-aqueous emulsion. In these embodiments, the layers also typically have a sliding (kinetic) coefficient of friction (μ) of less than 0.2, alternatively less than 0.15, alternatively less than 0.125, alternatively less than 0.10, alternatively less than 0.75, alternatively less than 0.50. Although coefficient of friction is unitless, it is often represented by (μ).

[00128] The non-aqueous emulsion of the invention forms layers having physical properties that are excellent as compared to the physical properties of conventional layers formed from conventional surface treatment compositions. Moreover, the non-aqueous emulsion of the invention may be prepared at a fraction of the cost of conventional surface treatment compositions and with significantly lower toxicity due to the significant presence of the organic vehicle (which results in a significant absence of the fluorinated vehicle) in the nonaqueous emulsion, which has a reduced cost and an improved health and environmental profile as compared to conventional solvents required to attain miscibility in conventional surface treatment compositions.

[00129] In some embodiments the invention is as described in any one of the following numbered aspects.

[00130] Aspect 1 . A method of preparing a non-aqueous emulsion, said method comprising: combining an organic vehicle and an additive compound to form an organic mixture; and combining the organic mixture and a polyfluoropolyether silane, thereby preparing the nonaqueous emulsion; wherein the non-aqueous emulsion comprises: a continuous organic phase comprising the organic vehicle; and a discontinuous phase comprising the polyfluoropolyether silane; and wherein the additive compound is different from the organic vehicle and the polyfluoropolyether silane.

[00131] Aspect 2. The method of aspect 1 further comprising combining the polyfluoropolyether silane and a fluorinated vehicle to pre-form a fluorinated composition such that the step of combining the organic mixture and the polyfluoropolyether silane comprises combining the organic mixture and the fluorinated composition.

[00132] Aspect 3. The method of aspect 1 or 2 wherein the additive compound comprises at least one of a silicone polymer and a drying agent.

[00133] Aspect 4. The method of aspect 3 wherein the additive compound comprises the drying agent, wherein the drying agent is (i) water- reactive or (ii) a desiccant.

[00134] Aspect 5. The method of aspect 4 wherein the drying agent is (i) water-reactive and is selected from the group of alkyltrialkoxysilane, disilazane, alkyltrioximosilane, alkyltri(carboxylic acid ester)silane, and trialkylhalosilane.

[00135] Aspect 6. The method of aspect 5 wherein the drying agent comprises disilazane and the disilazane is selected from the group of hexaalkyldisilazane, tetraalkyldialkenylsilazane, and diaryltetraalkyldisilazane.

[00136] Aspect 7. The method of any one preceding aspect wherein combining the organic mixture and the polyfluoropolyether silane forms a heterogeneous mixture and the method further comprises applying a shear force to the heterogeneous mixture to prepare the nonaqueous emulsion.

[00137] Aspect 8. The method of any one preceding aspect wherein combining the organic mixture and the polyfluoropolyether silane comprises disposing the polyfluoropolyether silane in the organic mixture.

[00138] Aspect 9. The method of any one preceding aspect further comprising forming a layer from the non-aqueous emulsion with the layer having a water contact angle of from 75 to 120^°.

[00139] Aspect 10. The method of aspect 9 wherein the layer has a water contact angle of from 90 to 120^°. [00140] Aspect 1 1 . The method of any one preceding aspect wherein the organic vehicle is selected such that the non-aqueous emulsion exhibits the Tyndall effect for a period of time of greater than 0 seconds.

[00141] Aspect 12. The method of aspect 1 1 wherein the organic vehicle is selected from the group consisting of t-butyl acetate, acetone, tetrahydrofuran, n-butyl acetate, dimethyl sulfoxide, methylene chloride, diglyme, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl 10-undecenoate, dimethylformamide, t-butyl acetoacetate, methyl isobutyl ketone, 2-pentanone, 2-butanone, acetylacetone, limonene, xylene, propylene carbonate, isopropanol, 1 -methoxy-2-propanol, propylene glycol monomethyl ether acetate, isoamyl acetate, diethyl fumarate, t-butanol, 1 -butanol, t-butyl methyl ether, toluene, ethylene glycol, and combinations thereof.

[00142] Aspect 13. The method of any one preceding aspect wherein the polyfluoropolyether silane has the general formula (B): Y-Z_a1 -(OC3F₆)_b1 -(OCF(CF3)CF2)ci -(OCF₂CF(CF3))_d1 -

(OC₂F₄)_ei -(CF(CF₃))_f1 -(OCF₂)_gi -(CH₂)_hi -B-(C_{n 1} H_2ni M(SiR ⁶ ₂-0)_{m 1} -SiR^"" ⁶ ₂)_M -

(Cj-| H₂j-| )-Si-(X)3_Z-| (R^{1 7})_z-| ; wherein Z is independently selected from -(CF₂)-, -

(CF(CF₃)CF₂0)-, -(CF₂CF(CF₃)0)-, -(CF(CF₃)0)-, -(CF(CF₃)CF₂)-, -(CF₂CF(CF₃))-, and -

(CF(CF₃))-; a1 is an integer from 1 to 200; b1 , c1 , d1 , e1 , f1 , and g1 are integers each independently selected from 0 to 200; hi , n1 and j1 are integers each independently selected from 0 to 20; i1 and ml are integers each independently selected from 0 to 5; B is a bivalent organic group or O; each R¹ ^ is an independently selected C-| -C₂₂ hydrocarbyl group; z1 is an integer independently selected from 0 to 2; each X is an independently selected hydrolysable group; each R^{1 7} is an independently selected C-| -C₂₂ hydrocarbyl group which is free of aliphatic unsaturation; and Y is selected from H, F, and Si-(X)₃. zl (R⁷)zl (Cjl H_{2j 1} )-((SiR6₂-0)m1 -SiR⁶2)i1 -(Cnl H_2nl )-X-(CH₂)_{h 1} -; wherein X, z1 , R16,

R^{1 7}, j1 , ml , i1 , n1 and hi are as defined above; provided that when subscript i1 is 0, subscript j1 is 0; when subscript i1 is an integer greater than 0, each of subscripts j1 and ml independently is an integer greater than 0.

[00143] Aspect 14. The method of aspect 13 wherein the hydrolysable group represented by X in general formula (B) of the polyfluoropolyether silane is independently selected from H, a halide, -OR¹ , -NHR¹ , -NR¹ R², -OC(0)-R¹ , -0-N=CR¹ R², 0-C(=CR¹ R²)R³, and -NRl COR2, wherein R1 , R^ and R^ are each independently selected from H and a C-1 -C22 hydrocarbon group, and wherein R1 and R^, together with the nitrogen atom to which they are both bonded in -NR^ R^, optionally can form a cyclic amino.

[00144] Aspect 15. A non-aqueous emulsion prepared in accordance with the method of any one preceding aspect.

[00145] Aspect 16. A method of preparing a surface-treated article, said method comprising: applying the non-aqueous emulsion of aspect 15 on a surface of an untreated article to form a wet layer on the surface of the untreated article; and removing the organic vehicle from the wet layer to form the surface-treated article.

[00146] Aspect 17. The method of aspect 16 wherein the step of applying the non-aqueous emulsion uses an application method selected from dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, slot coating, and combinations thereof.

[00147] Aspect 18. A method of preparing a surface-treated article, said method comprising the steps of: combining the non-aqueous emulsion of aspect 15 and a pellet to impregnate the pellet with the non-aqueous emulsion, thereby forming an impregnated pellet; removing the organic vehicle from the impregnated pellet to form a neat pellet; and forming a layer on a surface of an untreated article with the neat pellet via a deposition apparatus, thereby preparing the surface-treated article.

[00148] It is to be understood that the appended claims are not limited to express and particular compounds, non-aqueous emulsion, or methods described in the detailed description, which may vary between particular embodiments which fall within the scope of the appended claims. With respect to any Markush groups relied upon herein for describing particular features or aspects of various embodiments, different, special, and/or unexpected results may be obtained from each member of the respective Markush group independent from all other Markush members. Each member of a Markush group may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims.

[00149] Further, any ranges and subranges relied upon in describing various embodiments of the invention independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein. One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the invention, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on. As just one example, a range "of from 0.1 to 0.9" may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims. In addition, with respect to the language which defines or modifies a range, such as "at least," "greater than," "less than," "no more than," and the like, it is to be understood that such language includes subranges and/or an upper or lower limit. As another example, a range of "at least 10" inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims. Finally, an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims. For example, a range "of from 1 to 9" includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1 , which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.

[00150] The following examples are intended to illustrate the invention and are not to be viewed in any way as limiting to the scope of the invention.

EXAMPLES

[00151] Example 1 and Comparative Examples 1-2 :

[00152] Table 1 below illustrates the components utilized to prepare the non-aqueous emulsions (if formed) along with their respective amounts for Example 1 and Comparative Examples 1 -2. The same additive compound, organic vehicle, polyfluoropolyether silane, and fluorinated vehicle are utilized in Example 1 and Comparative Examples 1 -2 (where applicable, i.e., when a particular example includes such a component).

[00153] In Example 1 , the additive compound is disposed in the carrier solvent to form an organic composition. The organic composition is combined with the organic vehicle to form the organic mixture. The polyfluoropolyether silane is combined with the fluorinated vehicle to pre-form a fluorinated composition. The fluorinated composition and the organic mixture are combined to prepare the non-aqueous emulsion. This material exhibits the Tyndall effect. [00154] In Comparative Example 1 , the additive compound is disposed in the carrier solvent to form an organic composition. The polyfluoropolyether silane is combined with the fluorinated vehicle to form a fluorinated composition. The organic composition and the fluorinated composition are blended to form a mixture. However, Comparative Example 1 does not utilize the organic vehicle, and the fluorinated composition of Comparative Example 1 is distinguished from a non-aqueous emulsion.

[00155] In Comparative Example 2, the additive compound is disposed in the carrier solvent to form an organic composition. The polyfluoropolyether silane is disposed in the fluorinated vehicle pre-form a fluorinated composition. The organic composition and the fluorinated composition are combined to form an ingredient blend. The ingredient blend is combined with the organic vehicle to form a mixture. The mixture of Comparative Example 2 did not form a non-aqueous emulsion. Instead, the mixture of Comparative Example 2 had poor stability and settled heterogeneously.

[00156] In Table 1 below, "C.E." indicates "Comparative Example," "PFPE Silane" indicates "polyfluoropolyether silane," and "#" designates the number associated with the particular organic vehicle, fluorinated vehicle, additive compound, and polyfluoropolyether silane utilized, as defined following Table 1 .

[00157] Table 1 :

[00158] Organic Vehicle 1 is t-butyl acetate.

[00159] Fluorinated Vehicle 1 is ethoxy-nonafluorobutane (C4F9OC2H5).

[00160] Polyfluoropolyether (PFPE) Silane 1 has the general formula: F((CF₂)30)_c'CF2CF2CH₂0(CH2)3Si(OMe)3, where c' is from 17-25.

[00161] Additive Compound 1 is a siloxane polymer having the following general formula:

where e" is 800-850. Additive Compound 1 is utilized in a carrier solvent.

[00162] Carrier Solvent 1 comprises hexamethyldisiloxane.

[00163] Carrier Solvent 2 comprises t-butyl acetate.

Samples of the non-aqueous emulsion of Example 1 and the fluorinated composition of Comparative Example 1 are each applied to a surface of a substrate via spray coating. The mixture from Comparative Example 2 is not utilized in this manner as it undesirably settled and had poor stability. In particular, the non-aqueous emulsion of Example 1 and the fluorinated composition of Comparative Example 1 are applied to a glass substrate via a PVA-1000 dispensing machine (from Precision, Valve, & Automation of Cohoes, NY) having an atomization pressure of 8 psi, a liquid pressure of 3 psi, a stroke of 0.004", a nozzle height of 7 cm, a spacing of 10 mm, and a speed of about 200 mm/sec. Prior to applying Example 1 and the Comparative Example 1 to the glass substrate, the glass substrate is cleaned with detergent in an ultrasonic bath for 20 minutes, and then rinsed with deionized water three times for 2 min each in an ultrasonic bath (Fisher Scientific FS-220). After cleaning, the glass substrate is dried in a 125°C oven for 1 hour. After drying, the glass substrate is plasma treated using a March Plasma PX250 chamber (60mTorr base pressure using ionized Argon for 60 seconds, 300W RF power supply) to activate the glass substrates. The activated glass substrates are used immediately.

[00164] Once the non-aqueous emulsion (or fluorinated composition) was applied to the substrate, the non-aqueous emulsion (or fluorinated composition) was cured at 125 'C for 1 hour to form layers on the substrates. Coated substrates were then rinsed with Fluorinated Vehicle 1 to remove any excess, uncured material.

[00165] Physical properties of the layers formed from the non-aqueous emulsion and fluorinated composition are measured. In particular, the water contact angle of the respective layers are measured before and after subjecting the layers to an abrasion resistance test, as described below. Further, sliding coefficient of friction (COF) is also measured for each of the layers. [00166] More specifically, the sliding COF is measured via a TA-XT2 Texture Analyzer, commercially available from Texture Technologies of Scarsdale, NY. The sliding COF is measured by placing a sled having a load of about 156 grams onto each of the layers with a piece of standard paper disposed between each of the layers and the sled. The sled has an area of about 25 x 25 millimeters. A force is applied in a direction perpendicular to gravity to move the sled along each of the layers at a speed of about 2.5 millimeters/sec for a distance of about 42 millimeters to measure the sliding COF.

[00167] The abrasion resistance test utilizes a reciprocating abraser - Model 5900, which is commercially available from Taber Industries of North Tonawanda, New York. The abrading material utilized was a CS-10 Wearaser^® from Taber Industries. The abrading material has dimensions of 6.5 mm x 12.2 mm. The reciprocating abraser is operated for 25 cycles at a speed of 25 cycles per minute with a stroke length of 1 inch and a load of 7.5 N.

[00168] The water contact angle (WCA) of each of the layers is measured via a VCA Optima XE goniometer, which is commercially available from AST Products, Inc., Billerica, MA. The water contact angle measured is a static contact angle based on a 2 μΙ_ droplet on each of the layers. The water contact angle is measured before and after the abrasion resistance test described above. The WCA is measured for each of the layers as described above before and after subjecting these layers to the abrasion resistance test also described above (designated as "abraded" and "unabraded" below). Table 2 below illustrates the WCA for the layers formed from Example 1 and Comparative Example 1 . Generally, the greater the WCA after abrasion, the greater the durability of the layer. The WCA values in Table 2 are in degrees (°). The WCA values in Table 2 represent the mean values based on 18 different measurements for each WCA value. The sliding COF values in Table 2 represent the mean values based on 30 different measurements for each COF value. Although sliding COF is unitless, it is often represented by (μ).

[00169] Table 2:

[00170] As clearly illustrated in Table 2 above, the layer formed from the non-aqueous emulsion of Example 1 had a WCA before and after abrasion that corresponded to the layer formed from the fluorinated composition of Comparative Example 1 . Further, the layer formed from the non-aqueous emulsion of Example 1 had a lesser sliding COF than the layer formed from the composition of Comparative Example 1 , which is desirable. Notably, because the non-aqueous emulsion of Example 1 includes the organic vehicle, the nonaqueous emulsion can be prepared at a significantly lesser cost than the fluorinated composition of Comparative Example 1 while still providing excellent performance in regards to the layers formed therefrom. Further, this is particularly surprising, considering merely combining the components, as done in Comparative Example 2, failed to prepare a nonaqueous emulsion altogether.

[00171] Example 2 and Comparative Examples 3-4:

[00172] Table 3 below illustrates the components utilized to prepare the non-aqueous emulsions (if formed) along with their respective amounts for Example 2 and Comparative Examples 3-4. In Example 2 and Comparative Examples 3-4, the same organic vehicle, fluorinated vehicle, polyfluoropolyether silane, and additive compound are utilized as in Example 1 and Comparative Examples 1 -2 above.

[00173] In Example 2, the organic composition is combined with the organic vehicle to form the organic mixture. The polyfluoropolyether silane is combined with the fluorinated vehicle to pre-form a fluorinated composition. The fluorinated composition and the organic mixture are combined to prepare the non-aqueous emulsion. This material exhibits the Tyndall effect.

[00174] In Comparative Example 4, the organic composition and the fluorinated composition are blended to give a mixture. This mixture (which also includes the additive compound) is combined with the organic vehicle. The resulting mixture immediately settled and did not form a non-aqueous emulsion.

[00175] In Comparative Example 3, the polyfluoropolyether silane is disposed in the fluorinated vehicle pre-form a fluorinated composition. The fluorinated composition is combined with the organic vehicle to form a non-aqueous emulsion. The additive compound is then combined with the non-aqueous emulsion. However, the additive compound did not disperse or emulsify in the non-aqueous emulsion, and thus the addition of the additive compound resulted in a heterogeneous mixture that did not constitute a non-aqueous emulsion.

[00176] In Table 3 below, "C.E." indicates "Comparative Example," "PFPE Silane" indicates "polyfluoropolyether silane," and "#" designates the number associated with the particular organic vehicle, fluorinated vehicle, additive compound, and polyfluoropolyether silane utilized, as defined following Table 3. [00177] Table 3:

[00178] As clearly illustrated above, the non-aqueous emulsion only formed when the additive compound is first combined with the organic vehicle to form an organic mixture. Simultaneously combining the polyfluoropolyether silane, the additive compound, and the organic vehicle, as in Comparative Example 4, resulted in a mixture that undesirably settled. Further, combining the additive compound with a pre-formed non-aqueous emulsion does not result in the additive compound readily dispersing within the pre-formed non-aqueous emulsion.

[00179] Example 3 and Comparative Examples 5-7:

[00180] Table 4 below illustrates the components utilized to prepare the non-aqueous emulsions (if formed) along with their respective amounts for Example 3 and Comparative Examples 5-7. In Example 3 and Comparative Examples 5-7, the same organic vehicle, fluorinated vehicle, polyfluoropolyether silane, and additive compound are utilized as in Example 1 and Comparative Examples 1 -2 above.

[00181] In Example 3, the additive compound is combined with the organic vehicle to form the organic mixture. The polyfluoropolyether silane is combined with the fluorinated vehicle to pre-form a fluorinated composition. The fluorinated composition and the organic mixture are combined to prepare the non-aqueous emulsion. This material exhibits the Tyndall effect.

[00182] In Comparative Example 5, the additive compound is disposed in the fluorinated vehicle along with the polyfluoropolyether silane to form a fluorinated composition. However, Comparative Example 5 does not utilize the organic vehicle, and the fluorinated composition of Comparative Example 5 is distinguished from a non-aqueous emulsion.

[00183] In Comparative Example 6, the additive compound and the polyfluoropolyether silane are combined with the fluorinated vehicle to form a first fluorinated composition. This first fluorinated composition (which also includes the additive compound) is combined with the organic vehicle. The resulting mixture immediately settled and did not form a nonaqueous emulsion. The additive compound is disposed in the carrier solvent at the time of forming the first fluorinated composition.

[00184] In Comparative Example 7, the additive compound and the polyfluoropolyether silane are combined with the fluorinated vehicle to form a second fluorinated composition. This second fluorinated composition (which also includes the additive compound) is combined with the organic vehicle. The resulting mixture immediately settled and did not form a non-aqueous emulsion. The additive compound is disposed in the organic vehicle at the time of forming the second fluorinated composition. As such, the difference between Comparative Examples 6 and 7 is not the order of addition, but rather whether the carrier solvent is utilized along with the additive compound (or whether the organic vehicle is utilized for this purpose).

[00185] In Table 4 below, "C.E." indicates "Comparative Example," "PFPE Silane" indicates "polyfluoropolyether silane," "n/a" indicates the absence of a particular component, and "#" designates the number associated with the particular organic vehicle, fluorinated vehicle, additive compound, and polyfluoropolyether silane utilized, as defined following Table 3.

[00186] Table 4:

[00187] As clearly illustrated above, the non-aqueous emulsion formed when the additive compound is first combined with the organic vehicle to form an organic mixture.

[00188] Notwithstanding this fact, samples of the non-aqueous emulsions, fluorinated compositions, or heterogeneous mixtures of Example 3 and Comparative Examples 5-7 are utilized to prepare layers in accordance with the method described above for Example 1 , with the exception that the glass substrates are activated via a different method. Specifically, the glass substrates are cleaned with detergent in an ultrasonic bath for 20 minutes, and then rinsed with deionized water three times for 2 min each in the ultrasonic bath (Fisher Scientific FS-220). After cleaning, the glass substrates are dried in a 125°C oven for 1 hour. Before applying coatings, the glass substrates are plasma treated using an Enercon Dyna-A-Mite Air Plasma Surface Treater, 480W DC power supply to ionize air, 7mm nozzle height, 0 degree nozzle. A fixture containing a plasma treater is manually moved across the entire substrate from left to right, and then from top to bottom to active the glass substrates..

[00189] For Comparative Examples 6-7, although heterogeneous mixtures were formed that settled, these heterogeneous mixtures were shaken immediately prior to forming the layers so as to disperse the components (at least temporarily). Although layers could be formed from such heterogeneous mixtures, these heterogeneous mixtures had poor stability and shelf-life, and it is expected that performance would significantly decrease with ageing, i.e., over time prior to use.

[00190] Physical properties of the layers formed from the non-aqueous emulsion and fluorinated composition are measured. In particular, the water contact angle of the respective layers are measured before and after subjecting the layers to an abrasion resistance test, as described above. Further, sliding coefficient of friction (COF) is also measured for each of the layers as is also described above. Table 5 sets forth the results. The WCA values in Table 5 are in degrees ( °). The WCA values in Table 5 represent the mean values based on 18 different measurements for each WCA value. The sliding COF values in Table 5 represent the mean values based on 30 different measurements for each COF value. Although sliding COF is unitless, it is often represented by (μ).

[00191] Table 5:

[00192] As clearly illustrated in Table 5 above, the layer formed from the non-aqueous emulsion of Example 3 had a WCA before and after abrasion that corresponded to the layer formed from the fluorinated composition of Comparative Example 5. Further, the layer formed from the non-aqueous emulsion of Example 3 had a much lesser sliding COF than the layer formed from the composition of Comparative Example 5, which is desirable. Notably, because the non-aqueous emulsion of Example 3 includes the organic vehicle, the non-aqueous emulsion can be prepared at a significantly lesser cost than the fluorinated composition of Comparative Example 5 while still providing excellent performance in regards to the layers formed therefrom. Although desirable performance was also obtained from the layers formed from the heterogeneous mixtures of Comparative Examples 6-7, it is believed that this performance is attributable to the dispersing of the components prior to application as well as the immediate application to form the layers after shaking. Said differently, the heterogeneous mixtures of Comparative Examples 6-7 require immediate use and shear force.

[00193] The invention has been described in an illustrative manner, and it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation. Obviously, many modifications and variations of the invention are possible in light of the above teachings. The invention may be practiced otherwise than as specifically described.

Claims

What is claimed is:

1 . A method of preparing a non-aqueous emulsion, said method comprising:

combining an organic vehicle and an additive compound to form an organic mixture; and combining the organic mixture and a polyfluoropolyether silane, thereby preparing the nonaqueous emulsion;

wherein the non-aqueous emulsion comprises:

a continuous organic phase comprising the organic vehicle; and

a discontinuous phase comprising the polyfluoropolyether silane; and

wherein the additive compound is different from the organic vehicle and the polyfluoropolyether silane.

2. The method of claim 1 further comprising combining the polyfluoropolyether silane and a fluorinated vehicle to pre-form a fluorinated composition such that the step of combining the organic mixture and the polyfluoropolyether silane comprises combining the organic mixture and the fluorinated composition.

3. The method of claim 1 or 2 wherein the additive compound comprises at least one of a silicone polymer and a drying agent.

4. The method of claim 3 wherein the additive compound comprises the drying agent, wherein the drying agent is (i) water-reactive or (ii) a desiccant.

5. The method of claim 4 wherein the drying agent is (i) water-reactive and is selected from the group of alkyltrialkoxysilane, disilazane, alkyltrioximosilane, alkyltri(carboxylic acid ester)silane, and trialkylhalosilane.

6. The method of claim 5 wherein the drying agent comprises disilazane and the disilazane is selected from the group of hexaalkyldisilazane, tetraalkyldialkenylsilazane, and diaryltetraalkyldisilazane.

7. The method of any one preceding claim wherein combining the organic mixture and the polyfluoropolyether silane forms a heterogeneous mixture and the method further comprises applying a shear force to the heterogeneous mixture to prepare the non-aqueous emulsion.

8. The method of any one preceding claim wherein combining the organic mixture and the polyfluoropolyether silane comprises disposing the polyfluoropolyether silane in the organic mixture.

9. The method of any one preceding claim further comprising forming a layer from the nonaqueous emulsion with the layer having a water contact angle of from 75 to 120^°; or further comprising forming a layer from the non-aqueous emulsion wherein the layer has a water contact angle of from 90 to 120^°.

10. The method of any one preceding claim

wherein the organic vehicle is selected such that the non-aqueous emulsion exhibits the Tyndall effect for a period of time of greater than 0 seconds; or

wherein the organic vehicle is selected from the group consisting of t-butyl acetate, acetone, tetrahydrofuran, n-butyl acetate, dimethyl sulfoxide, methylene chloride, diglyme, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl 10-undecenoate, dimethylformamide, t-butyl acetoacetate, methyl isobutyl ketone, 2-pentanone, 2-butanone, acetylacetone, limonene, xylene, propylene carbonate, isopropanol, 1 -methoxy-2-propanol, propylene glycol monomethyl ether acetate, isoamyl acetate, diethyl fumarate, t-butanol, 1 - butanol, t-butyl methyl ether, toluene, ethylene glycol, and combinations thereof; or

wherein the organic vehicle is selected such that the non-aqueous emulsion exhibits the Tyndall effect for a period of time of greater than 5 seconds and the organic vehicle is selected from the group consisting of t-butyl acetate, acetone, tetrahydrofuran, n-butyl acetate, dimethyl sulfoxide, methylene chloride, diglyme, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl 10-undecenoate, dimethylformamide, t-butyl acetoacetate, methyl isobutyl ketone, 2-pentanone, 2-butanone, acetylacetone, limonene, xylene, propylene carbonate, isopropanol, 1 -methoxy-2-propanol, propylene glycol monomethyl ether acetate, isoamyl acetate, diethyl fumarate, t-butanol, 1 -butanol, t-butyl methyl ether, toluene, ethylene glycol, and combinations thereof.

1 1 . The method of any one preceding claim wherein the polyfluoropolyether silane has the general formula (B): Y-Z_a1 -(OC₃F₆)_b1 -(OCF(CF3)CF2)cl -(OCF2CF(CF3))_d1 -(OC2F4)ei -

(CF(CF₃))_f ! -(OCF₂)_gi -(CH₂)hl -B-(C_ni H_2r11 H(SiR^{1 6} ₂-0)_{m 1} -SiR^"" ⁶ ₂)ii -(C^ H_{2j 1} )

-Si-(X)₃._Z1 (R17)_{Z1 ;}

wherein Z is independently selected from -(CF₂)-, -(CF(CF3)CF₂0)-, -

(CF₂CF(CF₃)0)-, -(CF(CF₃)0)-, -(CF(CF₃)CF₂)-, -(CF₂CF(CF₃))-, and -(CF(CF₃))-; a1 is an integer from 1 to 200; b1 , c1 , d1 , e1 , f1 , and g1 are integers each independently selected from 0 to 200; hi , n1 and j1 are integers each independently selected from 0 to 20; i1 and ml are integers each independently selected from 0 to 5; B is a bivalent organic group or O; each R¹6 is an independently selected C-| -C₂₂ hydrocarbyl group; z1 is an integer independently selected from 0 to 2; each X is an independently selected hydrolysable group; each R^{1 7} is an independently selected C-| -C₂₂ hydrocarbyl group which is free of aliphatic unsaturation; and Y is selected from H, F, and Si-(X)₃._z-| (R⁷)_z-| (Cj-| H₂ji )-((SiR6₂-0)_m-| - SiR⁶ ₂)j-| -(C_n-| H_{2n 1} )-X-(CH₂)_{h 1} -; wherein X, z1 , R^{1 6}, R^{1 7}, j1 , ml , i1 , n1 and hi are as defined above;

provided that when subscript i1 is 0, subscript j1 is 0; when subscript i1 is an integer greater than 0, each of subscripts j1 and ml independently is an integer greater than 0.

12. The method of claim 1 1 wherein the hydrolysable group represented by X in general formula (B) of the polyfluoropolyether silane is independently selected from H, a halide, -

OR¹ , -NHR¹ , -NR¹ R², -OC(0)-R¹ , -0-N=CR¹ R², 0-C(=CR¹ R²)R³, and

-NR^ COR², wherein R1 , R² and R^ are each independently selected from H and a C-| -C₂₂ hydrocarbon group, and wherein R1 and R², together with the nitrogen atom to which they are both bonded in -NR1 R², optionally can form a cyclic amino.

13. A non-aqueous emulsion prepared in accordance with the method of any one preceding claim.

14. A method of preparing a surface-treated article, said method comprising: applying the non-aqueous emulsion of claim 13 on a surface of an untreated article to form a wet layer on the surface of the untreated article; and

removing the organic vehicle from the wet layer to form the surface-treated article.

15. A method of preparing a surface-treated article, said method comprising the steps of: combining the non-aqueous emulsion of claim 13 and a pellet to impregnate the pellet with the non-aqueous emulsion, thereby forming an impregnated pellet;

removing the organic vehicle from the impregnated pellet to form a neat pellet; and forming a layer on a surface of an untreated article with the neat pellet via a deposition apparatus, thereby preparing the surface-treated article.