TW201602248A - Non-aqueous emulsion and methods of preparing surface-treated articles therewith - Google Patents

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 method for preparing surface treated article therewith

The present invention relates generally to non-aqueous emulsions and more particularly to non-aqueous emulsions for treating surfaces and methods of making surface treated articles from such non-aqueous emulsions.

An "emulsion" is generally a fluid colloid system in which droplets and/or liquid crystals are dispersed in a liquid. Most known emulsions are aqueous emulsions. "Colloid" generally refers to a subdivision state in which (macromolecule) molecules or multimolecular particles are dispersed in a medium, and wherein the molecules or particles have a size of about 1 nanometer (nm) in at least one direction and Size between 1 micrometer (μm). A "colloidal dispersion" is generally a system in which colloidally sized particles of any nature (e.g., solid, liquid, or gas) are dispersed in a continuous phase of a different composition (or state). As used in polymer science, a "dispersion" is generally a material comprising a finely divided phase domain and a continuous phase domain, wherein the finely divided phase domains are distributed throughout the continuous phase domain of the dispersion. Fine-grained phase domains are often (but not always) within the colloidal size range. Thus, the emulsion is a subtype of the colloidal dispersion and the colloidal dispersion is a subtype of the dispersion. Not all dispersions are colloidal dispersions and not all colloidal dispersions are emulsions.

When the light scattering particulate matter is dispersed in the present light transmissive medium, when the cross section of the individual microparticles is in a range between about 40 nm and 900 nm, that is, slightly lower or closer to the visible light wavelength When (400 nm to 750 nm), the Tyndall effect can be seen. This effect was observed to give the medium a blue tint. The 40 nm to 900 nm particle size range given to the Tingal effect is a subset of the particle size range of 1 nm to 1,000 nm administered to the emulsion. Therefore, not all emulsions can exhibit the Tingde effect. Further, in such emulsions capable of exhibiting the Tingal effect, not all of these emulsions are capable of exhibiting the Tingle effect for a period of time. In order to exhibit the Tingal effect for a period of time, the emulsion must have a degree of stability so that the observer can have time to detect the Tingde effect. That is, the emulsion cannot be transient (i.e., has a lifetime of < 1 second) and cannot be rapidly disintegrated after formation. Once the unstable emulsion is formed, it will quickly disintegrate and thus cannot exhibit the Tingle effect for a while.

The surface of electronic and optical devices/components is often contaminated with stains and smudges due to oil from hands and fingers. For example, electronic devices that include interactive touch screen displays, such as smart phones, are often contaminated with fingerprints, skin oil, sweat, cosmetics, and the like. Once these stains and/or stains adhere to the surface of these devices, these stains and/or stains are not easily removed. In addition, these stains and/or smudges can reduce the usability of these devices.

In an attempt to minimize the occurrence and prevalence of such stains and stains, conventional surface treatment compositions have been applied to the surface of various devices/components to form a conventional layer thereon. Such conventional surface treatment compositions are typically composed of a fluorinated polymer and a solvent. However, the solvents employed in such conventional surface treatment compositions are typically limited to halogenated (e.g., fluorinated) solvents to properly dissolve the fluorinated polymer, and such halogenated solvents are relatively expensive. In addition, these halogenated solvents can have undesirable environmental characteristics. Alternative solvents such as organic solvents generally do not dissolve the fluorinated polymer. When the fluorinated polymer is not properly dispersed or uneven within the conventional treatment surface treatment, the resulting physical properties of the conventional layer formed therefrom may deteriorate.

The present invention provides a non-aqueous emulsion. The non-aqueous emulsion contains a continuous organic phase comprising an organic vehicle. The non-aqueous emulsion further contains a discontinuous phase comprising a polyfluoropolyether decane. The total water content of the non-aqueous emulsion is controlled from 0 to less than 1 weight percent based on the total weight of the non-aqueous emulsion.

The invention further provides a method of making a surface treated article. In a first method, the non-aqueous emulsion is applied to the surface of the article to be surface treated to form a wet layer of the non-aqueous emulsion on the surface of the article. The first method further includes removing the organic vehicle from the wet layer to form a layer on the surface of the article and obtaining the surface treated article. In a second method, the non-aqueous emulsion and pellets are combined to impregnate the pellet with the non-aqueous emulsion to form an impregnated pellet. The second method further comprises removing the organic vehicle from the impregnated pellet to form a pure pellet. The second method also includes preparing the surface treated article by forming a layer on the surface of the untreated article via the deposition apparatus using the pure pellet.

Non-aqueous emulsions form layers that are easy to clean and have excellent physical properties, including stain resistance and stain resistance. Moreover, the cost of forming the layer formed from the non-aqueous emulsion can be a fraction of the cost of conventional surface treatment compositions while still providing excellent and desirable physical properties.

The present invention provides non-aqueous emulsions and methods of making surface treated articles using non-aqueous emulsions. Non-aqueous emulsions form layers that are easy to clean and have excellent physical properties, including stain resistance and stain resistance. In addition, non-aqueous emulsions typically include fluorinated polymers and halogenated Compared to conventional compositions of solvents, there are significantly reduced costs and more favorable toxicological and environmental characteristics.

The non-aqueous emulsion contains a continuous organic phase comprising an organic vehicle and a discontinuous phase comprising a polyfluoropolyether decane. "Non-aqueous" means that the water does not constitute a continuous or discontinuous phase of the non-aqueous emulsion. The total water content of the non-aqueous emulsion is controlled from 0 to less than 1 weight percent based on the total weight of the non-aqueous emulsion, as described below.

The polyfluoropolyether decane of the discontinuous phase of the non-aqueous emulsion can be any known polyfluoropolyether decane commonly used in conventional surface treatment compositions. The polyfluoropolyether decane can be a monomer, oligomer or polymer. Alternatively, the polyfluoropolyether decane may comprise various combinations of different monomers, oligomers, and/or polymeric polyfluoropolyether decanes.

In various embodiments, the polyfluoropolyether decane has the following general formula (A): YZ _a -[(OC ₃ F ₆ ) _b -(OCF(CF ₃ )CF ₂ ) _c -(OCF ₂ CF(CF ₃ ) _d -(OC ₂ F ₄ ) _e -(CF(CF ₃ )) _f -(OCF ₂ ) _g ]-(CH ₂ ) _h -B-(C _n H _2n )-((SiR ¹ ₂ -O) _m -SiR ¹ ₂ ) _i -(C _j H _2j )-Si-(X) _3-z (R ² ) _z .

Although the polyfluoropolyether decane of the non-aqueous emulsion is not limited to the general formula (A), the specific aspect of the general formula (A) is explained in more detail below. The groups indicated by the subscripts b to g (i.e., the groups in the square brackets in the formula (A)) may be present in the polyfluoropolyether decane in any order, including the above formula (A) and the entire disclosure. The order presented in the order is different. Furthermore, these groups may be present in random or block form. Further, the group represented by the subscript b is typically a straight chain, that is, the group represented by the subscript b is alternatively written as (O-CF ₂ -CF ₂ -CF ₂ ) _b . In the following description, C _{p '} -C _{q '} (wherein p' and q' are each an integer) with respect to a hydrocarbon group or an alkyl group means that the group has p' to q' carbon atoms. When a group indicated by the subscript i is present, the polyfluoropolyether decane comprises a decane segment. Even in these examples, polyfluoropolyether decane is often referred to as decane in view of the terminal argon atoms that are not present in any of the decane segments.

In the above formula (A), the Z series is independently selected from -(CF ₂ )-, -(CF(CF ₃ )CF ₂ O)-, -(CF ₂ CF(CF ₃ )O)-, -(CF) (CF ₃ )O)-, -(CF(CF ₃ )-CF ₂ )-, -(CF ₂ -CF(CF ₃ ))-, and -(CF(CF ₃ ))-. Z is typically selected such that the polyfluoropolyether decane does not include an oxygen-oxygen (OO) bond in the backbone. Further, in the formula, a is an integer from 1 to 200; b, c, d, e, f and g are each independently selected from 0 or an integer from 1 to 200; h, n and j are each independently selected from 0 or an integer from 1 to 20; i and m are each independently selected from 0 or an integer from 1 to 5; B is a divalent organic group or an oxygen atom; each R ¹ is independently selected C ₁ -C ₂₂ hydrocarbon group; z is an integer independently selected from 0 to 2; each X is an independently selected hydrolyzable group; each R ² is independently selected from an aliphatically unsaturated C ₁ -C ₂₂ hydrocarbon group; and Y is selected from H, F, and (R ² ) _z (X) _3-z Si-(C _j H _2j )-((SiR ¹ ₂ -O) _m -SiR ¹ ₂ ) _i -(C _n H _2n )-B-(CH ₂ ) _h -; wherein X, B, z, R ¹ , R ² , j, m, i, n, and h are as defined above.

R ¹ which is an independently selected C ₁ -C ₂₂ hydrocarbyl group may be linear, branched, or cyclic. Further, R ¹ may include a hetero atom such as oxygen, nitrogen, sulfur, or the like in the hydrocarbon group, and may be substituted or unsubstituted. Typically, R ¹ is C ₁ -C ₄ alkyl. Further, the groups indicated by the subscripts n and j (i.e., the groups (C _n H _2n ) and (C _j H _2j )) may be independently linear or branched. For example, when n is 3, these groups may independently have the structure -CH ₂ -CH ₂ -CH ₂ , -CH(CH ₃ )-CH ₂ , or -CH ₂ -CH(CH ₃ )-, of which the latter two The structures have pendant alkyl groups, i.e., these structures are branched and non-linear.

Regarding the part represented by the subscripts m, i, and j: when the subscript i is 0, the subscript j is also 0; and when the subscript i is an integer greater than 0, the subscripts j and m are also greater than 0. Integer. In other words, when the group represented by the subscript i exists, the group represented by the subscript j also exists. Vice versa, that is, when the group represented by the subscript i does not exist, the group represented by the subscript j does not exist. In addition, when i is an integer greater than 0, the group represented by the subscript m exists, and m is also greater than An integer of 0. In some embodiments, the subscripts m and i are each one. Typically, the subscript i does not exceed 1, but the subscript m can be an integer greater than 1, such that a decane bond (i.e., a Si-O bond) is present in the group represented by the subscript i.

In certain embodiments, the polyfluoropolyether decane of the non-aqueous emulsion is limited by the following restrictions: when Y is F; Z is -(CF ₂ )-; a is an integer from 1 to 3; and subscript c , d, f, i, m, and j are each 0.

The hydrolyzable group represented by X in the formula (A) is independently selected from H, a halogen atom, an alkoxy group (-OR ³ ), an alkylamino group (-NHR ³ or -NR ³ R ⁴ ), a carboxyl group ( -OOC-R ³ ), alkyliminooxy (-ON=CR ³ R ⁴ ), alkenyloxy (OC(=CR ³ R ⁴ )R ⁵ ) or N-alkylnonylamino (-NR) ³ COR ⁴ ), wherein R ³ , R ⁴ and R ^{5 are} each independently selected from the group consisting of H and a C ₁ -C ₂₂ hydrocarbon group. When R ³ , R ⁴ and R ^{5 are} independently a C ₁ -C ₂₂ hydrocarbon group, R ³ , R ⁴ and R ⁵ may be straight-chain, branched or cyclic (for C ₃ -C ₂₂ hydrocarbon groups). Further, R ³ , R ⁴ and R ⁵ may independently include one or more hetero atoms in the hydrocarbon group, such as N, O and/or S, and may be substituted or unsubstituted. Typically, R ³ , R ⁴ and R ^{5 are} each independently selected C ₁ -C ₄ alkyl. In certain embodiments, in the formula (A) represented by X, the hydrolyzable group independently selected from alkoxy lines (-OR ³⁾ and alkylamino (-NHR ³ or -NR ³ R ^4). When the hydrolyzable group represented by X in the formula (A) is a NR ³ R ⁴ group, R ³ and R ⁴ may be optionally formed together with the nitrogen atom to which the two are bonded in NR ³ R ⁴ Cyclic amine group.

Non-limiting illustrative examples of specific species of polyfluoropolyether decane of non-aqueous emulsions are set forth in detail below. Typically in these examples, z is 0 such that the polyfluoropolyether decane comprises three hydrolyzable groups represented by X. However, as set forth above, z can be an integer other than 0 (eg, 1 or 2) such that these particular polyfluoropolyether decanes include less than three hydrolyzable groups.

In certain embodiments, Y in formula (A) is F. Typically, when Y in the formula (A) is F, the subscripts c, d and g in the formula (A) are each 0. Thus, in these examples, the polyfluoropolyether decane has the formula FZ _a -[(OC ₃ F ₆ ) _b -(OC ₂ F) when the group indicated by the subscripts c, d, and g is absent. ₄ ) _e -(CF(CF ₃ )) _f ]-(CH ₂ ) _h -B-(C _n H _2n )-((SiR ¹ ₂ -O) _m -SiR ¹ ₂ ) _i -(C _j H _2j )-Si-(X) _3-z (R ² ) _z .

In one embodiment of the non-aqueous emulsion (wherein Y in the formula (A) is F), as described above, Z in the formula (A) is -(CF ₂ )-, in the formula (A) The subscripts c, d, f, and g are 0 and the subscripts b, e, h, and n in the general formula (A) are each independently an integer greater than zero. As an example of this embodiment, the subscript a is 3, the subscript b is at least 1, the subscript e is 1, the subscript h is 1, B is an oxygen atom, the subscript n is 3, and the subscript m, i, and j are each 0. In this example, the polyfluoropolyether decane has the general formula: CF ₃ -CF ₂ -CF ₂ -(O-CF ₂ -CF ₂ -CF ₂ ) _b -O-CF ₂ -CF ₂ -CH ₂ - O-CH ₂ -CH ₂ -CH ₂ -Si-(X) _3-z (R ² ) _z . Thus, when the hydrolysable group represented by X is an alkoxy group (e.g., methoxy group), the specific polyfluoropolyether decane has the following formula: CF ₃ -CF ₂ -CF ₂ -(O-CF ₂ -CF ₂ -CF ₂ ) _b -O-CF ₂ -CF ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si-(OCH ₃ ) ₃ . Alternatively, when the hydrolyzable group represented by X is an alkylamino group (for example, an N(CH ₃ ) ₂ group), the specific polyfluoropolyether decane has the following formula: CF ₃ -CF ₂ - CF ₂ -(O-CF ₂ -CF ₂ -CF ₂ ) _b -O-CF ₂ -CF ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si-(N(CH ₃ ) ₂ ) ₃ . In these embodiments, the subscript b is typically an integer from 17 to 25.

In another embodiment of the non-aqueous emulsion wherein Y in the formula (A) is F and Z in the formula (A) is -(CF ₂ )-, as defined above, the formula (A) The lower subscripts c, d, f, and g are 0 and the subscripts b, e, h, n, m, i, and j in the general formula (A) are each independently an integer greater than zero. As an example of this embodiment, the subscript a is 3, the subscript b is at least 1, the subscript e is 1, the subscript h is 1, B is an oxygen atom, the subscript n is 3, subscripts m and i Each is 1 and the subscript j is 2. In this example, the polyfluoropolyether decane has the general formula: CF ₃ -CF ₂ -CF ₂ -(O-CF ₂ -CF ₂ -CF ₂ ) _b -O-CF ₂ -CF ₂ -CH ₂ - O-CH ₂ -CH ₂ -CH ₂ -Si(CH ₃ ) ₂ -O-Si(CH ₃ ) ₂ -CH ₂ -CH ₂ -Si-(X) _3-z (R ² ) _z . Therefore, when the hydrolyzable group represented by X is an alkoxy group (for example, methoxy group) and z is 0, the specific polyfluoropolyether decane has the following formula: CF ₃ -CF ₂ -CF ₂ -( O-CF ₂ -CF ₂ -CF ₂ ) _b -O-CF ₂ -CF ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si(CH ₃ ) ₂ -O-Si(CH ₃ ) ₂ -CH ₂ -CH ₂ -Si(OCH ₃ ) ₃ . In these embodiments, the subscript b is typically an integer from 17 to 25.

In another embodiment of the non-aqueous emulsion (wherein Y in the formula (A) is F), as described above, Z in the formula (A) is -(CF(CF ₃ )CF ₂ O)- . In this embodiment, the subscripts b, c, d, e and g in the formula (A) are 0, and the subscripts f, h and n in the formula (A) are each independently an integer greater than 0. As an example of this embodiment, the subscripts b, c, d, e, and g in the general formula (A) are 0, the subscript a is at least 1, the subscript f is 1, and the subscript h is 1, B. For the oxygen atom, the subscript n is 3, and the subscripts i, m, and j are each 0. In this example, the polyfluoropolyether decane has the general formula: F-(CF(CF ₃ )-CF ₂ -O) _a -CF(CF ₃ )-CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si-(X) _3-z (R ² ) _z . Thus, when the hydrolyzable group represented by X is an alkoxy group (e.g., methoxy group) and z is 0, the specific polyfluoropolyether decane has the following formula: F-(CF(CF ₃ )-CF ₂ -O) _a -CF(CF ₃ )-CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si-(OCH ₃ ) ₃ . Alternatively, when the hydrolyzable group represented by X is an alkylamino group (for example, an N(CH ₃ ) ₂ group), the specific polyfluoropolyether decane has the following formula: F-(CF(CF) ₃ ) -CF ₂ -O) _a -CF(CF ₃ )-CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si-(N(CH ₃ ) ₂ ) ₃ . In these embodiments, the subscript a is typically an integer from 14 to 20.

In another embodiment of the non-aqueous emulsion (wherein Y in the formula (A) is F and Z in the formula (A) is -(CF(CF ₃ )CF ₂ O)-), as described above In the formula (A), the subscripts b, c, d, e and g are 0, the subscript a is at least 1, the subscript f is 1, the subscript h is 1, B is an oxygen atom, and the subscript n 3, the subscripts m and i are each 1, and the subscript j is 2. In this example, the polyfluoropolyether decane has the general formula: F-(CF(CF ₃ )CF ₂ O) _a -CF(CF ₃ )-CH ₂ -O-CH ₂ -CH ₂ -CH ₂ - Si(CH ₃ ) ₂ -O-Si(CH ₃ ) ₂ -CH ₂ -CH ₂ -Si-(X) _3-z (R ² ) _z . Therefore, when the hydrolyzable group represented by X is an alkoxy group (for example, methoxy group) and z is 0, the specific polyfluoropolyether decane has the following formula: F-(CF(CF ₃ )CF ₂ O) _a -CF(CF ₃ )-CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si(CH ₃ ) ₂ -O-Si(CH ₃ ) ₂ -CH ₂ -CH ₂ -Si(OCH ₃ ) ₃ . In these embodiments, the subscript a is typically an integer from 14 to 20.

In other embodiments, Y in the general formula (A) is (R ² ) _z (X) _3-z Si-(C _j H _2j )-((SiR ¹ ₂ -O) _m -SiR ¹ ₂ ) _i -(C _n H _2n )-B-(CH ₂ ) _h -. Typically, when Y in the formula (A) is (R ² ) _z (X) _3-z Si-(C _j H _2j )-((SiR ¹ ₂ -O) _m -SiR ¹ ₂ ) _i -( When C _n H _2n )-B-(CH ₂ ) _h -, the subscripts b, c and f in the formula (A) are 0. Thus, in these examples, when the group indicated by the subscripts b, c and f is absent, the polyfluoropolyether decane has the general formula: YZ _a -[(OCF ₂ CF(CF ₃ )) _d - (OC ₂ F ₄ ) _e -(OCF ₂ ) _g ]-(CH ₂ ) _h -B-(C _n H _2n )-((SiR ¹ ₂ -O) _m -SiR ¹ ₂ ) _i -(C _j H _2j )-Si-(X) _3-z (R ² ) _z .

In one embodiment (wherein Y in the general formula (A) is (R ² ) _z (X) _3-z Si-(C _j H _2j )-((SiR ¹ ₂ -O) _m -SiR ¹ ₂ ) _i -(C _n H _2n )-B-(CH ₂ ) _h -), as just described above, Z is -(CF ₂ )-, B is an oxygen atom, subscript b in the general formula (A), c, d and f are 0, and the subscripts e and g in the general formula (A) are each independently an integer greater than zero. As an example of this embodiment, Z is -(CF ₂ )-, B is an oxygen atom, and subscripts b, c, d, f, m, i, and j in the 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 example, the polyfluoropolyether decane has the general formula: (R ² ) _z (X) _3-z Si-CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CF ₂ -(OCF ₂ CF ₂ ) _e -(OCF ₂ ) _g -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si- (X) _3-z (R ² ) _z . Therefore, when the hydrolyzable group represented by X is an alkoxy group (for example, methoxy group) and z is 0, the specific polyfluoropolyether decane has the following formula: (CH ₃ O) ₃ Si-CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CF ₂ -(OCF ₂ CF ₂ ) _e -(OCF ₂ ) _g -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si-(OCH ₃ ) ₃ . Alternatively, when the hydrolyzable group represented by X is an alkylamino group (for example, an N(CH ₃ ) ₂ group) and z is 0, the specific polyfluoropolyether decane has the following formula: (( CH ₃ ) ₂ N) ₃ Si-CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CF ₂ -(OCF ₂ CF ₂ ) _e -(OCF ₂ ) _g -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -Si-(N(CH ₃ ) ₂ ) ₃ .

Alternatively, in another embodiment (wherein Y in the formula (A) is (R ² ) _z (X) _3-z Si-(C _j H _2j )-((SiR ¹ ₂ -O) _m - In SiR ¹ ₂ ) _i -(C _n H _2n )-B-(CH ₂ ) _h -), as described above, Z is -(CF ₂ )-, and B is an oxygen atom, and is in the formula (A) The subscripts b, c, e, and f are 0, and the subscripts d and g in the general formula (A) are each independently an integer greater than zero.

It is noted that in the specific formula provided above, which represents an exemplary polyfluoropolyether decane, one or more of the polyfluoropolyether decanes may be replaced by other atoms. For example, other halogen atoms (e.g., Cl) may be present in the polyfluoropolyether decane, or the polyfluoropolyether decane may have a lower degree of fluorination. Lower fluorination means that any one or more of the fluorine atoms of the above formula may be replaced by a hydrogen atom.

Methods of preparing polyfluoropolyether decane are well known in the art. For example, polyfluoropolyether decane is typically prepared by a hydrazine hydrogenation reaction between an alkenyl-terminated polyfluoropolyether compound and a decane compound having a hydrazine-bonded hydrogen atom. The decane compound typically includes at least one hydrolyzable group, such as a hydrazine-bonded halogen atom. The hydrazine bonded halogen atom can be reacted and converted into other hydrolyzable groups. For example, a hydrazine-bonded halogen atom can be reacted with an alcohol such that the resulting polyfluoropolyether decane compound includes alkoxy functionality resulting from the alcohol. By-product salt of this reaction acid. It is within the skill of the art to understand how to modify the starting components to achieve the desired polyfluoropolyether decane structure. A specific example of a method of preparing various polyfluoropolyether decanes is disclosed in U.S. Patent Application Publication No. US 2009/0208728 A1, which is incorporated herein in its entirety by reference.

In various embodiments, the discontinuous phase of the non-aqueous emulsion further comprises a fluorinated vehicle. Fluorinated vehicles differ from polyfluoropolyether decanes and may be referred to as fluorinated solvents in certain embodiments. In these embodiments, the fluorinated vehicle can be any fluorinated vehicle capable of dissolving the polyfluoropolyether decane, and is typically selected such that the fluorinated vehicle does not interact with the polyfluoropolyether decane or non-aqueous emulsion. Any other component (particularly a discontinuous phase of the non-aqueous emulsion) reacts. Fluorinated vehicles generally have a lower molecular weight and increased volatility compared to polyfluoropolyether decane. Specific examples of the fluorinated vehicle 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, e.g. decafluoropentane; perfluoro aliphatic hydrocarbons, such as perfluoro C ₅ -C ₁₂ aliphatic hydrocarbons, e.g. perfluorohexane, perfluoro Methylcyclohexane and perfluoro-1,3-dimethylcyclohexane; polyfluorinated aromatic hydrocarbons such as bis(trifluoromethyl)benzene; hydrofluoroether (HFE), such as perfluorobutyl methyl ether ( C ₄ F ₉ OCH ₃ ), ethyl nonafluorobutyl ether (C ₄ F ₉ OC ₂ H ₅ ), ethyl nonafluoroisobutyl ether (C ₄ F ₉ OC ₂ H ₅ ), and similar HFE; perfluoro Polyether; perfluoroether; nitrogen-containing polyfluorinated vehicle, such as nitrogen-containing perfluorinated vehicle; Such fluorinated vehicles are well known in the art and are available from a variety of suppliers.

In various embodiments including a fluorinated vehicle in the discontinuous phase, the fluorinated vehicle comprises a perfluoropolyether vehicle. In these embodiments, the perfluoropolyether vehicle typically has a boiling point of at least 40 ° C, alternatively at least 60 ° C, alternatively at least 80 ° C, alternatively at least 100 ° C at atmospheric pressure (ie, 101.325 kPa). temperature. In a specific embodiment, the perfluoropolyether vehicle has a boiling temperature of from 125 ° C to 145 ° C, alternatively from 130 ° C to 140 ° C at atmospheric pressure. In another specific implementation In one embodiment, the perfluoropolyether vehicle has a boiling temperature of from 160 ° C to 180 ° C, alternatively from 165 ° C to 175 ° C at atmospheric pressure. Typically, the boiling point temperature of the perfluoropolyether vehicle is greater than 120 ° C to 180 ° C at atmospheric pressure, alternatively greater than 125 ° C to 180 ° C, alternatively greater than 160 ° C to 180 ° C. However, depending on the molecular weight of the perfluoropolyether vehicle, the boiling point temperature of the perfluoropolyether vehicle can be greater than the upper limit of 180 ° C to, for example, 200 ° C, 230 ° C or 270 ° C.

In embodiments wherein the fluorinated vehicle comprises a perfluoropolyether vehicle, the perfluoropolyether vehicle typically has the following general formula:

Where a" is an integer greater than 1 and b" is 0 or greater. Specifically, the labels a" and b" above the above formula are selected to provide the desired boiling point temperature of the perfluoropolyether vehicle. In particular, the relationship between the a) and b", boiling temperature and molecular weight of the perfluoropolyether vehicle is as follows:

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 wherein the nitrogen atom is a central atom having three polyfluorinated substituents (eg, three perfluorinated substituents), and The tertiary amine may optionally include a hetero atom such as oxygen, nitrogen and/or sulfur. Typically, the substituents bonded to the nitrogen atom are the same, although these substituents may differ in the number of carbon atoms present, the presence or absence of heteroatoms, and/or the fluorine content. These substituents generally comprise independently from 2 to 10 carbon atoms and are typically perfluorinated. As an example of such a nitrogen-containing perfluorinated vehicle, the structure representing C ₁₂ F ₂₇ N is presented for illustrative purposes only: Typically, when the fluorinated vehicle comprises a nitrogen-containing perfluorinated or polyfluorinated vehicle, the fluorinated vehicle comprises a combination of different nitrogen-containing perfluorinated or polyfluorinated vehicles.

The discontinuous phase of the non-aqueous emulsion can be a single fluorinated vehicle or a combination of two or more fluorinated vehicles. These fluorinated vehicles may be linear, branched, cyclic, alicyclic, aromatic or may contain combinations of the foregoing. 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; (HFE), such as Fluorobutyl methyl ether, ethoxy-nonafluorobutane and similar HFE and combinations thereof. Typically, the fluorinated vehicle comprises HFE.

When the discontinuous phase of the non-aqueous emulsion further comprises a fluorinated vehicle, the fluorinated vehicle and the polyfluoropolyether decane may be present in the discontinuous phase in varying amounts or ratios relative to each other. In general, during the preparation of the non-aqueous emulsion, the polyfluoropolyether decane is combined with a fluorinated vehicle to achieve better self-emulsifying properties prior to formation of the non-aqueous emulsion.

To this end, the discontinuous phase may comprise 100 parts by weight of polyfluoropolyether decane (when the discontinuous phase does not include a fluorinated vehicle) based on 100 parts by weight of the discontinuous phase of the non-aqueous emulsion. Alternatively, in the embodiment comprising a fluorinated vehicle in the discontinuous phase, the polyfluoropolyether decane is typically present in the discontinuity in an amount of from greater than 0 parts by weight to less than 100 parts by weight based on 100 parts by weight of the discontinuous phase. In the middle, and the actual value is selected based on the physical properties of the desired non-aqueous emulsion. For example, when the discontinuous phase contains more than 50 parts by weight of polyfluoropolyether decane based on 100 parts by weight of the discontinuous phase, the reproducibility of the non-aqueous emulsion generally decreases. Thus, in certain embodiments, the discontinuous phase comprises from 1 part by weight to 50 parts by weight, alternatively from 10 parts by weight to 30 parts by weight, alternatively from 15 parts by weight to 25 parts by weight, based on 100 parts by weight of the discontinuous phase. A portion, alternatively, a polyfluoropolyether decane in an amount of from 18 parts by weight to 22 parts by weight. The remainder of the discontinuous phase is typically a fluorinated vehicle. In other words, the discontinuous phase typically comprises from 51 parts by weight to 99 parts by weight, alternatively from 70 parts by weight to 90 parts by weight, alternatively from 75 parts by weight to 85 parts by weight, alternatively 78, based on 100 parts by weight of the discontinuous phase. A fluorinated vehicle is added in an amount of 82 parts by weight. In certain embodiments, the polyfluoropolyether decane and the fluorinated vehicle have similar densities such that the weight fractions set forth above are alternatively referred to as parts by volume, i.e., the ranges are also applicable to the discontinuous phases of these embodiments. The relative volume of the polyfluoropolyether decane and the fluorinated vehicle.

The relative amount of discontinuous phase present in the non-aqueous emulsion generally depends on whether the discontinuous phase further comprises a fluorinated vehicle. For example, in embodiments where the discontinuous phase does not include a fluorinated vehicle, the discontinuous phase is typically greater than 0 to 1.0 weight percent, alternatively greater than 0 to 0.50 weight percent, based on the total weight of the non-aqueous emulsion. It is present in the non-aqueous emulsion in an amount of from 0.10 to 0.30 weight percent, alternatively from 0.15 to 0.25 weight percent. In these embodiments, the discontinuous phase consists essentially of or consists of polyfluoropolyether decane. In these embodiments The discontinuous phase is typically greater than 0 to 0.56 volume percent, alternatively greater than 0 to 0.28 volume percent, alternatively 0.06 to 0.17 volume percent, alternatively 0.08 to 0.14 volume percent, based on the total volume of the non-aqueous emulsion. The amount is present in the non-aqueous emulsion.

Alternatively, in embodiments in which the fluorinated vehicle is included in the discontinuous phase, the discontinuous phase is typically greater than 0 to 10 weight percent, alternatively greater than 0 to 5 weight percent, based on the total weight of the non-aqueous emulsion, Alternatively, it may be present in the non-aqueous emulsion in an amount of from 25 to 2.0 weight percent, alternatively from 0.75 to 1.25 weight percent. In these embodiments, the discontinuous phase typically comprises the polyfluoropolyether decane and the fluorinated vehicle in the amounts just set forth above. In these embodiments, the discontinuous phase is typically greater than 0 to 5.86 volume percent, alternatively greater than 0 to 2.86 volume percent, alternatively 0.14 to 1.13 volume percent, alternatively 0.42, based on the total volume of the non-aqueous emulsion. An amount of up to 0.70 volume percent is present in the non-aqueous emulsion.

Thus, in certain embodiments, the discontinuous phase comprises from 1 part by weight to 50 parts by weight, alternatively from 10 parts by weight to 30 parts by weight, alternatively from 15 parts by weight to 25 parts by weight, based on 100 parts by weight of the discontinuous phase. A portion, alternatively, a polyfluoropolyether decane having a concentration of from 18 parts by weight to 22 parts by weight. The remainder of the discontinuous phase is typically a fluorinated vehicle. In other words, the discontinuous phase typically comprises from 51 parts by weight to 99 parts by weight, alternatively from 70 parts by weight to 90 parts by weight, alternatively from 75 parts by weight to 85 parts by weight, alternatively 78, based on 100 parts by weight of the discontinuous phase. A fluorinated vehicle is added in an amount of 82 parts by weight. In certain embodiments, the polyfluoropolyether decane and the fluorinated vehicle have similar densities such that the weight fractions set forth above are alternatively referred to as parts by volume, i.e., the ranges are also applicable to the discontinuous phases of these embodiments. The relative volume of the polyfluoropolyether decane and the fluorinated vehicle.

Concentration of polyfluoropolyether decane and fluorinated vehicle in discontinuous phase of non-aqueous emulsion The degree may vary from the range just set forth above, depending on the absence or presence of various optional components employed in the non-aqueous emulsion, as explained in more detail below.

As described above, the non-aqueous emulsion further contains a continuous phase comprising an organic vehicle. The continuous phase organic vehicle can be any organic vehicle capable of emulsifying a polyfluoropolyether decane (and optionally a fluorinated vehicle). Organic vehicles are generally referred to as organic vehicles in comparison to organic solvents because the organic vehicle only needs to disperse or emulsify the discontinuous phase, but does not require dissolution of the discontinuous phase.

In certain embodiments, the organic vehicle is selected such that the non-aqueous emulsion will exhibit a Tingal effect for a period of time. That is, the organic vehicle is a substance which causes the non-aqueous emulsion to exhibit the Tintre effect for a certain period of time. The Tindell effect, which is also known as Tintre scattering, is understood in the art to refer to light scattering by particles of a particular size range in a colloid or emulsion. More specifically, under the Tinter effect, shorter wavelength light is reflected by scattering and longer wavelength light is transmitted. In non-aqueous emulsions, light scattering is typically caused by a discontinuous phase, while a discontinuous phase is present in the continuous phase as dispersed particles. In particular, the organic phase of the continuous phase is typically a light transmissive medium, while the polyfluoropolyether decane of the discontinuous phase is typically a light scattering medium.

The organic vehicle can be combined with a polyfluoropolyether decane (either singly or alternatively with a fluorinated vehicle) to rapidly determine whether the resulting mixture exhibits a Tingal effect for a period of time. This determination is generally made via visual inspection or optical inspection. In particular, in order to determine whether a particular organic vehicle is suitable for use in a non-aqueous emulsion, a polyfluoropolyether decane is combined with a fluorinated vehicle to prepare a fluorinated composition, and then the fluorinated composition is combined with an organic vehicle. The fluorinated composition will generally self-disperse in the organic vehicle such that the fluorinated composition and the organic vehicle self-emulsify in the resulting non-aqueous emulsion and exhibit a Tingler effect for a period of time (in the case of certain organic vehicles) ). In general, if the resulting mixture exhibits a Tingler effect for a period of time, the resulting mixture is a non-aqueous emulsion. In other words, When the resulting mixture does not exhibit a Tingler effect for a period of time, the emulsion typically does not form from the organic vehicle and the polyfluoropolyether decane. In these examples (i.e., when the Tingler effect is not exhibited), the resulting mixture typically settles and/or phase separates.

For example, to quickly determine whether a particular organic vehicle is suitable for use in preparing a non-aqueous emulsion that exhibits a Tingler effect for a period of time, 0.02 grams of polyfluoropolyether decane can be combined with 0.08 grams of fluorinated vehicle to form a fluorinated composition. A fluorinated composition having a mass of 0.10 g can be placed dropwise in 9.90 g of an organic vehicle to form a mixture. The mixture can be shaken or stirred to determine if the mixture is emulsified to produce a non-aqueous emulsion exhibiting a Tingler effect for a period of time. While other amounts of organic vehicle, polyfluoropolyether decane, and/or fluorinated vehicle may be employed, this procedure allows for reproducible and reproducible high throughput analysis of many organic vehicles. In addition, this procedure allows for rapid determination of whether a particular organic vehicle is suitable for the preparation of a non-aqueous emulsion that exhibits a Tingde effect while requiring only a minimal amount of organic vehicle, polyfluoropolyether decane, and fluorinated vehicle.

In general, the longer the non-aqueous emulsion exhibits the Tingal 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 a Tingal effect for more 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, may be substituted The land is for 50 years. In general, the non-aqueous emulsion no longer exhibits the Tingle effect once the non-aqueous emulsion substantially settles or otherwise becomes a heterogeneous mixture. In these embodiments, the non-aqueous emulsion can be re-formed typically by applying a shear force to the heterogeneous mixture (e.g., by shaking or stirring). In other words, if the components settle, they will typically form a non-aqueous emulsion again upon application of shear. In some implementations In the case, the non-aqueous emulsion can exhibit the Tingde effect forever, that is, the non-aqueous emulsion may not settle and have excellent long-term stability.

Various classes of organic vehicles are suitable for the continuous phase of non-aqueous emulsions. For example, the organic vehicle can be aliphatic, aromatic, cyclic, alicyclic, and the like. While organic vehicles are typically derived from hydrocarbons, organic vehicles can include ethylenic unsaturation and can be substituted or unsubstituted. "Substituted" means that one or more hydrogen atoms of the organic vehicle may pass through a non-hydrogen atom (eg, a halogen atom such as chlorine, fluorine, bromine, etc.) or a substituent other than hydrogen (eg, a carbonyl group, an amine group) Alternatively, the carbon atom in the organic vehicle may be replaced by a non-carbon atom, that is, the organic vehicle may include one or more heteroatoms such as oxygen, sulfur, nitrogen, and the like.

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

The organic vehicle is not limited to an ester or a ketone. For example, in various embodiments, the organic vehicle is selected from the group consisting of tertiary butyl acetate, acetone, tetrahydrofuran, n-butyl acetate, dimethyl hydrazine, dichloromethane, diglyme, Tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl 10-undecenoate, dimethylformamide, butyl acetonitrile, methyl isobutyl ketone, 2-pentyl Ketone, 2-butanone, acetamidine, limonene, xylene, propylene carbonate, isopropanol, 1-methoxy Base-2-propanol, propylene glycol monomethyl ether acetate, isoamyl acetate, diethyl fumarate, tertiary butanol, 1-butanol, tertiary butyl methyl ether, toluene, ethylene glycol and A combination of the above.

In a particular embodiment, the organic vehicle is selected from the group consisting of acetone, dimethyl hydrazine, dichloromethane, xylene, n-butyl acetate, propylene carbonate, tetraethylene glycol dimethyl ether, three Ethylene glycol dimethyl ether, methyl isobutyl ketone, isoamyl acetate, diethyl fumarate, tertiary butanol, 2-butanone, tetrahydrofuran, tertiary 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, tertiary butyl acetate, and combinations thereof.

The continuous phase of the non-aqueous emulsion can consist essentially of or consist of an organic vehicle. The continuous phase typically comprises at least 10, alternatively at least 20, alternatively at least 30, alternatively at least 40, alternatively at least 50, alternatively at least 60, replaceable, based on the total weight of the continuous phase of the non-aqueous emulsion. 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 weight percent Organic vehicle. In these embodiments, the continuous phase typically comprises 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, based on the total volume of the continuous phase of the non-aqueous emulsion. 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 An organic vehicle in an amount of 99.44 volume percent. For example, if desired, the non-aqueous emulsion can be a concentrate in which the continuous phase is minimized within the ranges set forth above and the discontinuous phase is maximized. Alternatively, to reduce the overall cost of the non-aqueous emulsion, the continuous phase can be Maximize within the scope set forth above. The amount of organic vehicle in the continuous phase can vary from the range just set forth above, depending on the absence or presence of various optional components employed in the non-aqueous emulsion, as explained in more detail below.

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

For example, in embodiments where the discontinuous phase does not include a fluorinated vehicle, the continuous phase is typically from 99.0 to less than 100, alternatively from 99.5 to less than 100, alternatively from 99.7 to 99.9, based on the total weight of the non-aqueous emulsion. A percentage amount is present in the non-aqueous emulsion. In these embodiments, the continuous phase is typically 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 volume percent, based on the total volume of the non-aqueous emulsion. The amount is present in the non-aqueous emulsion.

Alternatively, in embodiments in which the fluorinated vehicle is included in the discontinuous phase, the continuous phase is typically from 70 to less than 100, alternatively from 80 to less than 100, alternatively 90 to less than the total weight of the non-aqueous emulsion. An amount of less than 100, alternatively from 95 to less than 100, alternatively from 98.0 to 99.75, alternatively from 98.75 to 99.25 weight percent, is present in the non-aqueous emulsion. In these embodiments, the continuous phase is typically 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, based on the total volume of the non-aqueous emulsion. The amount of 98.87 to 99.86, alternatively 99.3 to 99.58 volume percent, is present in the non-aqueous emulsion.

The discontinuous phase typically has a density greater than the continuous phase. Thus, depending on the choice of discontinuous phase and continuous phase, the relative weight or mass of the discontinuous phase and the continuous phase and the corresponding volume may vary.

The discontinuous phase typically forms particles in the continuous phase of the non-aqueous emulsion. The particles are liquid and are alternatively referred to as droplets. The size of the particles typically depends, for example, on whether the discontinuous phase also contains a fluorinated vehicle and the relative amounts of polyfluoropolyether decane and fluorinated vehicle in the discontinuous phase. In certain embodiments, the particles have a thickness of from 0.01 micrometers to 2.0 micrometers, alternatively from 0.05 micrometers to 1.5 micrometers, alternatively from 0.1 micrometers to 1.0 micrometers, alternatively 0.15 micrometers, as measured via dynamic light scattering techniques. An average particle size of 0.5 micrometers, alternatively 0.20 micrometers to 0.40 micrometers. The average particle size can vary with the technique used to measure the average particle size, and techniques other than dynamic light scattering can be employed herein.

The average particle size of the discontinuous phase of the non-aqueous emulsion can be selectively controlled. In particular, when the discontinuous phase comprises a fluorinated vehicle in combination with a polyfluoropolyether decane, increasing the concentration of the fluorinated vehicle in the fluorination concentration (ie, reducing the concentration of the polyfluoropolyether decane) results in smaller particles. path. Thus, varying the relative amount of fluorinated vehicle and polyfluoropolyether decane in the fluorinated composition affects the particle size of the discontinuous phase of the non-aqueous emulsion.

In a particular embodiment, the non-aqueous emulsion comprises an organic vehicle in an amount of from 90 to 99.9, alternatively from 95 to 99.8, alternatively from 98 to 99.7 weight percent, based on the total weight of the non-aqueous emulsion. In this embodiment, the non-aqueous emulsion comprises a fluorinated vehicle in an amount of greater than 0 to 5, alternatively 0.15 to 2.5, alternatively 0.30 to 2.0 weight percent, based on the total weight of the non-aqueous emulsion. Finally, in this embodiment, the non-aqueous emulsion comprises polyfluoropolyether decane in an amount of greater than 0 to 1, alternatively 0.05 to 0.5, alternatively 0.1 to 0.3 weight percent, based on the total weight of the non-aqueous emulsion. In this particular embodiment, the non-aqueous emulsion comprises an 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 volume percent, based on the total volume of the non-aqueous emulsion. In this embodiment, based on the total volume of the non-aqueous emulsion, The non-aqueous emulsion comprises a fluorinated vehicle in an amount of greater than 0 to 2.86, alternatively from 0.08 to 1.42, alternatively from 0.17 to 1.13 volume percent. Finally, in this embodiment, the non-aqueous emulsion comprises polyfluoropolyether decane 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 by volume, based on the total volume of the non-aqueous emulsion.

In various embodiments, the non-aqueous emulsion further comprises a surfactant. Surfactants may be present in the continuous phase and/or in the discontinuous phase (or at their interface). The surfactant may be nonionic, cationic, anionic, amphoteric, or zwitterionic. Surfactants can have, for example, monomeric, oligomeric or polymeric properties. While surfactants are generally required in conventional emulsions, the non-aqueous emulsions of the present invention can be prepared in the absence of any surfactant since the non-aqueous emulsions of the present invention are typically prepared by self-emulsification in the absence of significant shear. If employed, the surfactant may be present at the interface between the continuous phase and the discontinuous phase, depending on its ionic and other physical properties. Additionally or alternatively, the surfactant may be present in the continuous phase and/or discontinuous phase of the non-aqueous emulsion. Further, if employed, 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 weight percent, based on the total weight of the non-aqueous emulsion. However, since the preparation of the non-aqueous emulsion of the present invention does not require a surfactant, in certain embodiments, the non-aqueous emulsion consists essentially of the organic vehicle in the continuous phase and the fluorinated vehicle and polyfluoride in the discontinuous phase. The polyether decane composition or system consists of the above.

The non-aqueous emulsion may additionally include any other suitable components such as a coupling agent, an antistatic agent, a UV absorber, a plasticizer, a leveler, a pigment, a catalyst, and the like. These components may be present in the continuous phase and/or discontinuous phase of the non-aqueous emulsion.

Catalysts may alternatively be employed to promote surface modification by non-aqueous emulsions. These catalysts promote the transfer between any hydrolyzable groups of the polyfluoropolyether decane and the surface of the article. reaction. These catalysts may be used singly or in combination of two or more kinds in a non-aqueous emulsion. Examples of suitable catalytic compounds include acids such as carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid and/or valeric acid; bases; metal salts of organic acids such as tin dibutyl dioctoate, iron stearate and/or Or lead octoate; titanate, such as tetraisopropyl titanate and / or tetrabutyl titanate; chelating compounds, such as acetylacetonato titanium; aminopropyl triethoxy decane And similar. If employed, the catalyst is typically employed in an amount of from greater than 0 to 5, alternatively from 0.0001 to 1, alternatively from 0.001 to 0.1 weight percent, based on 100 parts by weight of the non-aqueous emulsion.

As described above, the total water content of the non-aqueous emulsion is controlled from 0 to less than 1 weight percent based on the total weight of the non-aqueous emulsion. More typically, the total water content of the non-aqueous emulsion is controlled 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 the total weight of the non-aqueous emulsion. 0.6, alternatively 0 to less than 0.5, alternatively 0 to less than 0.4, alternatively 0 to less than 0.3, 0 to less than 0.9, alternatively 0 to less than 0.2, alternatively 0 to less than 0.1 weight percent.

Even more typically, the total water content of the non-aqueous emulsion is controlled to be less than 500 parts per million (ppm) based on the total weight of the non-aqueous emulsion, for example from 0 to 500, based on the total weight of the non-aqueous emulsion, alternatively 0 Up to 250, alternatively 0 to 100, alternatively 0 to 50, alternatively 0 to 25, alternatively 0 to 10, alternatively 0 ppm. Maintaining a total water content of 0 ppm is typically difficult. Therefore, the lower limit in the above range is usually slightly larger than 0, for example, 1 part by billion (1 ppb), 10 ppb, 100 ppb, or 1 ppm.

When referring to the total water content of a non-aqueous emulsion, "control" generally means performing a definitive step to minimize the total water content of the non-aqueous emulsion. For example, water may be present in nominal amounts in various components employed in the non-aqueous emulsion, such as organic vehicles, polyfluoropolyether decane, and the like. Even the water When there is no desire, this is generally a fact and it is difficult to avoid. In other words, even if the components excluding water are combined to form a composition or emulsion, water is generally present therein. The presence of water may be due to, for example, atmospheric moisture, condensation, small amounts of water present in the components, and the like. Thus, the precise step of controlling the total water content of the non-aqueous emulsion differs from the preparation of only the non-aqueous emulsion without minimizing (alternatively eliminating) the total water content of the non-aqueous emulsion during its useful life.

In addition, controlling the total water content of the non-aqueous emulsion is generally maintained during the useful life of the non-aqueous emulsion. For example, water generally accumulates in a composition or a non-aqueous emulsion over time, i.e., conventional or non-aqueous emulsions generally accumulate water over time, which is not desirable. In contrast, the total water content of the non-aqueous emulsion will typically be controlled during the useful life of the non-aqueous emulsion, typically until a non-aqueous emulsion is used to prepare the layer of the surface treated article, as described below. In various embodiments, the total water content of the non-aqueous emulsion will be controlled during the period of time during which the non-aqueous emulsion exhibits the Tingler effect. In these or other embodiments, at 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, may be substituted Controlling the non-aqueous emulsion for 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 for up to 50 years Total water content. Since the non-aqueous emulsion can be stored and/or transported during its useful life, the total water content will generally be controlled over an extended period of time, such as at least 2 days, alternatively at least 1 week, alternatively at least 1 month. Alternatively, it may be at least 1 year, alternatively up to 50 years.

The total water content of the non-aqueous emulsion is controlled by placing the non-aqueous emulsion in a drying vessel which is separated from the moisture in the atmosphere such that the drying vessel is free of moisture. example For example, although not required, in certain embodiments, the total water content is controlled by a technique selected from the group consisting of: (i) placing the non-aqueous emulsion in a dry container; (ii) incorporating the desiccant into the non-aqueous emulsion. Or; (iii) simultaneous (i) and (ii). In certain embodiments, the drying vessel is evacuated with a drying gas (eg, nitrogen or argon), filled with a non-aqueous emulsion under vacuum, and then filled to atmospheric pressure with a dry gas. In certain embodiments, the drying container is an airtight container. In certain embodiments, a suitable drying container is generally a container that is substantially impervious to water vapor (ie, moisture in the atmosphere) such that the container ranges from 1 week to 50 years, from 5 weeks to 10 years, and from 26 weeks to 5 years. It does not contain water for a period of time from 1 to 3 years.

The drying vessel can have any shape or size in view of the desired volume of non-aqueous emulsion to be disposed therein. Further, the container 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 drying container is also substantially impervious to air or gas. For example, the drying vessel can comprise a layered structure of two or more different materials, wherein one or more of the materials are substantially impervious and one or more materials are not. Specific examples of materials suitable for use in drying containers include glass, metals or alloys, as well as certain polymeric materials such as certain performance plastics. Those of ordinary skill in the art will readily understand what materials are substantially impervious to air or gases.

Drying containers typically have an inlet for placing a non-aqueous emulsion therein. The inlet can be sealed by a variety of methods. For example, the inlet may be sealed by a plug or a stopcock, optionally with a tapered joint and/or threaded. The stopper or stopcock can be used in conjunction with a seal. The seal may comprise an o-ring, such as a polymer o-ring, sleeve, resin, wax, grease, and the like. For example, the seal is typically disposed between the plug or the stopcock and the container. Polytetrafluoroethylene (PTFE) is commonly used as the material for these seals.

While a dry vessel can be employed to control the total water content of the non-aqueous emulsion, the drying vessel generally does not reduce the total water content of the non-aqueous emulsion. Although a dry vessel can be used alone to control the total water content, the drying vessel does not improve the problems associated with water present in the non-aqueous emulsion at the time of preparation of the non-aqueous emulsion. For example, as noted above, certain components employed to prepare non-aqueous emulsions may inherently and undesirably include water. A specific example is an organic vehicle, and depending on its choice, organic vehicles often undesirably include a high concentration of water therein.

In certain embodiments, the total water content is controlled by incorporating a desiccant into the non-aqueous emulsion. The desiccant can be, for example, (i) water reactive or (ii) a dehydrating agent. The non-aqueous emulsion may contain both a water-reactive desiccant and a dehydrating desiccant.

When referring to a water-reactive desiccant, "water-reactive" means a desiccant that will chemically react with water if present in a non-aqueous emulsion. For example, a water-reactive desiccant can react with water to form a non-aqueous by-product or reaction product such as an acid, a base, an alcohol, and the like. The water-reactive desiccant can react with water to form a by-product of a non-water-single type of compound, or the water-reactive desiccant can react with water to form a combination of different by-products other than water.

The water reactive desiccant can comprise any suitable compound that will chemically react with water. The water reactive desiccant can be a solid, a liquid, a gas, or a combination of the above. Water-reactive desiccants typically do not ignite. In other words, the water-reactive desiccant generally does not burn or spontaneously ignite, for example, in the presence of atmospheric moisture. Therefore, the water-reactive desiccant is generally not selected from known pyrophoric reactive compounds (e.g., alkali metals, metal hydrides, etc.).

In certain embodiments, the water reactive desiccant is a monomeric compound having a water reactive functional group. By monomeric compound is meant that the water-reactive desiccant comprises three or fewer repeating units such that the water-reactive desiccant distinguishes it from the oligomer and the polymer. An exemplary water counter The functional group is a hydrolyzable group. Suitable hydrolyzable groups have been described above in reference to polyfluoropolyether decanes and include, for example, H, halogen atoms, alkoxy groups, alkylamino groups, carboxyl groups, alkyliminooxy groups, alkenyloxy groups, Or N-alkyl guanylamino.

In these or other embodiments, the water reactive desiccant is based on hydrazine. By hydrazine is meant that the water-reactive desiccant comprises at least one deuterium atom, such as a deuterium atom or two deuterium atoms. Water-reactive functional groups are typically bonded directly to the ruthenium atom. If two or more germanium atoms are present in the water-reactive desiccant, the germanium atoms may be bonded to each other via a covalent bond, or may be linked via a divalent linking group (which may be organic or non-organic) . Examples of the organic divalent linking group include a hydrocarbon group, a hetero group, and an organooheterylene linkage group. Specific examples of the non-organic divalent linking group include NH and O.

Alternatively, the water reactive desiccant may be free of deuterium atoms. Specific examples of the water-reactive desiccant in these examples include trialkyl orthoformate (e.g., trimethyl orthoformate), phosphorus pentoxide, and combinations thereof.

Specific examples of the water-reactive desiccant suitable for the non-aqueous emulsion include an alkyltrialkoxydecane, a diazane alkane, an alkyltrioximosilane, an alkyltri(carboxylate)decane, a trioxane. A halothane, and a combination thereof.

The alkyltrialkoxydecane has the formula: R ³ (OR ⁴ ) ₃ Si, wherein R ³ and R ^{4 are} each independently selected alkyl groups having from 1 to 10, alternatively from 1 to 6, alternatively 1 to 4, alternatively 1 to 2 carbon atoms. Specific examples of the alkyltrialkoxydecane include methyltrimethoxydecane, ethyltrimethoxydecane, methyltriethoxydecane, ethyltriethoxydecane, and methyldimethoxyethoxylate. Decane and so on.

The diazane can have the formula R ⁵ ₃ SiNHSiR ⁵ ₃ wherein each R ⁵ is independently selected alkyl, alkenyl, aryl, alkaryl, or aralkyl. Specific examples of the diazane alkane include a tetraalkyldienyldiazepine, a hexaalkyldiazepine, a diaryltetraalkyldiazepine, a tetraalkyldialkylaryldiazepine, Tetraalkyldiaralkyldiazane and the like.

The tetraalkyldienyldiazane has the formula: R ⁶ ₂ R ⁷ SiNHSiR ⁷ R ⁶ ₂ , wherein each R ⁶ is an independently selected alkyl group, as defined above for R ³ and R ⁴ and each R ⁷ 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 the tetraalkyldienyldiazepine include tetramethyldivinyldiazepine, tetraethyldivinyldiazepine, tetramethyldiallyldioxane, and dimethyl Diethyldivinyldioxane and the like.

Hexaalkyldioxane has the formula: R ⁸ ₃ SiNHSiR ⁸ ₃ wherein each R ⁸ is an independently selected alkyl group, as defined above for R ³ and R ⁴ . Specific examples of the hexaalkyldiazepine include hexamethyldioxane, diethyltetramethyldiazepine, and the like.

The diaryltetraalkyldiazepine has the formula: R ⁹ ₂ R ¹⁰ SiNHSiR ⁹ R ¹⁰ ₂ , wherein each R ⁹ is an independently selected alkyl group, as defined above for R ³ and R ⁴ and each R ¹⁰ An independently selected aryl group having from 3 to 12, alternatively from 3 to 8, alternatively from 3 to 6, alternatively 6 carbon atoms. Although not required, each R ¹⁰ may independently contain one or more heteroatoms (e.g., O, N, S, and P). Specific examples of R ¹⁰ include a phenyl group, a naphthyl group, a thienyl group, and an anthracenyl group. Specific examples of the diaryltetraalkyldiazepine include diphenyltetramethyldiazepine.

In certain embodiments, the diazane alkane is selected from the group consisting of tetraalkyldienyldioxane, hexaalkyldioxane, diaryltetraalkyldioxane, and combinations thereof Group.

The alkyltridecyldecane has the formula: R ¹¹ Si(ON=CH ₂ ) ₃ , wherein R ¹¹ is an alkyl group, as defined above for R ³ and R ⁴ . Specific examples of the alkyltridecyldecane include methyltridecyldecane, ethyltridecyldecane, propyltridecyldecane, and the like.

The alkyl tri(carboxylate) decane has the formula: R ¹² Si(OOCR ¹³ ) ₃ wherein R ¹² and each R ¹³ are independently selected alkyl groups, as defined above for R ³ and R ⁴ . Typically, each R ¹³ is a methyl group. In these embodiments, the alkyl tri(carboxylate)decane may alternatively be referred to as alkyltriethoxydecane. Specific examples thereof include methyltriethoxydecane, ethyltriethoxydecane, propyltriethoxydecane, and the like.

The trialkylhalodecane has the formula: R ¹⁴ ₃ SiX ¹ wherein each R ¹⁴ is independently selected alkyl, as defined above for R ³ and R ⁴ and X ¹ is selected from the group consisting of F, Cl, Br, and I. Halogen atom. Specific examples of the trialkylhalodecane include trimethylchlorodecane, triethylchlorodecane, trimethylbromodecane, dimethylethylchlorodecane, and the like.

In a specific embodiment, the water reactive desiccant comprises diazane, and the diazane is selected from the group consisting of hexaalkyldioxane, tetraalkyldienyl decazane, and diaryltetradecane Group of quinonezane groups. Exemplary species include hexamethyldioxane, diphenyltetramethyldiazepine, and tetramethyldivinyldioxane.

Alternatively, as described above, the desiccant may be a dewatering desiccant. The dehydrated desiccant can be any absorbent material suitable for use in reducing or eliminating any water in or from a non-aqueous emulsion. The hygroscopic material of the dehydrated desiccant typically absorbs water from its vicinity or otherwise removes water from its vicinity. As a comparison of the water-reactive desiccant, the dehydrated desiccant does not react with water, but instead absorbs or removes water. Like the water reactive desiccant, the dehydrated desiccant can be a solid, a liquid, a gas, or a combination of the above, although the dehydrated desiccant is typically a solid. In general, dehydrating desiccants absorb water through physical techniques that are contrary to chemical reactions (ie, dehydrating agents physically bind water), while chemical reactions are in the range of "water reactivity." Inside.

Specific examples of the dehydrating desiccant suitable for the non-aqueous emulsion include molecular sieves, sodium sulfate, calcium chloride, magnesium sulfate, calcium sulfate, magnesium chloride, lithium chloride, zeolite, aluminum citrate, and combinations thereof. Dehydrated desiccants are typically anhydrous or almost anhydrous.

Regardless of the desiccant employed, the desiccant can be included in the non-aqueous emulsion via a variety of methods. A desiccant may be present in a single component employed to prepare the non-aqueous emulsion. For example, a desiccant may be employed in the organic vehicle to dry the organic vehicle prior to preparing the non-aqueous emulsion with the organic vehicle. Alternatively, the desiccant can be incorporated as a separate component into the preformed non-aqueous emulsion.

Furthermore, the desiccant need not be present in the non-aqueous emulsion when using or applying a non-aqueous emulsion. For example, a desiccant can be incorporated into the non-aqueous emulsion to minimize (alternatively eliminate) any water therein and can then be separated from the non-aqueous emulsion. As an example below, the desiccant may be centrifuged or filtered from the non-aqueous emulsion depending on the choice of desiccant. Still alternatively, the desiccant need not be present in the non-aqueous emulsion itself. For example, the desiccant can be combined with one or more individual components of the non-aqueous emulsion prior to preparation of the non-aqueous emulsion to minimize (alternatively eliminate) any water, after which the desiccant can be used from the components in which the desiccant is employed. Separation. The components can then be combined to prepare a non-aqueous emulsion after separating the desiccant from the components in which the desiccant is employed. If the desiccant is removed, it is typically when the non-aqueous emulsion is to be stored in a dry container.

The concentration of the desiccant in the non-aqueous emulsion may vary depending, for example, on the storage container in which the non-aqueous emulsion is disposed, the relative humidity, the initial water content, and the like. For example, when the non-aqueous emulsion is also stored in a dry container, a lower concentration can be employed. Conversely, if the non-aqueous emulsion is exposed to moisture in the atmosphere, a higher concentration can be employed. Further, as described above, the concentration can be It varies depending on whether the desiccant is separated from the non-aqueous emulsion (or used before its preparation). Furthermore, when the desiccant comprises a water reactive desiccant, the concentration of the water reactive desiccant is generally dynamic over time. For example, the concentration of the water-reactive desiccant can be continuously reduced as the water-reactive desiccant reacts with any water in the non-aqueous emulsion and thus consumes. In certain embodiments where the non-aqueous emulsion comprises a desiccant, the desiccant in the non-aqueous emulsion is 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 desiccant is present in the molar ratio of polyfluoropolyether decane. The upper limit can be, for example, 1,000:1; 5,000:1; or even 10,000:1.

Non-aqueous emulsions can be prepared by a variety of methods. Typically, the organic vehicle and polyfluoropolyether decane are combined to produce a non-aqueous emulsion.

The organic vehicle and polyfluoropolyether decane can be combined in various ways. For example, the organic vehicle may be optionally added to the polyfluoropolyether decane in the presence of a stirrer or a mixer, or the polyfluoropolyether decane may be added to the organic vehicle, the agitator or mixer may be combined organically Used during and/or after the vehicle and polyfluoropolyether decane.

In various embodiments, the step of combining the organic vehicle and the polyfluoropolyether decane comprises disposing the polyfluoropolyether decane in an organic vehicle. The polyfluoropolyether decane can be disposed in the organic vehicle either manually (e.g., using a pipette or other glassware) or using suitable dispensing equipment.

Typically, the polyfluoropolyether decane is combined with a fluorinated vehicle to form a fluorinated composition, and then the fluorinated composition is disposed in an organic vehicle to prepare a non-aqueous emulsion.

As described above, the fluorinated composition (or polyfluoropolyether decane, as the case may be), once combined with an organic vehicle, will typically self-disperse and self-emulsify in an organic vehicle. Thus, in various embodiments, the method of preparing a non-aqueous emulsion does not involve applying any substantial shear force. To the step of non-aqueous emulsions, this step is usually required in the preparation of conventional emulsions. Alternatively, the components can be vortexed or otherwise mixed to prepare a non-aqueous emulsion. For example, minimal shear (e.g., vortexing the non-aqueous emulsion by hand or via a mixing device) is sufficient to initiate self-emulsification of the components of the non-aqueous emulsion.

As noted above, in embodiments including a desiccant, the desiccant can be incorporated into the non-aqueous emulsion or component thereof at any stage of the preparation of the non-aqueous emulsion. Similarly, the desiccant can be removed from the non-aqueous emulsion or its components at any stage of the preparation of the non-aqueous emulsion, if desired.

As set forth above, the present invention further provides surface treated articles and methods of making surface treated articles, which are described in greater detail below.

To prepare the surface treated article, a layer is deposited on the surface of the untreated article. Untreated items are prepared for surface treatment as described below. In certain embodiments, cerium oxide (SiO ₂ ) is pre-deposited on the untreated article prior to depositing the layer. Thus, in these embodiments, the untreated article surface comprises pre-deposited cerium oxide. The layer is formed from a non-aqueous emulsion which is applied to the surface of the untreated article to be surface treated to prepare a surface treated article. Although not necessary, in order to prepare untreated articles for surface treatment, the surface is activated using suitable activation techniques including, but not limited to, treatment with a base or treatment with atmospheric plasma.

For example, a method of preparing a surface treated article comprises applying a non-aqueous emulsion to a surface of an untreated article that is to be surface treated to form a wet layer of a non-aqueous emulsion on the surface of the untreated article. The method further comprises removing the organic vehicle from the wet layer to form a layer on the surface of the untreated article and obtaining a surface treated article. Although the article may be any article, the article is typically an electronic article, an optical article, a consumer appliance and component, an automobile body and components, etc. due to the superior physical properties obtained from the non-aqueous emulsion of the present invention. Most typically, the item is tied The following items are ideal: reduce stains and/or stains caused by fingerprints or skin oils, and make these contaminants easy to clean from surface treated items. An untreated item that is to be surface treated will differ from a surface treated item because the unprocessed item that is to be surface treated generally does not yet include the layer, although a combination of different layers may be employed, such as in a stacked form. If desired, the untreated article to be surface treated has a clean and dry surface which is optionally, for example, rinsed in a solvent and subsequently dried.

Examples of electronic articles typically include 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 commonly used in a variety of electronic devices. Among them, such as computer monitors, televisions, smart phones, global positioning systems (GPS), music players, remote controllers, handheld video games, portable readers, car dashboards, etc. Exemplary electronic items include An interactive touch screen display or other component that is often in contact with the skin and that constantly displays stains and/or smudges.

As described above, the item may also be a metal item, such as a consumer appliance and component. Exemplary articles are dishwashers, stoves, microwave ovens, refrigerators, freezers, etc., typically having a shiny metallic appearance, such as stainless steel, brushed nickel, and the like.

Alternatively, the item can be a carrier body or component, such as an automobile body or component. For example, a non-aqueous emulsion can be applied directly to the face of a car body to form the layer, which imparts a glossy appearance to the car body that is aesthetically pleasing and resistant to stains (eg, dust, etc.) and from fingerprints. Smudged.

Examples of suitable optical articles include inorganic materials such as glass plates, glass plates containing inorganic layers, ceramics, and the like. Additional examples of suitable optical articles include organic materials, examples Such as transparent plastic materials and transparent plastic materials containing inorganic layers. Specific examples of the optical article include an antireflection film, a filter, an optical lens, an eyeglass lens, a beam splitter, a crucible, a mirror, and the like.

Among the organic materials, examples of the transparent plastic material include materials containing various organic polymers. From the viewpoints of transparency, refractive index, dispersibility and similar optical properties and various other properties such as impact resistance, heat resistance and durability, materials used as optical members usually contain polyolefin (polyethylene, polypropylene). Etc.), polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), polydecylamine (Nylon 6, nylon 66, etc.), polystyrene, polyvinyl chloride, polyfluorene Imine, polyvinyl alcohol, ethylene vinyl alcohol, acrylic, cellulose (triethyl fluorenyl cellulose, diethyl acetyl cellulose, cellophane, etc.) or a copolymer of such organic polymers. It should be understood that these materials can be used in ophthalmic components. Non-limiting examples of ophthalmic elements include both corrective and non-corrective lenses, including single or multi-optical lenses (eg, bifocal, trifocal, and progressive lenses) that can be segmented or unsegmented, and used for correction Other components that protect or enhance vision, including but not limited to contact lenses, intraocular lenses, magnifiers, and protective lenses or goggles. Preferred materials for ophthalmic elements comprise one or more polymers selected from the group consisting of polycarbonate, polyamine, polyimine, polyfluorene, polyethylene terephthalate and polycarbonate copolymers. , polyolefins (especially polydecene), diethylene glycol-bis(allyl carbonate) polymers (called CR39) and copolymers, (meth)acrylic polymers and copolymers (especially derived from bisphenol) (meth)acrylic acid polymers and copolymers), sulfur (meth)acrylic acid polymers and copolymers, ethyl urethane and urethane polymers and copolymers, epoxy polymers and copolymers Epoxy sulfide polymers and copolymers.

In addition to the articles set forth above, the non-aqueous emulsions of the present invention can be applied to form the layer on other articles, such as automotive or aircraft window members, thus providing advanced functionality. In order to further improve the surface hardness, a non-aqueous emulsion can also be used by a so-called sol-gel process. A combination of TEOS (tetraethoxynonane) is used to effect surface modification.

A particular substrate may be applied based on a non-aqueous emulsion is formed of the layers Noticeable commercially available from Corning Incorporated of any of Corning, New York generation of Gorilla ^® glass. Another system worth noting that a particular substrate may be commercially available from Asahi Glass Company of Tokyo, Japan's Dragontrail ^® glass.

The method of applying a non-aqueous emulsion to the surface of an untreated article to prepare a surface treated article may vary.

For example, in certain embodiments, the step of applying a non-aqueous emulsion to the surface of the untreated article to form a wet layer will employ a wet coating application method. Specific examples of the wet coating application method suitable for the method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, sputtering, slit coating, ink jet printing, and combinations thereof. The organic vehicle can be removed from the wet layer via heat or other known methods.

In other embodiments, the step of applying a non-aqueous emulsion to the surface of the untreated article can include forming the layer on the surface of the untreated article using a deposition apparatus. For example, when a deposition apparatus is employed, the deposition apparatus typically includes a physical vapor deposition apparatus. In these embodiments, the deposition apparatus is typically selected from the group consisting of a sputtering apparatus, an atomic layer deposition apparatus, a vacuum apparatus, and a DC magnetron sputtering apparatus. The optimum operating parameters for each of these physical vapor deposition apparatus are based on the non-aqueous emulsion employed, the article on which the layer is to be formed, and the like. In certain embodiments, the deposition apparatus comprises a vacuum apparatus.

For example, when the layer is formed via physical vapor deposition (PVD), the method comprises combining a non-aqueous emulsion with a pellet to impregnate the pellet with a non-aqueous emulsion to form an impregnated pellet. Pellets typically comprise metals, alloys, or other strong materials such as iron, stainless steel, aluminum, carbon, copper, ceramics, and the like. Typically, the pellets have an extremely high surface area to volume ratio of the polyfluoropolyether decane used to contact the non-aqueous emulsion. The surface area to volume ratio of the pellets can be attributed to the porosity of the pellets, i.e., the pellets can be porous. Alternatively, the pellets may comprise woven, non-woven and/or randomized fibers (e.g., nanofibers) to provide the desired surface area to volume ratio. The pellets may comprise a material selected from the group consisting of SiO ₂ , TiO ₂ , ZrO ₂ , MgO, Al ₂ O ₃ , CaSO ₄ , Cu, Fe, Al, stainless steel, carbon, or a combination thereof. The material can be a plug within the casing that contains a metal, alloy, or other strong material. The non-aqueous emulsion can be introduced into the pill or introduced into the pill in any manner as long as the material of the pill and the polyfluoropolyether decane are combined or otherwise contacted. For example, the pellets can be immersed in a non-aqueous emulsion, or the non-aqueous emulsion can be placed in a sleeve such that the porous material is impregnated with a non-aqueous emulsion. Alternatively, the pellet may be immersed in an organic vehicle, or the organic vehicle may be placed in a sleeve such that the material of the pellet is impregnated with an organic vehicle, and then the polyfluoropolyether decane or fluorinated composition The material is disposed in an organic vehicle in the sleeve such that the material of the pellet is impregnated with a non-aqueous emulsion, and the polyfluoropolyether decane or fluorinated composition is formed in or on the pellet. In these embodiments, the method further comprises removing the organic vehicle (and fluorinated vehicle, if present) from the impregnated pellet prior to deposition to form a pure pellet. For example, the organic vehicle (and fluorinated vehicle, if present) can be rapidly evaporated from the pellet via the application of heat. Alternatively, the organic vehicle (and fluorinated vehicle, if present) can be removed from the pellet by drying at room temperature or at a slightly elevated temperature, optionally in the presence of vacuum or purge air.

Pure pellets can be stored until they are used in the deposition apparatus. In various embodiments, the pure pellets are stored in a vacuum sealed aluminum pouch.

A specific example of a vacuum apparatus suitable for forming this layer from a non-aqueous emulsion is available from Hanil Vacuum Machine Co., Ltd. of Incheon, South Korea. HVC-900DA vacuum equipment. Another example of a deposition apparatus is Edwards AUTO 306 from Edwards, Sanborn, NY.

Typically, the pure pellet is placed on a substrate in a chamber of a deposition apparatus together with the article to be coated, and the polyfluoropolyether decane is volatilized via electrical resistance heat evaporation to thereby form the layer on the surface of the untreated article, thereby preparing the Surface treatment items.

Regardless of the method of forming the layer, once the layer is formed from a non-aqueous emulsion on the surface of the untreated article, the layer may further undergo heating, humidification, catalytic post-treatment, light irradiation, electron beam irradiation, or the like. For example, when a non-aqueous emulsion is applied via a deposition apparatus, the layer formed therefrom is typically heated at a high temperature (e.g., 80 ° C to 150 ° C) for a period of time (e.g., 45 minutes to 75 minutes). Alternatively, the layer formed from the non-aqueous emulsion can be allowed to stand at room temperature and ambient conditions for a period of time (e.g., 24 hours).

Typically, the layer formed from the non-aqueous emulsion has a thickness of 1-1,000, alternatively 1-200, alternatively 1-100, alternatively 5-75, alternatively 10-50 nm (nm) .

As described above, the layer formed from the non-aqueous emulsion can have an excellent (i.e., low) coefficient of friction and excellent (i.e., high) durability. This is true whether or not a non-aqueous emulsion is applied via a wet coating process or via a deposition apparatus. For example, the sliding (dynamic) coefficient of friction can be measured by placing an object having a defined surface area and mass onto a surface treated article comprising a layer formed from a non-aqueous emulsion and the object There is a selected material between the layers (eg standard legal paper). A force perpendicular to gravity is then applied to cause the object to slide across the layer a predetermined distance, which allows calculation of the coefficient of sliding friction of the layer. The coefficient of sliding friction can be determined not only by the relative amounts of the discontinuous phase and the continuous phase in the non-aqueous emulsion, but also by the particular polyfluoropolyether decane employed in the non-aqueous emulsion. Typically after passing the layers to an abrasion test The durability of the layer formed from the non-aqueous emulsion is measured from the water contact angle of the layers. For example, for a layer with lower durability, the water contact angle will decrease after abrasion, which generally indicates that the layer has been at least partially degraded.

In certain embodiments, the layer formed from the non-aqueous emulsion has 75-120, alternatively 80-120, alternatively 90-120, alternatively 100-120 degrees before and after subjecting the layer to abrasion testing. Water contact angle of (°). Since the non-aqueous emulsion has an increased stability due to the control of the total water content, even after the non-aqueous emulsion is aged, for example, after 1 month, 2 months, 3 months, etc., the layer formed from the non-aqueous emulsion Typically there are such water contact angles. In certain embodiments, the layer formed from the non-aqueous emulsion has such water contact angles after aging the non-aqueous emulsion for up to 1 year, alternatively up to 2 years, alternatively up to 3 years. Aging refers to the non-aqueous emulsion itself, not the layer. For example, the non-aqueous emulsion can be optionally stored in a dry sealed receptacle or other container (e.g., a gas tight receptacle) while still being capable of forming a layer having excellent physical properties. Without being bound by any particular theory, it is believed that 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 based on the total weight of the non-aqueous emulsion. At (ppm), this contact angle performance is exhibited.

In these embodiments, the layers also typically have a slip 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) Dynamic) coefficient of friction. Although the coefficient of friction has no unit, it is usually represented by (μ).

The layer formed of the non-aqueous emulsion of the present invention has excellent physical properties as compared with the physical properties of the conventional layer formed by the self-learning surface treatment composition. In addition, the non-aqueous emulsion of the present invention can be compared to the conventional solvent in the conventional surface treatment composition to achieve miscibility. Prepared with a fraction of the cost of conventional surface treatment compositions, and in many cases significantly significant due to the significant presence of organic vehicles in non-aqueous emulsions which result in the significant absence of fluorinated vehicles Low toxicity, resulting in reduced cost and improved health and environmental characteristics.

Aspect 1. A non-aqueous emulsion comprising: a continuous organic phase comprising an organic vehicle; and a discontinuous phase comprising a polyfluoropolyether decane; wherein the total water content of the non-aqueous emulsion is based on the total weight of the non-aqueous emulsion Control is from 0 to less than 1 weight percent.

Aspect 2. A non-aqueous emulsion according to aspect 1, wherein the total water content is controlled by a technique selected from the group consisting of: (i) placing the non-aqueous emulsion in a dry container; (ii) incorporating a desiccant into the non-aqueous agent In aqueous emulsions; or (iii) simultaneous (i) and (ii).

Aspect 3. A non-aqueous emulsion according to aspect 1 or 2, wherein the total water content is controlled from 0 to less than 100 parts per million (ppm) based on the total weight of the non-aqueous emulsion.

A non-aqueous emulsion according to any one of the preceding aspects, wherein the total water content is controlled from 0 to less than 50 parts per million (ppm) based on the total weight of the non-aqueous emulsion.

A non-aqueous emulsion according to any one of aspects 2 to 4, wherein (ii) the desiccant is present in the non-aqueous emulsion to control the total water content of the non-aqueous emulsion.

Aspect 6. A non-aqueous emulsion according to aspect 5, wherein the desiccant is (i) water reactive or (ii) a dehydrating agent.

Aspect 7. A non-aqueous emulsion according to aspect 6, wherein the desiccant is (j) water reactive and is selected from the group consisting of alkyl trialkoxy decane, diazane, alkyl tridecyl decane, alkyl A group of tri(carboxylate)decane, and a trialkylhalodecane.

Aspect 8. The non-aqueous emulsion according to aspect 7, wherein the desiccant comprises the diazoxide and the diazane is selected from the group consisting of hexaalkyldioxane, tetraalkyldidecyl decazane, And two Group of aryl tetraalkyl diazane.

Aspect 9. The non-aqueous emulsion of any of the preceding aspects, wherein the discontinuous phase further comprises a fluorinated vehicle.

Aspect 10. The non-aqueous emulsion of any of the preceding aspects, wherein the organic vehicle is selected such that the non-aqueous emulsion exhibits a Tingle effect for a period of time.

Aspect 11. The non-aqueous emulsion according to aspect 10, wherein the organic vehicle is selected from the group consisting of: tertiary butyl acetate, acetone, tetrahydrofuran, n-butyl acetate, dimethyl hydrazine, dichloromethane , diglyme, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl 10-undecenoate, dimethylformamide, butyl acetate, dimethyl ester, methyl Butyl ketone, 2-pentanone, 2-butanone, acetamidine acetone, limonene, xylene, propylene carbonate, isopropanol, 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate, Isoamyl acetate, diethyl fumarate, tertiary butanol, 1-butanol, tertiary butyl methyl ether, toluene, ethylene glycol, and combinations thereof.

A non-aqueous emulsion according to any one of the preceding aspects, wherein the polyfluoropolyether decane has the formula (A): YZ _a -[(OC ₃ F ₆ ) _b -(OCF(CF ₃ )CF ₂ ) _c -(OCF ₂ CF(CF ₃ )) _d -(OC ₂ F ₄ ) _e -(CF(CF ₃ )) _f -(OCF ₂ ) _g ]-(CH ₂ ) _h -B-(C _n H _2n )-((SiR ¹ ₂ -O) _m -SiR ¹ ₂ ) _i -(C _j H _2j )-Si-(X) _3-z (R ² ) _z ; wherein the Z series is independently selected from -(CF ₂ ) -, -(CF(CF ₃ )CF ₂ O)-, -(CF ₂ CF(CF ₃ )O)-, -(CF(CF ₃ )O)-, -(CF(CF ₃ )CF ₂ )-, -(CF ₂ CF(CF ₃ ))-, and -(CF(CF ₃ ))-; a is an integer from 1 to 200; b, c, d, e, f, and g are each independently selected integer of from 0 to 200; h, n and j are each independently selected from an integer of 0 to 20; I and m are each independently selected from an integer of from 0 to 5; B is a divalent organic group or O; each R ¹ is Independently selected C ₁ -C ₂₂ hydrocarbyl groups; each z is an integer independently selected from 0 to 2; each X is an independently selected hydrolyzable group; each R ² is an independently selected C ₁ free of aliphatic unsaturation -C ₂₂ hydrocarbyl; and Y is selected from H, F, and Si-(X) _3-z (R ² ) _z (C _j H _2j )-((SiR ¹ ₂ -O) _m -SiR ¹ ₂ ) _i -(C _n H _2n )-B-(CH ₂ ) _h -; wherein X, B, z, R ¹ , R ² , j, m, i , n, and h are as defined above; the constraint is that when the subscript i is 0, the subscript j is also 0; and when the subscript i is an integer greater than 0, the subscripts j and i are each an integer greater than 0. , m is also an integer greater than zero.

Aspect 13. A non-aqueous emulsion according to aspect 12, wherein the hydrolyzable group represented by X in the general formula (A) of the polyfluoropolyether decane is independently selected from the group consisting of H, a halogen atom, -OR ³ , ^{-NHR 3, -NR 3 R 4,} -OOC-R 3, ON = CR 3 R 4, OC (= CR 3 R 4) R 5, and -NR ³ COR ^4, wherein R ^3, R ⁴ and R ⁵ Each is independently selected from the group consisting of H and a C ₁ -C ₂₂ hydrocarbyl group, and wherein R ³ and R ⁴ may optionally form a cyclic amine group together with the nitrogen atom to which the two are bonded in -NR ³ R ⁴ .

Aspect 14. A method of preparing a surface treated article, the method comprising: applying a non-aqueous emulsion of any of the foregoing aspects to a surface of an untreated article to form a wet layer on a 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.

Aspect 15. The method of Aspect 14, wherein the step of applying the non-aqueous emulsion uses an application method selected from the group consisting of dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, sputtering, and slitting. Slot coating, inkjet printing, and combinations of the above.

Aspect 16. The method of Aspect 14 or 15, wherein the layer has a water contact angle of 75 to 120°.

Aspect 17. The method of Aspect 16, wherein the layer has a water contact angle of from 90 to 120°.

Aspect 18. A method of preparing a surface treated article, the method comprising the steps of: combining a non-aqueous emulsion of any of Aspects 1 to 13 with a pellet to use the non-aqueous emulsion Dissolving the pellet to form an impregnated pellet; removing the organic vehicle from the impregnated pellet to form a pure pellet; and forming a layer on the surface of the untreated article via the deposition apparatus using the pure pellet to prepare the surface treated Items.

The accompanying aspects are not limited to any particular compound, non-aqueous emulsion or method described in the embodiments, which may vary between particular embodiments falling within the scope of the appended claims. With regard to the Markush group in this specification for the specific features or aspects of the various embodiments, different, special and/or unexpected results may be obtained from each member of the respective Markusi group. And independent of all other Markusi members. The individual members of the Markusi group may be individually or in combination, and sufficient support is provided for specific embodiments falling within the scope of the accompanying claims.

In addition, any range and sub-ranges that are used to describe the various embodiments of the present invention are independent of the scope of the accompanying claims, and all ranges including the whole and/or some of the values are described and envisioned, even if These values are not clearly understood in this specification. It is readily recognized by those skilled in the art that the scope and sub-ranges are fully described and the various embodiments of the invention can be practiced, and such ranges and sub-ranges can be further described as related halved, Three equal parts, four equal parts, five equal parts, and so on. The following is only an example. The range of "0.1 to 0.9" can be further described as the lower third (ie 0.1 to 0.3), the middle third (ie 0.4 to 0.6) and the upper third (ie 0.7). To 0.9), individually and collectively within the scope of the accompanying patent application, and which can be relied upon individually and/or collectively, and fully support the specific embodiments falling within the scope of the accompanying claims . In addition, with respect to words defining or modifying a range, such as "at least", "greater than", "less than", "not exceeding" and the like, such words include sub-ranges and/or upper or lower limits. As an example below, "to The range of 10" naturally includes at least a sub-range of 10 to 35, a sub-range of at least 10 to 25, a sub-range of 25 to 35, etc., and may depend on each sub-range individually and/or collectively, and will fall on The specific embodiments in the scope of the claims are fully supported. Finally, the individual numbers falling within the scope of the disclosure are fully provided, and the specific embodiments that fall within the scope of the appended claims are fully supported. For example, the range "from 1 to 9" includes various individual integers such as 3, and individual numbers including decimal points (or fractions) such as 4.1, which can be relied upon and specific to the scope of the accompanying patent application. The embodiments provide sufficient support.

The following examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention in any way.

Instance

Examples 1 to 3 and Comparative Examples 1 to 2:

Table 1 below illustrates the components used to prepare the non-aqueous emulsions of Examples 1 to 3 and Comparative Examples 1 to 2, and the respective amounts thereof. In the following Examples 1 to 3 and Comparative Example 2, a fluorinated vehicle was combined with a polyfluoropolyether decane to form a fluorinated composition. The fluorinated composition is then added dropwise to the organic vehicle via an elongated fine-tip ball-type pipette to prepare a non-aqueous emulsion, optionally when the fluorinated composition is placed in the organic vehicle. The components of the aqueous emulsion are subjected to eddy currents. Comparative Example 1 relates to a fluorinated composition which does not constitute a non-aqueous emulsion, and there is no continuous organic phase in the fluorinated composition of Comparative Example 1. Therefore, the fluorinated composition of Comparative Example 1 was formed only by disposing the polyfluoropolyether decane in a fluorinated vehicle. In Table 1 below, "C.E." means "Comparative Example" and "PFPE decane" means "polyfluoropolyether decane".

Organic vehicle 1 is a tertiary butyl acetate.

Fluorinated vehicle 1 is ethoxy-pellethofluorobutane (C ₄ F ₉ OC ₂ H ₅ ).

Polyfluoropolyether (the PFPE) Silane 1 having the general _{formula: F ((CF 2) 3} O) c. CF ₂ CF ₂ CH ₂ O(CH ₂ ) ₃ Si(OMe) ₃ , wherein c' is 17-25.

The fluorinated composition 1 comprises a mixture of a fluorinated vehicle 1 and a polyfluoropolyether decane 1.

Desiccant 1 was combined with the non-aqueous emulsions of Examples 1 to 3 to control its total water content. In particular, the desiccant 1 comprises a water reactive desiccant. Specifically, the desiccant 1 contains hexamethyldioxane.

Table 2 illustrates the molar ratio of desiccant to PFPE decane in each of Examples 1 to 3. The values in Table 2 are initial values because desiccant 1 can react with any water present in a particular non-aqueous emulsion, thus reducing its concentration over time.

The non-aqueous emulsions of Examples 1 to 3 and Comparative Examples 1 to 2 were spray coated (or The composition, as the case may be, is each applied to the surface of the substrate. Specifically, via a PVA-1000 dispenser with an atomization pressure of 8 psi, a stroke of 0.004", a nozzle height of 7 cm, an interval of 10 mm, and a speed of about 200 mm/sec (Precision, Valve, & Automation from Cohoes, NY) These non-aqueous emulsions and compositions were applied to a glass substrate. The glass substrates were washed in an ultrasonic bath for 20 minutes with a cleaning agent before applying Examples 1 to 3 and Comparative Examples 1 to 2 to the glass substrate. And then rinsed in deionized water three times for 2 minutes in an ultrasonic bath (Fisher Scientific FS-220). After washing, the glass substrate was dried in an oven at 125 ° C for 1 hour. After drying, use March Plasma. The PX250 chamber plasma treated the glass substrate (using ionized argon at 60 mTorr for 60 seconds, 300 W of RF power supply) to activate the glass substrate. The activated glass substrate was used immediately. At 3 psi liquid pressure A non-aqueous emulsion is applied, although the fluorinated composition is applied at a liquid pressure of 5 psi. After applying the respective non-aqueous emulsion (or composition) to the substrate, the non-aqueous emulsion (or composition) is allowed to pass at 125 ° C. Cured down for 1 hour on the substrate The layers are formed. The layers are rinsed with a fluorinating vehicle 1 to remove any portion of the curable composition or components thereof that remain after curing.

The physical properties of the layer formed from the non-aqueous emulsion and the composition are measured. In particular, the physical properties of the individual layers were measured before and after subjecting the layer to abrasion resistance testing, as described below.

The abrasion resistance test utilizes a reciprocating grinder - Model 5900, available from Taber Industries of North Tonawanda, New York. The abrasive materials used were from CS-10 Wearaser ^® from Taber Industries. The abrasive material has a size of 6.5 mm x 12.2 mm. The reciprocating grinder was operated for 25 cycles at a rate of 25 cycles per minute and with a stroke length of 1 inch and a load of 7.5 N.

The water contact angle (WCA) of each layer was measured via a VCA Optima XE angle measurement available from AST Products, Inc., Billerica, MA. The measured water contact angle is based on the static contact angle of 2 [mu]L of droplets on each layer. The water contact angle was measured before and after the abrasion resistance test described above. Further, a part of the non-aqueous emulsion (or composition, as the case may be) of Examples 1 to 3 and Comparative Examples 1 to 2 was stored in a sealed container to be aged. Specifically, these fractions were stored in dry sealed glass vials at 23 ± 2 ° C and 50 ± 5% relative humidity. After a specific time interval (2 weeks, 1 month, 2 months, and 3 months), the additional layers were subjected to the aged non-aqueous emulsions (or compositions) of Examples 1 to 3 and Comparative Examples 1 to 2 according to the above method. The material, as the case may be, is formed onto a fresh substrate. Before and after the layers were subjected to the abrasion resistance test as also described above, the WCA of each layer (hereinafter referred to as "abrasive" and "unabrasive") was measured as described above. Tables 3 and 4 below illustrate the WCA of the layers formed from Examples 1 to 3 and Comparative Examples 1 to 2. In general, the greater the WCA after abrasion, the higher the durability of the layer. The units of the values in Tables 3 and 4 below are degrees (°).

As clearly illustrated in Tables 3 and 4 above, the inclusion of Desiccant 1 in the non-aqueous emulsion of Examples 1 to 3 provides significant benefits compared to the non-aqueous emulsion without Desiccant 1 (eg, Comparative Example 2). . In particular, water can undesirably affect the durability of layers formed from non-aqueous emulsions. Therefore, the inclusion of desiccant 1 in the non-aqueous emulsion controls the total water content of the non-aqueous emulsion. Furthermore, increasing the initial concentration of desiccant 1 would provide improved results, with Example 3 including the highest concentration and Example 1 including the second highest concentration.

For example, the non-aqueous emulsions of Examples 1 to 3 were almost the same as the non-aqueous emulsion of Comparative Example 2 except that the total water content of the non-aqueous emulsions of Examples 1 to 3 was controlled via the desiccant 1. After aging the non-aqueous emulsion for an extended period of time (eg, 3 months), the effect is best displayed. For example, after 3 months, the layers formed from the non-aqueous emulsions of Examples 1 through 3 all have at least 113.6 (unabrasive) WCA. In contrast, the layer formed from the non-aqueous emulsion of Comparative Example 2 was only 99.9. This effect is more pronounced after abrasion, where the layer formed from the non-aqueous emulsions of Examples 1 and 3 will maintain WCA at least 107.4, while the layer formed from the non-aqueous emulsion of Comparative Example 2 will drop sharply to 62.8. Due to the higher concentration of desiccant 1 in the non-aqueous emulsions of Examples 1 and 3, the performance of the layer formed from the non-aqueous emulsions of Examples 1 and 3 may be better than the layer formed from the non-aqueous emulsion of Example 2.

Comparative Example 1 demonstrates control of total water content for non-aqueous emulsions including continuous organic phases The liquid has a unique effect. For example, Comparative Example 1 does not include the desiccant 1 which controls the total water content of its composition. Further, the composition of Comparative Example 1 represents a conventional fluorinated composition including a fluorinated vehicle and a polyfluoropolyether decane but no continuous organic phase. As clearly explained above, the performance of the layer formed from the composition of Comparative Example 1 did not deteriorate even after the composition was aged. Therefore, controlling the total water content is particularly important for non-aqueous emulsions compared to the composition.

Examples 4 to 8 and Comparative Examples 3 to 4:

Table 5 below illustrates the components used to prepare the non-aqueous emulsions of Examples 4 to 8 and Comparative Examples 3 to 4, and the respective amounts thereof. In the following Examples 4 to 8 and Comparative Examples 3 to 4, a fluorinated vehicle was combined with a polyfluoropolyether decane to form a fluorinated composition. The fluorinated composition is then added dropwise to the organic vehicle via an elongated fine-tip ball-type pipette to prepare a non-aqueous emulsion, optionally when the fluorinated composition is placed in the organic vehicle. The components of the aqueous emulsion are subjected to eddy currents. Comparative Example 3 relates to a fluorinated composition which does not constitute a non-aqueous emulsion, and there is no continuous organic phase in the fluorinated composition of Comparative Example 3. Therefore, the fluorinated composition of Comparative Example 3 was formed only by disposing the polyfluoropolyether decane in a fluorinated vehicle. In Table 5 below, "C.E." means "Comparative Example" and "PFPE decane" means "polyfluoropolyether decane".

Organic vehicle 2 is anhydrous acetone (<50 ppm H ₂ O).

Desiccant 1 was combined with the non-aqueous emulsions of Examples 4 to 8 to control its total water content. Table 6 illustrates the molar ratio of desiccant to PFPE decane in each of Examples 4 through 8 and the corresponding mass of Desiccant 1 present in each non-aqueous emulsion. The values in Table 6 are initial values because desiccant 1 can react with any water present in a particular non-aqueous emulsion, thus reducing its concentration over time.

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

The physical properties of the layer formed from the non-aqueous emulsion and the composition are measured. In particular, the physical properties of the individual layers were measured before and after subjecting the layer to abrasion resistance testing, as described above. Further, a portion of the non-aqueous emulsions (or compositions, as the case may be) of Examples 4 to 8 and Comparative Examples 3 to 4 were stored in a sealed container for aging. Specifically, the portions were stored in dry sealed glass vials at 23 ± 2 ° C and 50 ± 5% relative humidity. After a certain time interval (1 month, 2 months, and 3 months), an additional layer was obtained from the aged non-aqueous emulsions (or compositions of Examples 4 to 8 and Comparative Examples 3 to 4) according to the above method. Subject to availability) Formed on a fresh substrate. Before and after the layers were subjected to the abrasion resistance test as also described above, the WCA of each layer (hereinafter referred to as "abrasive" and "unabrasive") was measured as described above. Tables 7 and 8 below illustrate the WCA of the layers formed from Examples 4 to 8 and Comparative Examples 3 to 4. In general, the greater the WCA after abrasion, the higher the durability of the layer. The units of the values in Tables 7 and 8 below are degrees (°).

As illustrated in Tables 7 and 8 above, the inclusion of Desiccant 1 in the non-aqueous emulsions of Examples 4 to 8 provided significant benefits over the non-aqueous emulsions containing Desiccant 1 (e.g., Comparative Example 4). In particular, water can undesirably affect the durability of layers formed from non-aqueous emulsions. Therefore, the inclusion of desiccant 1 in the non-aqueous emulsion controls the total water content of the non-aqueous emulsion. Further, as shown in Example 8, increasing the concentration of the desiccant 1 beyond a certain threshold may affect durability.

For example, the non-aqueous emulsions of Examples 4 to 8 were almost identical to the non-aqueous emulsion of Comparative Example 4 except that the total water content of the non-aqueous emulsions of Examples 4 to 8 was controlled via Desiccant 1. After aging the non-aqueous emulsion for an extended period of time (eg, 3 months), the effect is best displayed. For example, after 3 months, the layers formed from the non-aqueous emulsions of Examples 4 through 8 all have at least 104.5 (unabrasive) WCA, while the layers formed from the non-aqueous emulsions of Examples 4 through 7 have at least 3 months later. 110.7 (unabrasive) WCA. In contrast, the layer formed from the non-aqueous emulsion of Comparative Example 4 after 3 months was only 99.7 (unabrasive).

Comparative Example 3 (which is similar to Comparative Example 1) again confirmed that for the reasons described above, controlling the total water content has a unique effect on non-aqueous emulsions including continuous organic phases.

Examples 9 to 15 and Comparative Examples 5 to 6:

Table 9 below illustrates the components used to prepare the non-aqueous emulsions of Examples 9 to 15 and Comparative Examples 5 to 6, and the respective amounts thereof. In the following Examples 9 to 15 and Comparative Examples 5 to 6, a fluorinated vehicle was combined with a polyfluoropolyether decane to form a fluorinated composition. The fluorinated composition is then added dropwise to the organic vehicle via an elongated fine-tip ball-type pipette to prepare a non-aqueous emulsion, optionally when the fluorinated composition is placed in the organic vehicle. The components of the aqueous emulsion are subjected to eddy currents. Comparative Example 5 relates to a fluorinated composition which does not constitute a non-aqueous emulsion, and there is no continuous organic phase in the fluorinated composition of Comparative Example 5. Therefore, the fluorinated composition of Comparative Example 5 was formed only by disposing the polyfluoropolyether decane in a fluorinated vehicle. In Table 9, below, "C.E." means "Comparative Example" and "PFPE decane" means "polyfluoropolyether decane".

It is worth noting that to further illustrate the effect of desiccant 1, water was deliberately added to the non-aqueous emulsions of Examples 14 and 15. Specifically, in addition to any intrinsic water present in the non-aqueous emulsions of Examples 14 and 15, 0.0075 grams of water was added to the non-aqueous emulsion of Example 14, and 0.0898 grams of water was added to the non-aqueous emulsion of Example 15. Typically, this water content is detrimental to the nature of the layer formed from the non-aqueous emulsion containing the same.

The total water content of the non-aqueous emulsions of Examples 9 to 15 was controlled. In particular, the total water content of these non-aqueous emulsions is controlled via a desiccant. Table 10 below shows the specific desiccants employed in each of Examples 9 through 15 and the corresponding mass of each desiccant employed. The values in Table 10 are initial values because the desiccant can react with or otherwise absorb/remove water from any water present in a particular non-aqueous emulsion, thus reducing its concentration over time.

Desiccant 2 is trimethyl orthoformate which is a water reactive desiccant.

Desiccant 3 is phosphorus pentoxide, which is a water reactive desiccant.

The desiccant 4 is 1,1,3,3,5,5-hexamethylcyclotriazane which is a water-reactive desiccant.

The desiccant 5 is magnesium sulfate, which is a dehydrating desiccant.

The samples of the non-aqueous emulsions (or compositions, as the case may be) of Examples 9 to 15 and Comparative Examples 5 to 6 were each applied to the surface of the substrate as described above with respect to Examples 1 to 3 and Comparative Examples 1 to 2. .

The physical properties of the layer formed from the non-aqueous emulsion and the composition are measured. In particular, the physical properties of the individual layers were measured before and after subjecting the layer to abrasion resistance testing, as described above. Further, a portion of the non-aqueous emulsions (or compositions, as the case may be) of Examples 9 to 15 and Comparative Examples 5 to 6 were stored in a sealed container for aging. Specifically, the portions were stored in dry sealed glass vials at 23 ± 2 ° C and 50 ± 5% relative humidity. After a certain time interval (1 month, 2 months, and 3 months), an additional layer was obtained from the aged non-aqueous emulsions (or compositions of Examples 9 to 15 and Comparative Examples 5 to 6 according to the above method). Formed as the case may be. Before and after the layers were subjected to the abrasion resistance test as also described above, the WCA of each layer (hereinafter referred to as "abrasive" and "unabrasive") was measured as described above. Tables 11 and 12 below illustrate the WCA of the layers formed from Examples 9 to 15 and Comparative Examples 5 to 6. The units of the values in Tables 11 and 12 below are degrees (°).

As shown in Tables 11 and 12 above, controlling the total water content of the non-aqueous emulsion via certain desiccants provides a significant benefit to the performance of the layer formed from the non-aqueous emulsion, even after an extended period of time (e.g., 3 months). For example, after 3 months, the layer formed from the non-aqueous emulsions of Examples 13 to 15 still had at least 100.0 (unabrasive) WCA.

Examples 16 to 21 and Comparative Example 7:

Table 13 below illustrates the non-aqueous emulsions used to prepare Examples 16 to 21 and Comparative Example 7. The components of the liquid and their respective amounts. In the following Examples 16 to 21 and Comparative Example 7, a fluorinated vehicle was combined with a polyfluoropolyether decane to form a fluorinated composition. The fluorinated composition is then added dropwise to the organic vehicle via an elongated fine-tip ball-type pipette to prepare a non-aqueous emulsion, optionally when the fluorinated composition is placed in the organic vehicle. The components of the aqueous emulsion are subjected to eddy currents. In Table 13, below, "C.E." means "Comparative Example" and "PFPE decane" means "polyfluoropolyether decane".

The total water content of the non-aqueous emulsions of Examples 16 to 21 was controlled. In particular, the total water content of these non-aqueous emulsions is controlled via a desiccant. Table 14 below shows the specific desiccants employed in each of Examples 16 through 21 and the corresponding mass of each desiccant employed. The values in Table 14 are initial values because the desiccant can react with or otherwise absorb/remove water from any water present in a particular non-aqueous emulsion, thus reducing its concentration over time.

Desiccant 6 is methyltrimethoxydecane which is a water reactive desiccant.

The desiccant 7 is tetramethyldivinyldioxane which is a water reactive desiccant.

Desiccant 8 is methyltridecyldecane which is a water reactive desiccant.

Desiccant 9 is a blend of methyl/ethyltriethoxymethoxydecane which is a water reactive desiccant.

The desiccant 10 is trimethylchloromethane, which is a water reactive desiccant.

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

The physical properties of the layer formed from the non-aqueous emulsion were measured. In particular, the physical properties of the individual layers were measured before and after subjecting the layer to abrasion resistance testing, as described above. Further, a portion of the non-aqueous emulsions of Examples 16 to 21 and Comparative Example 7 were stored in a sealed container to be aged. Specifically, the portions were stored in dry sealed glass vials at 23 ± 2 ° C and 50 ± 5% relative humidity. After a certain time interval (1 month, 2 months, and 3 months), additional layers were formed on the brand new substrate from the aged non-aqueous emulsions of Examples 16 to 21 and Comparative Example 7 according to the above method. Before and after the layers were subjected to the abrasion resistance test as also described above, the WCA of each layer (hereinafter referred to as "abrasive" and "unabrasive") was measured as described above. Tables 15 and 16 below illustrate the WCA of the layers formed from Examples 16 to 21 and Comparative Example 7. The units of the values in Tables 15 and 16 below are degrees (°). The values in Tables 15 and 16 represent the average values based on 18 different measurements for each WCA value.

As shown in Tables 15 and 16 above, controlling the total water content of the non-aqueous emulsion via certain desiccants provides a significant benefit to the performance of the layer formed from the non-aqueous emulsion, even after an extended period of time (e.g., 3 months). For example, after 3 months, the layer formed from the non-aqueous emulsions of Examples 18 through 19 still had at least 103.0 (abrasive) WCA. It is particularly desirable to maintain such WCA even after abrasion after 3 months of storage of the non-aqueous emulsion.

The present invention has been described in an illustrative manner, and the terms used are intended to be illustrative of the nature of the words. Obviously many modifications and variations of the present invention are possible in the light of the teachings herein. The invention may be embodied in other specific forms than those specifically described.

Claims (11)

A non-aqueous emulsion comprising: a continuous organic phase comprising an organic vehicle; and a discontinuous phase comprising a polyfluoropolyether decane; wherein the total water content of the non-aqueous emulsion is controlled to 0 based on the total weight of the non-aqueous emulsion Less than 1 weight percent. The non-aqueous emulsion of claim 1, wherein the total water content is controlled by a technique selected from the group consisting of: (i) placing the non-aqueous emulsion in a drying vessel; (ii) incorporating a desiccant into the non-aqueous emulsion; Or (iii) simultaneous (i) and (ii). The non-aqueous emulsion of claim 1, wherein the total water content is controlled from 0 to less than 100 parts per million (ppm) based on the total weight of the non-aqueous emulsion; or wherein the total water is based on the total weight of the non-aqueous emulsion The content is controlled from 0 to less than 50 parts per million (ppm). A non-aqueous emulsion according to claim 2, wherein (ii) the desiccant is present in the non-aqueous emulsion to control the total water content of the non-aqueous emulsion; wherein the desiccant is (i) water reactive or (ii) dehydrated Or the desiccant is (i) water reactive or (ii) a dehydrating agent, and wherein the desiccant is (i) water reactive and is selected from the group consisting of alkyl trialkoxy decane, diazane, a group of alkyl tridecyl decane, alkyl tri(carboxylate) decane, and trialkyl halodecane; or wherein the desiccant is (i) water reactive or (ii) a dehydrating agent, and wherein the drying The agent is (i) water-reactive and is selected from the group consisting of alkyl trialkoxy decane, diazirane, alkyl tridecyl decane, alkyl tri(carboxylate) decane, and trialkyl halodecane. Group and wherein the desiccant comprises the diterpenes The azane and the diazane are selected from the group consisting of hexaalkyldioxane, tetraalkyldienylazane, and diaryltetraalkyldioxane. A non-aqueous emulsion according to any of the preceding claims, wherein the discontinuous phase further comprises a fluorinating vehicle. A non-aqueous emulsion according to claim 1, wherein the organic vehicle is selected such that the non-aqueous emulsion exhibits a Tingal effect for a period of time; or wherein the organic vehicle is selected from the group consisting of: Ester, acetone, tetrahydrofuran, n-butyl acetate, dimethyl hydrazine, dichloromethane, diglyme, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl 10-undecenoate , dimethylformamide, acetoacetate tertiary butyl ester, methyl isobutyl ketone, 2-pentanone, 2-butanone, acetoacetone, limonene, xylene, propylene carbonate, isopropanol, 1-methoxy-2-propanol, propylene glycol monomethyl acetate, isoamyl acetate, diethyl fumarate, tertiary butanol, 1-butanol, tertiary butyl methyl ether, toluene, Ethylene glycol and a combination thereof; or wherein the organic vehicle is selected such that the non-aqueous emulsion exhibits a Tingler effect for a period of time, wherein the organic vehicle is selected from the group consisting of: Ester, acetone, tetrahydrofuran, n-butyl acetate, dimethyl hydrazine, dichloromethane, diglyme, tetraethyl Alcohol dimethyl ether, triethylene glycol dimethyl ether, methyl 10-undecenoate, dimethylformamide, butyl acetate acetate, methyl isobutyl ketone, 2-pentanone, 2 -butanone, acetoacetone, limonene, xylene, propylene carbonate, isopropanol, 1-methoxy-2-propanol, propylene glycol monomethyl acetate, isoamyl acetate, fumaric acid Diethyl ester, tertiary butanol, 1-butanol, tertiary butyl methyl ether, toluene, ethylene glycol, and combinations thereof. A non-aqueous emulsion according to claim 1, wherein the polyfluoropolyether decane has the formula (A): YZ _a -[(OC ₃ F ₆ ) _b -(OCF(CF ₃ )CF ₂ ) _c -(OCF ₂ CF (CF ₃ )) _d -(OC ₂ F ₄ ) _e -(CF(CF ₃ )) _f -(OCF2) _g ]-(CH ₂ ) _h -B-(C _n H _2n )-((SiR ¹ ₂ -O) _m -SiR ¹ ₂ ) _i -(C _j H _2j )-Si-(X) _3-z (R ² ) _z ; wherein the Z series are independently selected from -(CF ₂ )-, -(CF(CF ₃ ) CF ₂ O)-, -(CF ₂ CF(CF ₃ )O)-, -(CF(CF ₃ )O)-, -(CF(CF ₃ )CF ₂ )-, -(CF ₂ CF( CF ₃ ))-, and -(CF(CF ₃ ))-; a is an integer from 1 to 200; b, c, d, e, f, and g are each independently selected from an integer from 0 to 200; n and j are each independently selected from 0 to 20 integers; i and m are each independently selected from 0 to 5 integers; B is a divalent organic group or O; each R ¹ is independently selected C ₁ -C ₂₂ a hydrocarbyl group; each z is an integer independently selected from 0 to 2; each X is an independently selected hydrolyzable group; each R ² is an independently selected aliphatically unsaturated C ₁ -C ₂₂ hydrocarbyl group; From H, F, and Si-(X) _3-z (R ² ) _z (C _j H _2j )-((SiR ¹ ₂ -O) _m -SiR ¹ ₂ ) _i -(C _n H _2n )-B - (CH _{2) h} -; wherein ^{X, B, z, R 1} , R 2, j, m, i, n, and h are as above based Yi; with the proviso that the subscript i is 0, subscript j is also 0; and when subscript i is an integer greater than 0, the subscript i and j are each an integer greater than 0, m is also an integer greater than 0's. The non-aqueous emulsion according to claim 7, wherein the hydrolyzable group represented by X in the formula (A) of the polyfluoropolyether decane is independently selected from the group consisting of H, a halogen atom, -OR ³ , -NHR ³ , -NR ³ R ⁴ , -OOC-R ³ , ON=CR ³ R ⁴ , OC(=CR ³ R ⁴ )R ⁵ , and -NR ³ COR ⁴ , wherein R ³ , R ⁴ and R ^{5 are} each independently selected from H and a C ₁ -C ₂₂ hydrocarbyl group, and wherein R ³ and R ⁴ may optionally form a cyclic amine group together with the nitrogen atom to which the two are bonded in -NR ³ R ⁴ . A method of preparing a surface treated article, the method comprising: applying a non-aqueous emulsion of any of the preceding claims to a surface of an untreated article to form a wet layer on the surface of the untreated article; The organic vehicle is removed from the wet layer to form a layer on the surface of the untreated article to prepare the surface treated article. The method of claim 9, wherein the layer has a water contact angle of 75 to 120°; or wherein the layer has a water contact angle of 90 to 120°. A method of preparing a surface-treated article, the method comprising the steps of: combining the non-aqueous emulsion of any one of claims 1 to 8 with a pill to impregnate the pill with the non-aqueous emulsion to form an impregnated pill; The organic vehicle is removed by impregnation of the pellet to form a pure pellet; and the surface is treated by forming a layer on the surface of the untreated article via the deposition apparatus using the pure pellet.