WO2015142561A1

WO2015142561A1 - Non-aqueous emulsion and methods of preparing surface-treated articles therewith

Info

Publication number: WO2015142561A1
Application number: PCT/US2015/019565
Authority: WO
Inventors: Michael L. Bradford; Donald Liles; 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: TW201602248A

Abstract

A non-aqueous emulsion comprises a continuous organic phase comprising an organic vehicle. The non-aqueous emulsion further comprises a discontinuous phase comprising a polyfluoropolyether silane. A 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 said non¬ aqueous emulsion. Methods of preparing surface treated articles therewith are also disclosed.

Description

NON-AQUEOUS EMULSION AND METHODS OF PREPARING SURFACE- TREATED ARTICLES THEREWITH

FIELD OF THE INVENTION

[0001] The invention generally relates to a non-aqueous emulsion and, more specifically, to a non-aqueous emulsion for treating a surface 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

[0006] The invention provides a non-aqueous emulsion. The non-aqueous emulsion comprises a continuous organic phase comprising an organic vehicle. The non-aqueous emulsion further comprises a discontinuous phase comprising a polyfluoropolyether silane. A 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.

[0007] The invention additionally provides methods of preparing a surface-treated article. In a first method, the non-aqueous emulsion is applied to a surface of an article ready for surface treatment to form a wet layer thereof on the surface of the article. The first method further comprises removing the organic vehicle from the wet layer to form a layer on the surface of the article and give the surface-treated article. In a second method, the nonaqueous emulsion and a pellet are combined to impregnate the pellet with the non-aqueous emulsion, thereby forming 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, thereby preparing the surface-treated article.

[0008] 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

[0009] The invention provides a non-aqueous emulsion 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 non-aqueous emulsion has a significantly reduced cost and more favorable toxicological and environmental profile as compared to conventional compositions that typically include fluorinated polymers and halogenated solvents.

[0010] The non-aqueous emulsion comprises a continuous organic phase comprising an organic vehicle and a discontinuous phase comprising a polyfluoropolyether silane. By "nonaqueous," it is meant that water does not constitute either the continuous or the discontinuous phase of the non-aqueous emulsion. As described below, a 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.

[0011] The polyfluoropolyether silane of the discontinuous phase of the non-aqueous emulsion may be any known polyfluoropolyether 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.

[0012] In various embodiments, the polyfluoropolyether silane has the following general formula (A):

Y-Z_a-[(OC3F₆)_b-(OCF(CF3)CF2)c-(OCF₂CF(CF3))_d-(OC2F4)e-(CF(CF3))_f-(OCF2)g]- (CH₂)_h-B-(C_nH2n)-((SiR¹2-0)_m-SiRl 2)i-(C_jH_2j)-Si-(X)3._z(R2)_z.

[0013] While the polyfluoropolyether silane of the non-aqueous emulsion is not limited to that of general formula (A), specific aspects of general formula (A) are described in greater detail below. The groups indicated by subscripts b-g, i.e., the groups within the square brackets in formula (A), may be present in any order within the polyfluoropolyether silane, including a different order as that which is represented in general formula (A) 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 b may alternatively be written as (0-CF2-CF2-CF2) - In the description below, Cp' - 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 i 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.

[0014] In general formula (A) 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, a is an integer from 1 to 200; b, c, d, e, f, and g are integers each independently selected from 0 or from 1 to 200; h, n and j are integers each independently selected from 0 or from 1 to 20; i and m are integers each independently selected from 0 or from 1 to 5; B is a divalent organic group or an oxygen atom; each R¹ is an independently selected C-1 -C22 hydrocarbyl group; each z is an integer independently selected from 0 to 2; each X is an independently selected hydrolysable group; each R² is an independently selected C-1 -C22 hydrocarbyl group which is free of aliphatic unsaturation; and Y is selected from H, F, and (R²)_z(X)3-zSi-(CjH2j)-

((SiR¹2-0)_m-SiR¹2)j-(C_nH2n)-B-(CH2)n-; wherein X, B, z, R¹ , R², j, m, i, n, and h are as defined above.

[0015] R1 , which is an independently selected C-1 -C-22 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, R¹ is C-1 -C4 alkyl group. In addition, the groups indicated by subscripts n and j, i.e., groups

(C_nH2n) and (CjH2j), may also be independently linear or branched. For example, when n is

3, these groups may independently have the structure -CH2-CH2-CH2, -CH(CH₃)-CH2, or - CH2-CH(CH3)-, wherein the latter two structures have pendant alkyl groups, i.e., these structures are branched and not linear.

[0016] With respect to the moieties represented by subscripts m, i, and j: when subscript i is 0, subscript j is also 0; and when subscript i is an integer greater than 0, each of subscripts j and m is also an integer greater than 0. Said differently, when the group represented by subscript i is present, the group represented by subscript j is also present. The inverse is also true, i.e., when the group represented by subscript i is not present, the group represented by subscript j is also not present. In addition, when i is an integer greater than 0, the group represented by subscript m is present, and m is also an integer greater than 0. In certain embodiments, subscripts m and i are each 1 . Typically, the subscript i does not exceed 1 , although the subscript m may be an integer greater than 1 such that siloxane bonds (i.e., Si-0 bonds) are present within the group represented by subscript i.

[0017] In certain embodiments, the polyfluoropolyether silane of the non-aqueous emulsion is subject to the proviso that when Y is F; Z is -(CF2)-; a is an integer from 1 to 3; and subscripts c, d, f, i, m, and j are each 0.

[0018] The hydrolysable group represented by X in general formula (A) is independently selected from H, a halogen atom, an alkoxy (-OR³) group, an alkylamino (-NHR³ or - NR³R⁴) group, a carboxy (-OOC-R³) group, an alkyliminoxy (-0-N=CR³R⁴) group, an alkenyloxy (0-C(=CR³R⁴)R⁵) group, or an N-alkylamido (-NR³COR⁴) group, wherein R³, R⁴ and R^ are each independently selected from H and a C1 -C22 hydrocarbyl group. When

R³, R⁴ and R^ are independently C1 -C22 hydrocarbyl groups, R³, R⁴ and R^ may be linear, branched, or cyclic (for C3-C22 hydrocarbyl groups). In addition, R³, R⁴ and R^ may independently include one or more heteroatoms, such as N, O, and/or S, within the hydrocarbyl group, and may be substituted or unsubstituted. Typically, R³, R⁴ and R^ are each independently selected C1 -C4 alkyl groups. In certain embodiments, the hydrolysable group represented by X in general formula (A) is independently selected from an alkoxy (-

OR³) group and an alkylamino (-NHR³ or -NR³R⁴) group. When the hydrolysable group represented by X in general formula (A) is the NR³R⁴ group, R³ and R⁴,together with the nitrogen atom to which they are both bonded in NR³R⁴, optionally can form a cyclic amino group.. [0019] 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, z 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.

[0020] In certain embodiments, Y in general formula (A) is F. Typically, when Y in general formula (A) is F, subscripts c, d, and g in general formula (A) are each 0. As such, in these embodiments, when the groups indicated by subscripts c, d, and g are absent, the polyfluoropolyether silane has the general formula F-Z_a-[(OC3Fg)b-(OC2F4)_e-(CF(CF3))f]-

(CH2)_h-B-(C_nH2n)-((SiR¹2-0)_m-SiRl ₂)i-(CjH2j)-Si-(X)3._z(R2)_z.

[0021] In one embodiment of the non-aqueous emulsion in which Y in general formula (A) is F, as introduced above, Z in general formula (A) is -(CF2)-, subscripts c, d, f, and g in general formula (A) are 0 and subscripts b, e, h, and n in general formula (A) are each independently an integer greater than 0. As but one example of this embodiment, subscript a is 3, subscript b is at least 1 , subscript e is 1 , subscript h is 1 , B is an oxygen atom, subscript n is 3, and subscripts m, i, and j are each 0. In this one example, the polyfluoropolyether silane has the following general formula: CF3-CF2-CF2-(0-CF2-CF2-CF2) -0-CF2-CF2-

CH2-0-CH2-CH2-CH2-Si-(X)3__z(R²)_z. 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)b-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 b is typically an integer from 17 to 25.

[0022] In another embodiment of the non-aqueous emulsion in which Y in general formula (A) is F and Z in general formula (A) is -(CF2)-, as described above, subscripts c, d, f, and g in general formula (A) are 0 and subscripts b, e, h, n, m, i, and j in general formula (A) are each independently an integer greater than 0. As but one example of this embodiment, subscript a is 3, subscript b is at least 1 , subscript e is 1 , subscript h is 1 , B is an oxygen atom, subscript n is 3, subscript m and i are each 1 , and subscript j is 2. 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(CH3)2-0-Si(CH₃)2-CH2-CH2-Si-(X)3._z(R²)_z.

Thus, when the hydrolysable groups represented by X are all alkoxy groups, e.g. methoxy groups, and z is 0, 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(CH₃)2-0-

Si(CH3)2-CH2-CH2-Si(OCH3)3. In these embodiments, subscript b is typically an integer from 17 to 25.

[0023] In another embodiment of the non-aqueous emulsion in which Y in general formula (A) is F, as introduced above, Z in general formula (A) is -(CF(CF3)CF20)-. In this embodiment, subscripts b, c, d, e, and g in general formula (A) are 0, and subscripts f, h, and n in general formula (A) are each independently an integer greater than 0. As but one example of this embodiment, subscripts b, c, d, e, and g in general formula (A) are 0, subscript a is at least 1 , subscript f is 1 , subscript h is 1 , B is an oxygen atom, subscript n is 3, and subscripts i, m, and j 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-_Z(R²)_Z. Thus, when the hydrolysable groups represented by X are all alkoxy groups, e.g. methoxy groups, and z 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 a is typically an integer from 14 to 20.

[0024] In another embodiment of the non-aqueous emulsion in which Y in general formula (A) is F and Z in general formula (A) is -(CF(CF3)CF20)-, as introduced immediately above, subscripts b, c, d, e, and g in general formula (A) are 0, subscript a is at least 1 , subscript f is 1 , subscript h is 1 , B is an oxygen atom, subscript n is 3, subscripts m and i are each 1 , and subscript j is 2. In this one example, the 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-(X)3__Z(R²)_Z. Thus, when the hydrolysable groups represented by X are all alkoxy groups, e.g. methoxy groups, and z 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 a is typically an integer from 14 to 20.

[0025] In other embodiments, Y in general formula (A) is (R²)_z(X)3-z^Si-(^cj^H2j)-((^{SiR l} 2-°)m-

SiR¹2)i-(C_nH2n)-B-(CH2)h-- Typically, when Y in general formula (A) is (R²)_z(X)3-z^Si-

(CjH2j)-((SiR¹2-0)_m-SiR¹2)i-(C_nH2n)-B-(CH2) -> subscripts b, c, and f in general formula (A) are 0. As such, in these embodiments, when the groups indicated by subscripts b, c, and f are absent, the polyfluoropolyether silane has the following general formula: Y-Z_a-

[(OCF2CF(CF3))_d-(OC2F4)e-(OCF2)g]-(CH2)_h-B-(C_nH2n)-((SiR¹2-0)_m-SiRl ₂)i-(C_jH2_j)-Si- (X)3-z(R²)z-

[0026] In one embodiment in which Y in general formula (A) is (R²)z(X)3-zSi-(CjH2j)-

((SiR¹2-0)_m-SiR¹2)j-(C_nH2n)-B-(CH2)h-, ^as introduced immediately above, Z is -(CF2)-, B is an oxygen atom, subscripts b, c, d, and f in general formula (A) are 0, and subscripts e and g in general formula (A) are each independently an integer greater than 0. As but one example of this embodiment, Z is -(CF2)-, B is an oxygen atom, subscripts b, c, d, f, m, i, and j in general formula (A) are 0, subscript e is at least 1 , subscript g is at least 1 , subscript h is 1 , B is an oxygen atom, and subscript n is 3. In this one example, the polyfluoropolyether silane has the following general formula: (R²)_z(X)3._zSi-CH₂-CH2-CH2-0-CH2-CF₂-

(OCF2CF2)e-(OCF₂)g-CH2-0-CH2-CH2-CH2-Si-(X)3._z(R²)_z. Thus, when the hydrolysable groups represented by X are all alkoxy groups, e.g. methoxy groups, and z 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 z is 0, this particular polyfluoropolyether silane has the following general formula: ((CH3)2N)3Si-CH2-CH2-CH2-0-CH2-CF2-(OCF₂CF2)e-(OCF2)g-CH2-0-CH2- CH2-CH₂-Si-(N(CH₃)2)3.

[0027] Alternatively, in another embodiment in which Y in general formula (A) is (R²)_Z(X)3- _zSi-(CjH2j)-((SiR¹2-0)_m-SiR¹2)j-(C_nH2n)-B-(CH2)h-_! as introduced above, Z is -(CF₂)-, B is an oxygen atom, subscripts b, c, e, and f in general formula (A) are 0, and subscripts d and g in general formula (A) are each independently an integer greater than 0.

[0028] 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.

[0029] 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.

[0030] In various embodiments, the non-continuous phase of the non-aqueous emulsion further comprises a fluorinated vehicle. 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, particularly the discontinuous phase of the nonaqueous 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.

[0031] 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.

[0032] In embodiments in which the fluorinated vehicle comprises the perfluoropolyether vehicle, the perfluoropolyether vehicle typically has the following general formula:

F,C- -O— CF— OF. ^■O— CF_; -O— CF,

b"

CF₃

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:

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

[0033] 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 C12F27 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. [0034] The discontinuous phase of the non-aqueous emulsion 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] As introduced above, the non-aqueous emulsion further comprises a continuous phase comprising an organic vehicle. The organic vehicle of the continuous phase may be any organic vehicle capable of emulsifying the polyfluoropolyether silane (and optionally the fluorinated vehicle). 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, but not solubilize the discontinuous phase.

[0042] 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.

[0043] The organic vehicle may be combined with the polyfluoropolyether silane (either singularly or optionally in combination with the fluorinated vehicle) 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 prepare a 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 nonaqueous emulsion. 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 phase separates.

[0044] 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.

[0045] 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 or otherwise becomes a heterogeneous mixture. 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] The continuous phase of the non-aqueous emulsion may consist essentially of, or consist of, the organic vehicle. 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 nonaqueous 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. [0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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. 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] As introduced above, 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 nonaqueous 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 non-aqueous emulsion.

[0062] 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. It is typically difficult to maintain a total water content of 0 ppm. As such, the lower limit in the ranges above is typically slightly greater than 0, e.g. 1 part per billion (1 ppb), 10 ppb, 100 ppb, or 1 ppm.

[0063] "Controlled," with reference to the total water content of the non-aqueous emulsion, generally indicates that a positive step is carried out so as to minimize the total water content of the non-aqueous emulsion. For example, water may be present in nominal amounts in various components that may be utilized in the non-aqueous emulsion, e.g. the organic vehicle, the polyfluoropolyether silane, etc. This is generally true and difficult to avoid even when the presence of water is undesirable. Said differently, even combining components to the exclusion of water to form a composition or emulsion generally results in water being present therein. The presence of water may be attributable to, for example, atmospheric moisture, condensation, small amounts of water present in components, etc. As such, controlling the total water content of the non-aqueous emulsion is distinguished from merely preparing the non-aqueous emulsion without carrying out a positive step so as to minimize, alternatively eliminate, the total water content of the non-aqueous emulsion, particularly over its useful life.

[0064] Further, controlling the total water content of the non-aqueous emulsion is generally maintained over a useful life of the non-aqueous emulsion. For example, water generally accumulates in a composition or non-aqueous emulsion over time, i.e., conventional compositions or non-aqueous emulsions generally accumulate water over time, which is undesirable. In contrast, the total water content of the non-aqueous emulsion is controlled, typically over the useful life of the non-aqueous emulsion, which is generally until the nonaqueous emulsion is utilized to prepare a layer of a surface treated article, as described below. In various embodiments, the total water content of the non-aqueous emulsion is controlled for the period of time during which the non-aqueous emulsion exhibits the Tyndall effect. In these or other embodiments, the total water content of the non-aqueous emulsion is controlled 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. Because the non-aqueous emulsion may be stored and/or transported during its useful life, the total water content is generally controlled for extended periods of time, e.g. at least 2 days, alternatively at least 1 week, alternatively at least 1 month, alternatively at least 1 year, alternatively up to 50 years.

[0065] The total water content of the non-aqueous emulsion is controlled by disposing the non-aqueous emulsion in a dry vessel which is isolated from atmospheric moisture such that the dry vessel is dry. For example, although not required, in certain embodiments, the total water content is controlled by a technique selected from: (i) disposing the non-aqueous emulsion in a dry vessel; (ii) incorporating a drying agent in the non-aqueous emulsion; or (iii) both (i) and (ii). In certain embodiments, the dry vessel is evacuated with a dry gas (e.g. nitrogen or argon), filled with the non-aqueous emulsion under vacuum, and subsequently brought to atmospheric pressure with a dry gas. In certain embodiments, the dry vessel is a hermetically sealed vessel. In certain embodiments, suitable dry vessels are vessels that are generally substantially impermeable to water vapor (i.e., atmospheric moisture) such that the vessel is free of moisture for a period of time ranging from 1 week to 50 years, from 5 weeks to 10 years, from 26 weeks to 5 years or from 1 year to 3 years.

[0066] The dry vessel may have any shape or size in view of a desired volume of the nonaqueous emulsion to be disposed therein. Further, the vessel may comprise any suitable material that is substantially impermeable to water vapor, alternatively a combination of two or more different materials. In certain embodiments, the dry vessel is also substantially impermeable to air or gas. For example, the dry vessel may comprise a layered structure of two or more different materials wherein one or more of the materials is substantially impermeable and one or more of the materials is not. Specific examples of materials suitable for the dry vessel include glass, metal or alloys, and certain polymeric materials, e.g. certain performance plastics. One of skill in the art readily understands which materials are substantially impermeable to air or gas.

[0067] The dry vessel generally has an inlet for disposing the non-aqueous emulsion therein. The inlet may be sealed via various methods. For example, the inlet may be sealed with a stopper or stopcock, optionally with a taper joint and/or threading. The stopper or stopcock may be utilized along with a seal. The seal may comprise an o-ring, such as a polymeric o- ring, a sleeve, a resin, a wax, a grease, etc. For example, the seal is generally disposed between the stopper or stopcock and the vessel. Polytetrafluoroethylene (PTFE) is commonly utilized as a material for such seals.

[0068] Although the dry vessels may be utilized to control the total water content of the nonaqueous emulsion, the dry vessels generally do not reduce the total water content of the non-aqueous emulsion. While the dry vessels may be utilized alone to control the total water content, the dry vessels do not ameliorate issues relating to water being present in the nonaqueous emulsion at the time of its preparation. For example, as described above, certain components utilized to prepare the non-aqueous emulsion may inherently and undesirably include water. One specific example is the organic vehicle, which, contingent on its selection, commonly includes undesirably high concentrations of water therein.

[0069] In certain embodiments, the total water content is controlled by incorporating a drying agent in the non-aqueous emulsion. The drying agent may be, for example, (i) water-reactive or (ii) a desiccant. The non-aqueous emulsion may comprise both a water- reactive drying agent and a desiccant drying agent.

[0070] "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.

[0071] 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.

[0072] 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 polyfluoropolyether silane 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.

[0073] 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 water-reactive functional group is typically bonded directly to the silicon atom. 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.

[0074] 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.

[0075] 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.

[0076] Alkyltrialkoxysilanes have the general formula: R3(OR4)3Si, where and R⁴ 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.

[0077] 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.

[0078] Tetraalkyldialkenyldisilazanes have the general formula: R^R^SiNHSiR^R^, where each R6 is an independently selected alkyl group as defined above for R3 and R⁴ and each R⁷ 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.

[0079] Hexaalkyldisilazanes have the general formula: R^SiNHSiR^, where each R^ is an independently selected alkyl group as defined above for R3 and R⁴. Specific examples of hexaalkyldisilazanes include hexamethyldisilazane, diethyltetramethyldisilazane, etc.

[0080] Diaryltetraalkyldisilazanes have the general formula: R⁹2R^{1 0}SiNHSiR⁹R^{1 0}2, where each R⁹ is an independently selected alkyl group as defined above for R^ and R⁴ and each

R¹0 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 R10 may independently also contain from one or more heteroatoms (e.g. O, N, S, and P). Specific examples of R¹ ^ include phenyl, naphthyl, thienyl, and indolyl groups. A specific example of diaryltetraalkyldisilazane includes diphenyltetramethyldisilazane.

[0081] In certain embodiments, the disilazanes are selected from the group of tetraalkyldialkenyldisilazane, hexaalkyldisilazane, diaryltetraalkyldisilazane, and combinations thereof.

[0082] Alkyltrioximosilanes have the general formula: R^ Si(ON=CH2)3, where R^ is an alkyl group as defined above for R3 and R⁴. Specific examples of alkyltrioximosilanes include methyltrioximosilane, ethyltrioximosilane, propyltrioximosilane, etc.

[0083] Alkyltri(carboxylic acid ester)silanes have the general formula: R^{1 2}Si(OOCR¹3)3, where and each R13 is an independently selected alkyl group as defined above for R^ and R⁴. Typically, each R13 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.

[0084] Trialkylhalosilanes have the general formula: R^SiX^ , where each R^ ⁴ is an independently selected alkyl group as defined above for R3 and R⁴ and X¹ is a halogen atom selected from F, CI, Br, and I. Specific examples of trialkylhalosilanes include trimethylchlorosilane, triethylchlorosilane, trimethylbromosilane, dimethylethylchlorosilane, etc. [0085] 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.

[0086] 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."

[0087] 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.

[0088] Independent of the drying agent utilized, the drying agent may be included in the nonaqueous emulsion via various methods. The drying agent may be present in a single component utilized to prepare the non-aqueous emulsion. For example, the drying agent may be utilized in the organic vehicle to dry the organic vehicle prior to preparing the nonaqueous emulsion therewith. Alternatively, the drying agent may be incorporated into a preformed non-aqueous emulsion as a discrete component.

[0089] Further, the drying agent need not be present in the non-aqueous emulsion at the time of its use or application. For example, the drying agent may be incorporated into the non-aqueous emulsion to minimize, alternatively eliminate, any water therein and may be subsequently separated from the non-aqueous emulsion. As one example, the drying agent may, depending on its selection, be centrifuged or filtered from the non-aqueous emulsion. Alternatively still, the drying agent need not be present in the non-aqueous emulsion itself. For example, the drying agent may be combined with one or more individual components of the non-aqueous emulsion prior to its preparation to minimize, alternatively eliminate, any water, after which the drying agent may be separated from the components in which the drying agent is utilized. The components may then be combined to prepare the non-aqueous emulsion after separation of the drying agent and any components in which the drying agent is utilized. Removal of the drying agent, if carried out, is typically when the non-aqueous emulsion is to be stored in the dry vessel.

[0090] A concentration of the drying agent in the 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 non-aqueous emulsion is also stored in the dry vessel. Conversely, greater concentrations may be utilized if the non-aqueous emulsion is exposed to atmospheric moisture. Further, as noted above, the concentration may vary based on whether the drying agent is separated from the non-aqueous emulsion (or utilized prior to preparation thereof). 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 non-aqueous emulsion and is so consumed. In certain embodiments in which the non-aqueous emulsion 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 .

[0091] The non-aqueous emulsion may be prepared via various methods. Typically, the organic vehicle and the polyfluoropolyether silane are combined to prepare the non-aqueous emulsion.

[0092] The organic vehicle and the polyfluoropolyether silane may be combined in various manners. For example, the organic vehicle may be added to the polyfluoropolyether silane, or the polyfluoropolyether silane may be added to the organic vehicle, optionally in the presence of a stirrer or mixer, which may be utilized during and/or after combining the organic vehicle and the polyfluoropolyether silane.

[0093] In various embodiments, the step of combining the organic vehicle and the polyfluoropolyether silane comprises disposing the polyfluoropolyether silane in the organic vehicle. The polyfluoropolyether silane may be disposed in the organic vehicle manually (e.g. with a pipette or other glassware) or with an appropriate dispensing apparatus. [0094] Typically, the polyfluoropolyether silane is combined with the fluorinated vehicle to form the fluorinated composition, and the fluorinated composition is disposed in the organic vehicle to prepare the non-aqueous emulsion.

[0095] As introduced above, the fluorinated composition (or just the polyfluoropolyether silane, as the case may be) generally self-disperses and self-emulsifies in the organic vehicle once combined with the organic vehicle. As such, in various embodiments, the method of preparing the non-aqueous emulsion is free from the step of applying any substantial shear forces to the non-aqueous emulsion, which is generally required in the preparation of a conventional emulsion. Alternatively, the components may be vortexed or otherwise mixed to prepare the non-aqueous emulsion. For example, minimal shear, such as swirling the nonaqueous emulsion gently by hand or via a mixing device is sufficient for initiating self- emulsification of the components of the non-aqueous emulsion.

[0096] As described above, in embodiments including the drying agent, the drying agent may be incorporated into the non-aqueous emulsion, or a component thereof, at any stage of preparing the non-aqueous emulsion. Similarly, if desired, the drying agent may be removed from the non-aqueous emulsion, or a component thereof, at any stage of preparing the nonaqueous emulsion.

[0097] 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.

[0098] 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 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 ready for surface treatment to prepare the surface-treated article. Although not required, to prepare the untreated article for surface treatment, the surface is activated using a suitable activating technique including, but not limited to, treatment with base or with atmospheric plasma.

[0099] For example, the method of preparing the surface-treated article comprises applying the non-aqueous emulsion on the surface of the untreated article ready for surface treatment 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 and to render these contaminants easy to clean from the surface- treated article. The untreated article ready for surface treatment is distinguished from the surface-treated article because the untreated article ready for surface treatment generally does not yet include the layer, although combinations of different layers, e.g. in the form of a stack, may be utilized. If desired, the untreated article ready for surface treatment has a clean and dry surface, e.g. from rinsing, optionally in a solvent, and subsequent drying.

[00100] Examples of electronic articles typically include those having electronic displays, such as liquid crystal displays (LCDs), light-emitting diode (LED) displays, organic light- emitting diode (OLED) displays, plasma displays, etc. These electronic displays are often utilized in various electronic devices, such as computer monitors, televisions, smart phones, global positioning systems (GPS), music players, remote controls, hand-held video games, portable readers, automobile display panels, 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.

[00101] 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.

[00102] 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.

[00103] 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.

[00104] 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.

[00105] 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).

[00106] 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. [00107] 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.

[00108] 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.

[00109] 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.

[00110] 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.

[00111] 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.

[00112] One 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.

[00113] The neat pellet is generally placed on a substrate 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 untreated article, thereby preparing the surface-treated article..

[00114] Independent of the method by which the layer is formed, once the layer is formed on the surface of the untreated 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 °C, 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. [00115] 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, nanometers (nm).

[00116] 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.

[00117] 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.

[00118] In these embodiments, the layers also typically have a sliding (kinetic) coefficient of friction 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, (μ). Although coefficient of friction is unitless, it is often represented by (μ).

[00119] The non-aqueous emulsion of the present 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 present invention may be prepared at a fraction of the cost of conventional surface treatment compositions and with, in many instances, significantly lower toxicity due to the significant presence of the organic vehicle (which results in a significant absence of the fluorinated vehicle) in the non-aqueous 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.

[00120] Aspect 1 . A non-aqueous emulsion, comprising: a continuous organic phase comprising an organic vehicle; and a discontinuous phase comprising a polyfluoropolyether silane; wherein a total water content of said non-aqueous emulsion is controlled at from 0 to less than 1 weight percent based on the total weight of said non-aqueous emulsion.

[00121] Aspect 2. The non-aqueous emulsion of aspect 1 wherein the total water content is controlled by a technique selected from: (i) disposing said non-aqueous emulsion in a dry vessel; (ii) incorporating a drying agent in said non-aqueous emulsion; or (iii) both (i) and (ii).

[00122] Aspect 3. The non-aqueous emulsion of aspects 1 or 2 wherein said total water content is controlled at from 0 to less than 100 parts per million (ppm) based on the total weight of said non-aqueous emulsion.

[00123] Aspect 4. The non-aqueous emulsion of any one preceding aspect wherein said total water content is controlled at from 0 to less than 50 parts per million (ppm) based on the total weight of said non-aqueous emulsion.

[00124] Aspect 5. The non-aqueous emulsion of any one of aspects 2-4 wherein (ii) said drying agent is present in said non-aqueous emulsion so as to control said total water content of said non-aqueous emulsion. [00125] Aspect 6. The non-aqueous emulsion of aspect 5 wherein said drying agent is (i) water-reactive or (ii) a desiccant.

[00126] Aspect 7. The non-aqueous emulsion of aspect 6 wherein said drying agent is (i) water-reactive and is selected from the group of alkyltrialkoxysilane, a disilazane, alkyltrioximosilane, alkyltri(carboxylic acid ester)silane, and trialkylhalosilane.

[00127] Aspect 8. The non-aqueous emulsion of aspect 7 wherein said drying agent comprises said disilazane and said disilazane is selected from the group of hexaalkyldisilazane, tetraalkyldialkenylsilazane, and diaryltetraalkyldisilazane.

[00128] Aspect 9. The non-aqueous emulsion of any one preceding aspect wherein said discontinuous phase further comprises a fluorinated vehicle.

[00129] Aspect 10. The non-aqueous emulsion of any one preceding aspect wherein said organic vehicle is selected such that said non-aqueous emulsion exhibits the Tyndall effect for a period of time.

[00130] Aspect 1 1 . The non-aqueous emulsion of aspect 10 wherein said 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.

[00131] Aspect 12. The non-aqueous emulsion of any one preceding aspect wherein said polyfluoropolyether silane has the general formula (A): Y-Z_a-[(OC3Fg)|-₎-(OCF(CF3)CF2)_c-

(OCF2CF(CF3))_d-(OC2F4)e-(CF(CF3))_f-(OCF2)g]-(CH2)_h-B-(C_nH2n)-((SiR¹2-0)_m-SiRl ₂)i-

(CjH₂j)-Si-(X)₃._z(R²)_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))-; a is an integer from 1 to 200; b, c, d, e, f, and g are integers each independently selected from 0 to 200; h, n and j are integers each independently selected from 0 to 20; i and m are integers each independently selected from 0 to 5; B is a bivalent organic group or O; each R¹ is an independently selected C-1 -C22 hydrocarbyl group; each z is an integer independently selected from 0 to 2; each X is an independently selected hydrolysable group; each R² is an independently selected C1 -C22 hydrocarbyl group which is free of aliphatic unsaturation; and Y is selected from H, F, and Si-(X)3._z(R²)_z(CjH2j)-((SiR¹2-0)_m-SiR¹2)j-(C_nH2n)-B-(CH₂) -; wherein X, B, z, R¹ , R², j, m, i, n and h are as defined above; provided that when subscript i is 0, subscript j is also 0; and when subscript i is an integer greater than 0, each of subscripts j and i is an integer greater than 0, m is also an integer greater than 0.

[00132] Aspect 13. The non-aqueous emulsion of aspect 12 wherein said hydrolysable group represented by X in general formula (A) of said polyfluoropolyether silane is independently selected from H, a halogen atom, -OR³, -NHR³, -NR³R⁴, -OOC-R³, 0-N=CR³R⁴, O- C(=CR³R⁴)R⁵, and -NR³COR⁴, wherein R³, R⁴ and R⁵ are each independently selected from H and a C-1 -C22 hydrocarbyl group, and wherein R³ and R⁴, together with the nitrogen atom to which they are both bonded in -NR³R⁴, optionally can form a cyclic amino group.

[00133] Aspect 14. A method of preparing a surface-treated article, said method comprising: applying the non-aqueous emulsion of any one preceding aspect 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 a layer on the surface of the untreated article, thereby preparing the surface-treated article.

[00134] Aspect 15. The method of aspect 14 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.

[00135] Aspect 16. The method of aspect 14 or 15 wherein the layer has a water contact angle of from 75 to 120^°.

[00136] Aspect 17. The method of aspect 16 wherein the layer has a water contact angle of from 90 to 120^°.

[00137] Aspect 18. A method of preparing a surface-treated article, said method comprising the steps of: combining the non-aqueous emulsion of any one of aspects 1 -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.

[00138] The appended aspects are not limited to express any particular compounds, nonaqueous emulsions, 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.

[00139] Further, any ranges and subranges relied upon in describing various embodiments of the present invention independently and collectively fall within the scope of the appended claims, and 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 present 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, 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.

[00140] 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

[00141] Examples 1-3 and Comparative Examples 1-2:

[00142] Table 1 below illustrates the components utilized to prepare the non-aqueous emulsions along with their respective amounts for Examples 1 -3 and Comparative Examples 1 -2. In Examples 1 -3 and Comparative Example 2 below, a fluorinated vehicle is combined with a polyfluoropolyether silane to form a fluorinated composition. Each fluorinated composition is then added to an organic vehicle dropwise via an extended fine tip small bulb pipette to prepare non-aqueous emulsions, optionally subjecting the components thereof to a vortex upon disposing the fluorinated composition in the organic vehicle. Comparative Example 1 involves a fluorinated composition that does not constitute a non-aqueous emulsion, as there is no continuous organic phase in the fluorinated composition of Comparative Example 1 . As such, the fluorinated composition of Comparative Example 1 is formed merely by disposing the polyfluoropolyether silane in the fluorinated vehicle. In Table 1 below, "C.E." indicates "Comparative Example," and "PFPE Silane" indicates "polyfluoropolyether silane."

[00143] Table 1 :

[00144] Organic Vehicle 1 is t-butyl acetate.

[00145] Fluorinated Vehicle 1 is ethoxy-nonafluorobutane (C4F9OC2H5).

[00146] Polyfluoropolyether (PFPE) Silane 1 has the general formula: F((CF₂)30)_c'CF2CF2CH₂0(CH2)3Si(OMe)3, where c' is from 17-25. [00147] Fluorinated Composition 1 comprises a mixture of Fluorinated vehicle 1 and Polyfluoropolyether Silane 1 .

[00148] Drying Agent 1 is combined with the non-aqueous emulsions of Examples 1 -3 to control a total water content thereof. In particular, Drying Agent 1 comprises a water-reactive drying agent. Specifically, Drying Agent 1 comprises hexamethyldisilazane.

[00149] Table 2 illustrates the molar ratio of the drying agent to the PFPE silane in each of Examples 1 -3. The values in Table 2 are initial values, as the Drying Agent 1 may react with any water present in the particular non-aqueous emulsion, thus reducing its concentration over time.

[00150] Table 2:

[00151] Samples of the non-aqueous emulsions (or composition, as the case may be) of Examples 1 -3 and Comparative Examples 1 -2 are each applied to a surface of a substrate via spray coating. In particular, these non-aqueous emulsions and composition 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 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 Examples 1 -3 and Comparative Examples 1 -2 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 the 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 substrate is used immediately. The non-aqueous emulsions are applied at a liquid pressure of 3 psi, although the fluorinated composition is applied at a liquid pressure of 5 psi. Once the respective non-aqueous emulsions (or composition) were applied to the substrates, the non-aqueous emulsions (or composition) were cured at 125 'C for 1 hour to form layers on the substrates. The layers are rinsed with fluorinated Vehicle 1 to remove any portion of the curable composition or component thereof that remained after curing.

[00152] Physical properties of the layers formed from the non-aqueous emulsions and composition are measured. In particular, physical properties of the respective layers are measured before and after subjecting the layers to an abrasion resistance test, as described below.

[00153] 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.

[00154] 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. Further, a portion of the non-aqueous emulsions (or composition, as the case may be) of Examples 1 -3 and Comparative Examples 1 -2 are stored in a sealed container to age. Specifically, portions are stored in a dry sealed glass vial at 23 ± 2 ^<C and 50 ± 5 % relative humidity. After certain intervals (2 weeks, 1 month, 2 months, and 3 months), additional layers are formed onto fresh substrates from the aged non-aqueous emulsions (or composition, as the case may be) of Examples 1 -3 and Comparative Examples 1 -2 according to the method 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). Tables 3 and 4 below illustrate the WCA for the layers formed from Examples 1 -3 and Comparative Examples 1 -2. Generally, the greater the WCA after abrasion, the greater the durability of the layer. The values in Tables 3 and 4 below are in degrees (°).

[00155] Table 3:

C.E.1 1 16.1 109.5 1 15.6 106.8 1 16.8 1 12.9

C.E.2 1 16.6 1 10.5 1 15.7 99.7 1 14.1 95.5

[00156] Table 4:

[00157] As clearly illustrated in Tables 3 and 4 above, inclusion of the Drying Agent 1 in the non-aqueous emulsions of Examples 1 -3 provided significant benefits as compared to a nonaqueous emulsion free from the Drying Agent 1 (e.g. of Comparative Example 2). In particular, water undesirably impacts the durability of the layers formed from the nonaqueous emulsions. As such, inclusion of the Drying Agent 1 in the non-aqueous emulsions controls the total water content of the non-aqueous emulsions. Further, increased initial concentrations of the Drying Agent 1 provided improved results, with Example 3 including the highest concentration, and Example 1 including the second highest concentration.

[00158] For example, the non-aqueous emulsions of Examples 1 -3 are nearly identical to the non-aqueous emulsion of Comparative Example 2, but for the control of the total water content of the non-aqueous emulsions of Examples 1 -3 via the Drying Agent 1 . The impact is best shown after aging the non-aqueous emulsions over an extended period of time, e.g. 3 months. For example, after 3 months, the layers formed from the non-aqueous emulsions of Examples 1 -3 all had a WCA of at least 1 13.6 (unabraded). In contrast, the layer formed from the non-aqueous emulsion of Comparative Example 2 was merely 99.9. This impact is more pronounced after abrasion, where the layers formed from the non-aqueous emulsions of Examples 1 and 3 maintained a WCA of at least 107.4, whereas the layer formed from the non-aqueous emulsion of Comparative Example 2 dropped precipitously to 62.8. Performance of the layer formed from the non-aqueous emulsions of Examples 1 and 3 is likely better than that of the layer formed from the non-aqueous emulsion of Example 2 due to the higher concentration of the Drying Agent 1 in the non-aqueous emulsions of Examples 1 and 3. [00159] Comparative Example 1 confirms that controlling the total water content is unique to non-aqueous emulsions including a continuous organic phase. For example, Comparative Example 1 does not include the Drying Agent 1 to control the total water content of its composition. Further, the composition of Comparative Example 1 is representative of a conventional fluorinated composition including a fluorinated vehicle and polyfluoropolyether silane, but no continuous organic phase. As clearly illustrated above, the performance of the layers formed from the composition of Comparative Example 1 did not deteriorate even after aging the composition. As such, controlling the total water content is particularly salient for non-aqueous emulsions as compared to compositions.

[00160] Examples 4-8 and Comparative Examples 3-4:

[00161] Table 5 below illustrates the components utilized to prepare the non-aqueous emulsions along with their respective amounts for Examples 4-8 and Comparative Examples 3-4. In Examples 4-8 and Comparative Examples 3-4 below, a fluorinated vehicle is combined with a polyfluoropolyether silane to form a fluorinated composition. Each fluorinated composition is then added to an organic vehicle dropwise via an extended fine tip small bulb pipette to prepare non-aqueous emulsions, optionally subjecting the components thereof to a vortex upon disposing the fluorinated composition in the organic vehicle. Comparative Example 3 involves a fluorinated composition that does not constitute a nonaqueous emulsion, as there is no continuous organic phase in the fluorinated composition of Comparative Example 3. As such, the fluorinated composition of Comparative Example 3 is formed merely by disposing the polyfluoropolyether silane in the fluorinated vehicle. In Table 5 below, "C.E." indicates "Comparative Example," and "PFPE Silane" indicates "polyfluoropolyether silane."

[00162] Table 5:

Continuous Phase Discontinuous Phase

Example Amount Fluorinated Amount PFPE Amount

Organic Vehicle

(g) Vehicle (g) Silane (g)

7 2 29.9 1 0.242 1 0.06

8 2 29.7 1 0.24 1 0.06

C.E. 3 n/a n/a 1 32.79 1 0.066

C.E. 4 2 28.9 1 0.234 1 0.058

[00163] Organic Vehicle 2 is dry acetone (< 50 ppm H2O).

[00164] Drying Agent 1 is combined with the non-aqueous emulsions of Examples 4-8 to control a total water content thereof. Table 6 illustrates the molar ratio of the drying agent to the PFPE silane in each of Examples 4-8 as well as the corresponding mass of the Drying Agent 1 present in each of these non-aqueous emulsions. The values in Table 6 are initial values, as the Drying Agent 1 may react with any water present in the particular nonaqueous emulsion, thus reducing its concentration over time.

[00165] Table 6:

[00166] Samples of the non-aqueous emulsions (or composition, as the case may be) of Examples 4-8 and Comparative Examples 3-4 are each applied to a surface of a substrate as described above with respect to Examples 1 -3 and Comparative Examples 1 -2.

[00167] Physical properties of the layers formed from the non-aqueous emulsions and composition are measured. In particular, physical properties of the respective layers are measured before and after subjecting the layers to an abrasion resistance test, as described above. Further, a portion of the non-aqueous emulsions (or composition, as the case may be) of Examples 4-8 and Comparative Examples 3-4 are stored in a sealed container to age. Specifically, portions are stored in a dry sealed glass vial at 23 ± 2 ^<C and 50 ± 5 % relative humidity. After certain intervals (1 month, 2 months, and 3 months), additional layers are formed onto fresh substrates from the aged non-aqueous emulsions (or composition, as the case may be) of Examples 4-8 and Comparative Examples 3-4 according to the method 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). Tables 7 and 8 below illustrate the WCA for the layers formed from Examples 4-8 and Comparative Examples 3-4. Generally, the greater the WCA after abrasion, the greater the durability of the layer. The values in Tables 7 and 8 below are in degrees (°).

[00168] Table 7:

[00169] Table

[00170] As illustrated in Tables 7 and 8 above, inclusion of the Drying Agent 1 in the nonaqueous emulsions of Examples 4-8 provided significant benefits as compared to a nonaqueous emulsion free from the Drying Agent 1 (e.g. of Comparative Example 4). In particular, water undesirably impacts the durability of the layers formed from the non- aqueous emulsions. As such, inclusion of the Drying Agent 1 in the non-aqueous emulsions controls the total water content of the non-aqueous emulsions. Further, as shown by Example 8, increasing a concentration of the Drying Agent 1 beyond a certain threshold may impact durability.

[00171] For example, the non-aqueous emulsions of Examples 4-8 are nearly identical to the non-aqueous emulsion of Comparative Example 4, but for the control of the total water content of the non-aqueous emulsions of Examples 4-8 via the Drying Agent 1 . The impact is best shown after aging the non-aqueous emulsions over an extended period of time, e.g. 3 months. For example, after 3 months, the layers formed from the non-aqueous emulsions of Examples 4-8 all had a WCA of at least 104.5 (unabraded), with the layers formed from the non-aqueous emulsions of Examples 4-7 having a WCA of at least 1 10.7 after 3 months (unabraded). In contrast, the layer formed from the non-aqueous emulsion of Comparative Example 4 was merely 99.7 after 3 months (unabraded).

[00172] Comparative Example 3, which is similar to Comparative Example 1 , again confirms that controlling the total water content is unique to non-aqueous emulsions including a continuous organic phase for the reasons described above.

[00173] Examples 9-15 and Comparative Examples 5-6:

[00174] Table 9 below illustrates the components utilized to prepare the non-aqueous emulsions along with their respective amounts for Examples 9-15 and Comparative Examples 5-6. In Examples 9-15 and Comparative Examples 5-6 below, a fluorinated vehicle is combined with a polyfluoropolyether silane to form a fluorinated composition. Each fluorinated composition is then added to an organic vehicle dropwise via an extended fine tip small bulb pipette to prepare non-aqueous emulsions, optionally subjecting the components thereof to a vortex upon disposing the fluorinated composition in the organic vehicle. Comparative Example 5 involves a fluorinated composition that does not constitute a nonaqueous emulsion, as there is no continuous organic phase in the fluorinated composition of Comparative Example 5. As such, the fluorinated composition of Comparative Example 5 is formed merely by disposing the polyfluoropolyether silane in the fluorinated vehicle. In Table 9 below, "C.E." indicates "Comparative Example," and "PFPE Silane" indicates "polyfluoropolyether silane."

[00175] Table 9:

Example Continuous Phase Discontinuous Phase Amount Fluorinated Amount PFPE

Organic Vehicle Amount (g)

(g) Vehicle (g) Silane

9 29.7 0.25 1 0.06

10 29.7 0.25 1 0.06

1 1 29.7 0.24 1 0.06

12 29.7 0.24 1 0.06

13 29.4 0.19 1 0.05

14 29.4 0.24 1 0.06

15 28.4 0.23 1 0.06

C.E. 5 n/a n/a 30.95 1 0.06

C.E. 6 1 29.7 1 0.25 1 0.06

[00176] Notably, to further illustrate effectiveness of the Drying Agent 1 , water is intentionally added to the non-aqueous emulsions of Examples 14 and 15. In particular, in addition to any inherent water present in the non-aqueous emulsions of Examples 14 and 15, 0.0075 grams of water are added to the non-aqueous emulsion of Example 14, and 0.0898 grams of water are added to the non-aqueous emulsion of Example 15. Typically, such water content would be deleterious to the properties of the layers formed from the non-aqueous emulsions containing the same.

[00177] The total water content of the non-aqueous emulsions of Examples 9-15 is controlled. In particular, the total water content of these non-aqueous emulsions is controlled via drying agents. Table 10 below indicates the particular drying agents utilized in each of Examples 9-15, along with the corresponding mass of each drying agent utilized. The values in Table 10 are initial values, as the drying may react with or otherwise absorb/remove any water present in the particular non-aqueous emulsion, thus reducing its concentration over time. [00178] Table 10:

[00179] Drying Agent 2 is trimethylorthoformate, which is a water-reactive drying agent.

[00180] Drying Agent 3 is phosphorous pentoxide, which is a water-reactive drying agent.

[00181] Drying agent 4 is 1 ,1 ,3,3,5,5-thexamethylcyclotrisilazane, which is a water-reactive drying agent.

[00182] Drying agent 5 is magnesium sulfate, which is a desiccant drying agent.

[00183] Samples of the non-aqueous emulsions (or composition, as the case may be) of Examples 9-15 and Comparative Examples 5-6 are each applied to a surface of a substrate as described above with respect to Examples 1 -3 and Comparative Examples 1 -2.

[00184] Physical properties of the layers formed from the non-aqueous emulsions and composition are measured. In particular, physical properties of the respective layers are measured before and after subjecting the layers to an abrasion resistance test, as described above. Further, a portion of the non-aqueous emulsions (or composition, as the case may be) of Examples 9-15 and Comparative Examples 5-6 are stored in a sealed container to age. Specifically, portions are stored in a dry sealed glass vial at 23 ± 2 °C and 50 ± 5 % relative humidity. After certain intervals (1 month, 2 months, and 3 months), additional layers are formed from the non-aqueous emulsions (or composition, as the case may be) of Examples 9-15 and Comparative Examples 5-6 according to the method 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). Tables 1 1 and 12 below illustrate the WCA for the layers formed from Examples 9-15 and Comparative Examples 5-6. The values in Tables 1 1 and 12 below are in degrees (°). [00185] Table 1 1 :

[00186] Table

[00187] As shown in Tables 1 1 and 12 above, controlling the total water content of nonaqueous emulsions via certain drying agents provides significant benefits as to performance of layers formed from the non-aqueous emulsions even after an extended period of time (e.g. 3 months). For example, the layers formed from the non-aqueous emulsions of Examples 13- 15 still had a WCA after 3 months (unabraded) of at least 100.0.

[00188] Examples 16-21 and Comparative Example 7:

[00189] Table 13 below illustrates the components utilized to prepare the non-aqueous emulsions along with their respective amounts for Examples 16-21 and Comparative Example 7. In Examples 16-21 and Comparative Example 7 below, a fluorinated vehicle is combined with a polyfluoropolyether silane to form a fluorinated composition. Each fluorinated composition is then added to an organic vehicle dropwise via an extended fine tip small bulb pipette to prepare non-aqueous emulsions, optionally subjecting the components thereof to a vortex upon disposing the fluorinated composition in the organic vehicle. In Table 13 below, "C.E." indicates "Comparative Example," and "PFPE Silane" indicates "polyfluoropolyether silane."

[00190] Table 13:

[00191] The total water content of the non-aqueous emulsions of Examples 16-21 is controlled. In particular, the total water content of these non-aqueous emulsions is controlled via drying agents. Table 14 below indicates the particular drying agents utilized in each of Examples 16-21 , along with the corresponding mass of each drying agent utilized. The values in Table 14 are initial values, as the drying may react with or otherwise absorb/remove any water present in the particular non-aqueous emulsion, thus reducing its concentration over time.

[00192] Table 14:

19 8 0.528

20 9 0.498

21 10 0.497

[00193] Drying Agent 6 is methyltrimethoxysilane, which is a water-reactive drying agent.

[00194] Drying Agent 7 is tetramethyldivinyldisilazane, which is a water-reactive drying agent.

[00195] Drying agent 8 is methyltrioximosilane, which is a water-reactive drying agent.

[00196] Drying agent 9 is a blend of methyl/ethyl triacetoxysilane, which is a water-reactive drying agent.

[00197] Drying agent 10 is trimethylchlorosilane, which is a water-reactive drying agent.

[00198] Samples of the non-aqueous emulsions of Examples 16-21 and Comparative Example 7 are each applied to a surface of a substrate as described above with respect to Examples 1 -3 and Comparative Examples 1 -2.

[00199] Physical properties of the layers formed from the non-aqueous emulsions are measured. In particular, physical properties of the respective layers are measured before and after subjecting the layers to an abrasion resistance test, as described above. Further, a portion of the non-aqueous emulsions Examples 16-21 and Comparative Example 7 are stored in a sealed container to age. Specifically, portions are stored in a dry sealed glass vial at 23 ± 2 °C and 50 ± 5 % relative humidity. After certain intervals (1 month, 2 months, and 3 months), additional layers are formed on new substrates from the non-aqueous emulsions of Examples 16-21 and Comparative Example 7 according to the method 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). Tables 15 and 16 below illustrate the WCA for the layers formed from Examples 16-21 and Comparative Example 7. The values in Tables 15 and 16 below are in degrees (°). The values in Tables 15 and 16 represent the mean values based on 18 different measurements for each WCA value.

[00200] Table 15:

18 1 17.1 1 1 1 .4 1 16.0 108.8

19 103.2 104.7 104.3 100.0

20 1 15.0 98.3 1 16.5 96.3

21 1 15.8 1 1 1 .2 103.3 75.3

C.E. 7 1 17.1 1 10.9 74.6 85.4

[00201] Table 16:

[00202] As shown in Tables 15 and 16 above, controlling the total water content of nonaqueous emulsions via certain drying agents provides significant benefits as to performance of layers formed from the non-aqueous emulsions even after an extended period of time (e.g. 3 months). For example, the layers formed from the non-aqueous emulsions of Examples 18- 19 still had a WCA after 3 months (abraded) of at least 103.0. Maintaining such a WCA even after abrasion after storing the non-aqueous emulsion for 3 months is particularly desirable.

[00203] The invention has been described in an illustrative manner, and 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 present 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 non-aqueous emulsion, comprising:

a continuous organic phase comprising an organic vehicle; and

a discontinuous phase comprising a polyfluoropolyether silane;

wherein a total water content of said non-aqueous emulsion is controlled at from 0 to less than 1 weight percent based on the total weight of said non-aqueous emulsion.

2. The non-aqueous emulsion of claim 1 wherein the total water content is controlled by a technique selected from: (i) disposing said non-aqueous emulsion in a dry vessel; (ii) incorporating a drying agent in said non-aqueous emulsion; or (iii) both (i) and (ii).

3. The non-aqueous emulsion of claims 1 or 2 wherein said total water content is controlled at from 0 to less than 100 parts per million (ppm) based on the total weight of said non-aqueous emulsion; or wherein said total water content is controlled at from 0 to less than 50 parts per million (ppm) based on the total weight of said non-aqueous emulsion.

4. The non-aqueous emulsion of any one of claims 2-3 wherein (ii) said drying agent is present in said non-aqueous emulsion so as to control said total water content of said nonaqueous emulsion.

5. The non-aqueous emulsion of claim 4

wherein said drying agent is (i) water- reactive or (ii) a desiccant; or

wherein said drying agent is (i) water-reactive or (ii) a desiccant and wherein said drying agent is (i) water-reactive and is selected from the group of alkyltrialkoxysilane, a disilazane, alkyltrioximosilane, alkyltri(carboxylic acid ester)silane, and trialkylhalosilane; or

wherein said drying agent is (i) water-reactive or (ii) a desiccant and wherein said drying agent is (i) water-reactive and is selected from the group of alkyltrialkoxysilane, a disilazane, alkyltrioximosilane, alkyltri(carboxylic acid ester)silane, and trialkylhalosilane and wherein said drying agent comprises said disilazane and said disilazane is selected from the group of hexaalkyldisilazane, tetraalkyldialkenylsilazane, and diaryltetraalkyldisilazane.

6. The non-aqueous emulsion of any one preceding claim wherein said discontinuous phase further comprises a fluorinated vehicle.

7. The non-aqueous emulsion of any one preceding claim wherein said organic vehicle is selected such that said non-aqueous emulsion exhibits the Tyndall effect for a period of time.

8. The non-aqueous emulsion of claim 7 wherein said 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.

9. The non-aqueous emulsion of any one preceding claim wherein said polyfluoropolyether silane has the general formula (A): Y-Z_a-[(OC3Fg)b-(OCF(CF3)CF2)c-

(OCF2CF(CF3))_d-(OC2F4)e-(CF(CF3))f-(OCF2)g]-(CH2)_h-B-(C_nH2n)-((SiR¹2-0)_m-SiRl ₂)i-

(CjH₂j)-Si-(X)₃__z(R2)_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))-; a is an integer from 1 to 200; b, c, d, e, f, and g are integers each independently selected from 0 to 200; h, n and j are integers each independently selected from 0 to 20; i and m are integers each independently selected from 0 to 5; B is a bivalent organic group or O; each R¹ is an independently selected C1 -C22 hydrocarbyl group; each z is an integer independently selected from 0 to 2; each X is an independently selected hydrolysable group; each R² is an independently selected C1 -C22 hydrocarbyl group which is free of aliphatic unsaturation; and

Y is selected from H, F, and Si-(X)3._z(R²)_z(CjH2j)-((SiR¹2-0)_m-SiR¹2)j-(C_nH2n)-B-(CH₂) -; wherein X, B, z, R¹ , R², j, m, i, n and h are as defined above;

provided that when subscript i is 0, subscript j is also 0; and when subscript i is an integer greater than 0, each of subscripts j and i is an integer greater than 0, m is also an integer greater than 0.

10. The non-aqueous emulsion of claim 9 wherein said hydrolysable group represented by X in general formula (A) of said polyfluoropolyether silane is independently selected from H, a halogen atom, -OR³, -NHR³, -NR³R⁴, -OOC-R³, 0-N=CR³R⁴, O-

C(=CR³R⁴)R⁵, and -NR³COR⁴, wherein R³, R⁴ and R⁵ are each independently selected from H and a C-1 -C22 hydrocarbyl group, and wherein R³ and R⁴, together with the nitrogen atom to which they are both bonded in -NR³R⁴, optionally can form a cyclic amino group.

1 1 . A method of preparing a surface-treated article, said method comprising:

applying the non-aqueous emulsion of any one preceding claim 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 a layer on the surface of the untreated article, thereby preparing the surface-treated article.

12. The method of claim 1 1 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.

13. The method of claim 1 1 or 12 wherein the layer has a water contact angle of from 75 to 120^°; or wherein the layer has a water contact angle of from 90 to 120^°.

14. A method of preparing a surface-treated article, said method comprising the steps of:

combining the non-aqueous emulsion of any one of claims 1 -1 0 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.