Background

Surfaces of e.g. rubber tires of motor vehicles and the like are frequently treated with compositions configured to impart a glossy appearance to the surface.

Summary

In broad summary, herein is disclosed a water-based composition in the form of an aqueous emulsion. The aqueous emulsion comprises water; a hydrophobic, silicone-based material; a siliconepolyether surfactant that serves both as a wetting agent and as an emulsifier; and a water-soluble thickener. These and other aspects will be apparent from the detailed description below. In no event, however, should this broad summary be construed to limit the claimable subject matter, whether such subject matter is presented in claims in the application as initially filed or in claims that are amended or otherwise presented in prosecution.

Brief Description of the Drawings

Fig. 1 is a perspective view of an exemplary trigger-actuated spray head assembly suitable for attaching to a spray bottle.

Fig. 2 is a perspective view of a portion of an exemplary spray bottle that can accept a trigger- actuated spray head assembly.

Detailed Description

The term “configured to” and like terms is at least as restrictive as the term “adapted to”, and requires actual design intention to perform the specified function rather than mere capability of performing such a function. Terms such as “a” and “an”, when used in combination with “comprises”, “comprising”, and like terms, will be understood to mean “at least one”; e.g. the phrase “comprises a surfactant” means “comprises at least one surfactant”. The term “emulsion” is understood to refer to an aqueous macroemulsion as defined herein, unless otherwise specified.

Disclosed herein are water-based compositions, by which is meant compositions comprising at least 50 wt. % water. In some embodiments the compositions are sprayable, meaning that they are configured (e.g. with suitable viscosity) so that they can be dispensed from a container by spraying, e.g. using a trigger-type spray assembly 1 mounted onto a container 2 as depicted in generic, representative embodiment in Figs. 1 and 2. The water-based compositions are aqueous, oil-in-water emulsions. Any such composition can be dispensed onto a surface e.g. by spraying, in order to treat the surface with the composition. This will cause the composition to be deposited onto the surface, e.g. in the form of droplets of the composition that are distributed across the surface.

The composition is configured (in particular, to include a wetting agent as discussed in detail herein, and to be of a suitable viscosity) so that even on a relatively hydrophobic surface such as rubber, the droplets of the composition, when disposed on the surface at a sufficient density of droplets per area, will spread on the surface, encounter each other, and consolidate (merge) to form an at least semi- continuous layer (coating) of the composition on the surface. Here and elsewhere herein, by at least semi-continuous means that the layer will be continuous and uninterrupted over much (e.g. greater than 85 %) of the area of the treated surface. However, as may be expected for any statistically-governed process such as consolidation of droplets, there may be occasional pinholes, craters, cracks, or the like. This is particularly true for disposing the composition on the surface of a tire, which may contain various textured areas, raised or recessed molded-in features, and so on. This accounts for the terminology of the layer being described as semi-continuous rather than being required to be truly continuous. However, the present work has found that a layer of the herein-disclosed composition, when applied e.g. to a sidewall of a tire, typically exhibits a uniform, glossy appearance even in the presence of molded-in letters, grooves, and so on.

At least after the formation of the semi-continuous layer of the composition, water will exit the layer by evaporation (a portion of the water may leave during the droplet-consolidation process as well), Upon sufficient drying of water from the composition, the parcels of hydrophobic material will coalesce (that is, the emulsion will “break”) to form an at least semi-continuous layer of the hydrophobic material on the treated surface. The layer of hydrophobic material will provide a visually -attractive layer (e.g., the layer may be glossy and shiny in appearance) on the treated surface.

Emulsion

A water-based composition as disclosed herein is an aqueous emulsion, defined herein as meaning that it is an aqueous oil-in-water emulsion. An aqueous emulsion as disclosed herein will comprise (at least 50 wt. %) water that provides a continuous phase of the aqueous emulsion, and will comprise a hydrophobic material in the form of parcels that provide a discontinuous phase of the aqueous emulsion. By definition, the discontinuous parcels of the aqueous emulsion are in the form of surfactant-stabilized oil-in-water micelles, comprising a core of the hydrophobic material with surfactant molecules clustered around the core, with hydrophobic segments of the surfactant molecules oriented inward toward the hydrophobic core and with hydrophilic segments of the surfactant molecules oriented outward toward the surrounding continuous water phase. The hydrophobic parcels and materials thereof will be referred to herein as a second, hydrophobic phase; the continuous aqueous phase will be referred to as a first, aqueous phase.

Again by definition, the herein-disclosed aqueous oil-in-water emulsions are macroemulsions. By this is meant that the micelles exhibit a size (diameter or equivalent diameter) of greater than 100 nanometers with the micelles being kinetically stabilized (against aggregation and large-scale phase separation; i.e., against “breaking” of the emulsion) by the action of the surfactant molecules. Such macroemulsions are distinguished from microemulsions, which characteristically comprise parcels of smaller size (e.g., 100 nanometers or considerably less) and that are thermodynamically stable rather than kinetically stable.

By definition, the herein-disclosed aqueous oil-in-water macroemulsions are also distinguished from rheologically-stabilized dispersions of hydrophobic material in water. The latter are arrangements in which special (water-soluble or water-swellable) polymers are used to increase the viscosity of the aqueous phase of an aqueous/hydrophobic phase-separated system, so that hydrophobic parcels are kinetically stabilized against agglomeration, by the high viscosity of the aqueous phase rather than by the above-described stabilizing of hydrophobic parcels by surfactant molecules. Rheologically- stabilized dispersions thus differ in a fundamental way from the herein-disclosed oil-in-water macroemulsions, in which hydrophobic parcels are present in micelles that are stabilized by surfactant molecules. Arrangements that involve Theologically -stabilized dispersions of hydrophobic material in water, and that are attested to differ fundamentally from, and to be distinguished from, the herein- disclosed oil-in-water macroemulsions, are described e.g. in U.S. Patent 8168578. By definition, the herein-disclosed aqueous oil-in-water macroemulsions are also distinguished from arrangements in which hydrophobic phases and aqueous phases are purposefully formulated to be non-stabilized; such non-stabilized arrangements are described e.g. in International Publication No. WO 2021/148930.

Hydrophobic phase

The above-described hydrophobic parcels may comprise any suitable amount of any suitable hydrophobic material or materials. In various embodiments, such a material or materials may be present in the composition in a (total) amount of at least 2.0, 3.0, 4.0, 5.0, 8.0, 10, 12, or 14 wt. %. In further embodiments, any such material or materials may be included in the composition at less than 25, 16, 11, 9.0, or 7.0 wt. %. All references herein to percent are to weight percent, relative to the entire waterbased composition, unless otherwise noted. Also, as discussed in detail below, these weight percent ranges of hydrophobic material(s) include both any liquid material (e.g. silicone fluid), and any solid or semi-solid material (e.g. silicone resin) that may be e.g. dissolved or otherwise disposed within the liquid material.

As mentioned briefly above, the parcels of hydrophobic material will coalesce to form a hydrophobic layer on the surface that is to be treated. In some embodiments, such a layer may be formed and/or maintained in place on the surface, purely by “physical” means, e.g. by processes that do not involve the formation of covalent chemical bonds involving constituents of the hydrophobic material. Such processes may take the form of e.g. Van der Waals interactions, aromatic pi-stacking, induced- dipole forces, and so on. In some embodiments, the process may involve at least some formation of chemical bonds between at least some constituents of the hydrophobic phase (for example, the hydrophobic phase may comprise silicone fluids and/or resins with active groups that may react with each other). In some embodiments the hydrophobic phase may not comprise any constituents that form chemical bonds to the surface that is being treated. In some embodiments, the hydrophobic phase may comprise one or more components (e.g. polydimethylsiloxanes that are functionalized to comprise reactive groups such as e.g. hydroxyl and/or amino groups, as discussed in detail later herein) that are configured to form bonds with moieties on the surface to be treated. Variations and/or combinations are possible; for example in some embodiments the hydrophobic phase may include materials with reactive groups that react with other reactive groups of the hydrophobic phase, and/or may include materials with reactive groups that react with moieties on the surface to be treated. In some embodiments, interactions between constituents of the hydrophobic phase, and/or interactions of such constituents with the surface to be treated, may occur e.g. by way of hydrogen bonding. It will be appreciated that with many hydrophobic materials and surfaces to be treated, the formation of the layer of hydrophobic material on the surface, and the maintenance of the layer thereon, may occur by a combination of multiple such mechanisms. For example, some arrangements may involve the formation of at least some covalent bonds, and may also involve the formation of at least some hydrogen bonds.

In general, a hydrophobic phase of an aqueous macroemulsion as disclosed herein may comprise any single material or combination, blend, mixture, solution, etc. of materials, that is capable of being incorporated into an aqueous macroemulsion and deposited onto a surface to form a hydrophobic layer in the general manner described herein, and to maintain the hydrophobic layer on the surface for an appropriate period of time (e.g. for several days or weeks).

In some embodiments the hydrophobic phase may comprise one or more silicone materials. The term silicone material is used in general to refer to a large class of materials that are based on chains and/or networks of Si-0 units. In some embodiments, such a silicone material may include, or be, a silicone liquid that is e.g. polydimethylsiloxane (PDMS) or a related material. Such liquids are often comprised of generally linear-chain polymers; the physical properties (e.g. melting point, viscosity, and so on) of such materials may depend on the molecular weight of the polymers. Many such liquids are available, of various properties (e.g. viscosity and so on).

In some embodiments, such a silicone material may include, or be, a silicone resin. The terminology of a silicone “resin” is used herein to specifically refer to three-dimensional networks comprising Si-0 units. In many embodiments such materials may be highly crosslinked to form a cagelike network of SiO4 units (often referred to as Q units) and to additionally bear, e.g. at outer surfaces of the network, at least some silicon atoms bearing methyl groups. Such methyl-bearing silicon atoms are often referred to as M units in the case of three methyl groups, and as D or T units in the case of two or one methyl groups. Such silicone resins are commonly referred to in the trade as MQ resins (or, as MTQ resins, and so on, depending on the particular structure). Such resins, depending e.g. on their molecular weight, may be e.g. soluble or insoluble in various liquids and at various temperatures. Various such resins may be referred to e.g. as trimethylated silica, trimethyl siloxysilicate, silicic acid (trimethylsilyl ester), silicic acid (diethyoxyoctylsilyl trimethylsilyl ester) and so on. Any such silicone resin, of any suitable structure and composition, may be used. It will be appreciated that any such silicone resin, in order to be able to form a hydrophobic layer, should comprise a sufficient number of nonpolar groups (e.g. methyl groups, whether in the form of M, D or T units), e.g. at the outer surfaces of the silicone network, to impart the desired hydrophobicity.

In some embodiments, it may be advantageous to include one or more silicone resins in the second, hydrophobic phase. However, some such resins may not be liquid at room temperature. Accordingly, in some embodiments one or more silicone resins may be mixed with one or more silicone liquids (e.g. linear polydimethylsiloxane (PDMS) liquids). In some embodiments (depending e.g. on the molecular weight of the silicone resin, its concentration in the silicone liquid, and so on), the silicone resin may become dissolved in the silicone liquid. However, this is not strictly necessary. That is, in some embodiments a silicone resin may merely need to be adequately wetted and suspended in a silicone liquid to an extent that allows the mixture of the two to be used in the hydrophobic phase. Thus, in some embodiments, a second, hydrophobic phase may comprise a mixture of one or more silicone resins and one or more silicone (e.g. PDMS) liquids.

A large variety of silicone liquids, silicone resins, and blends of silicone liquids and silicone resins are available for use in the second, hydrophobic phase. In some embodiments, such materials may be e.g. silicone fluids (e.g. of 350 centistokes (cSt), of 1000 cSt, or blends thereof). Other materials which may be suitable for use include for example: products available from Momentive under the trade designations YR 3370 M/T and SS 4230; products available from Dow under the trade designations DOWSIL 2405, DOWSIL MQ-1640, DOWSIL MQ-1600, DOWSIL 2-1912, DOWSIL RSN-0220, DOWSIL RSN-9118, AND DOWSIL 2-2078; products available from Shin-Etsu under the trade designations KR-480, KR-251, and KR-282; products available from Siltech under the trade designations SILMER Q25 AND SILMER Q30; and, products available from Wacker under the trade designations WACKER TPR, SILRES REN 80, BELSIL Bl 10, AND SILRES 604. (Such products may be referred to by various vendors as, for example, silicone oils, silicone fluids, modified silicone resins, silicone waxes, silicone liquids, silicone mixtures and blends, and so on.) Various silicone materials (e.g. fluids, resins, and blends thereof) are described in detail in U.S. Patents 7541323 and 8168578 and in U.S. Patent Application Publication 2005/0250668, all of which are incorporated by reference in their entirety herein. In various embodiments, any such silicone resin and silicone liquid may be combined to form a mixture upon which a second, hydrophobic phase of an aqueous emulsion is based. If desired, any such material that comprises a silicone oil and/or a silicone resin, may include additional ingredients, e.g. any of the hydrophobic organic waxes and oils described later. While neat silicone materials (silicone liquids or mixtures of silicone liquids and silicone resins, at essentially 100 % actives) may be used, in some embodiments a silicone-based hydrophobic material may be obtained e.g. as a premade emulsion, as discussed in detail later herein.

In some embodiments, at least one of a silicone liquid and/or a silicone resin that is present in a second, hydrophobic phase of an aqueous macroemulsion may comprise at least some number of reactive groups. Such silicones are sometimes referred to as functional silicones. Such reactive groups may e.g. facilitate the formation of a layer, the adherence (e.g. bonding) of the layer to a surface, and/or may enhance the ability of the layer to be maintained on the surface e.g. for days or weeks. Such a reactive group or groups e.g. on one polydimethylsiloxane molecule may react with a similar group or groups on another polydimethylsiloxane molecule; and/or, such a reactive group or groups may react with a moiety on the surface that the layer is disposed on. For example, in some embodiments polydimethylsiloxane (PDMS) molecules (e.g. of a silicone fluid) may comprise hydroxyl (-OH) groups; such groups may be able to react with other such groups (e.g. to condense) to form covalent bonds, and/or to form hydrogen bonds. Likewise, such -OH groups may be able to form covalent bonds or hydrogen bonds with moieties on the surface that the layer is disposed on. Such -OH groups may be present e.g. at least at terminal ends of a linear PDMS molecule (such silicones may be referred to as a, co-dihydroxy poly dimethylsiloxane); in some embodiments, multiple such groups may be present e.g. on pendant groups along the PDMS chain. In some embodiments, poly dimethylsiloxane molecules may comprise amine groups (e.g., -NH ₂ groups, but including derivatives of such groups), which again may be at terminal ends and/or on pendant groups along a PDMS chain. In other examples, a silicone fluid or a silicone resin (e.g. an MQ resin) may comprise a number of silanol groups that allow the formation of chemical bonds by condensation.

Some such groups have been found to enhance the ability of a hydrophobic layer to bond to the surface of rubber, particularly of rubber tires. It is hypothesized that this may be due to the ability of such groups to interact with moieties that are present on the surface of the rubber tire. Such moieties may include e.g. oxidized double bonds in the rubber, vulcanization residues (containing e.g. sulfur atoms) in the rubber; such moieties may also be e.g. present on additives and reinforcing fillers (e.g. fumed silica, carbon black, and so on) that are often present in rubber tires.

Although hydroxyl-functional and amino-functional silicones were mentioned above, any suitable functionality may be used, for example acrylo groups, epoxy groups, mercapto groups, silane groups, and so on. Various reactive silicone materials which may be suitable for use include for example: products available from Momentive under the trade designation SEM-253; products available from Dow under the trade designations XIAMETER MEM-1785 EMULSION, XIAMETER OFX- 0531, XIAMETER OFX-0536, DOWSIL 2-8566, XIAMETER OFX-8468, and XIAMETER OFX- 840; and products available from Siltech under the trade designations SILAMINE MUE, SILAMINE C50, and SILAMINE AS. Various reactive silicones and their use are discussed in detail in U.S. Patents 6475934 and 8829092, which are incorporated by reference herein in their entirety for this purpose.

Any silicone material with reactive groups may be e.g. mixed or blended at an appropriate level with other (non-reactive) silicone fluids and/or resins. In some embodiments, the hydrophobic, silicone- based material of a second, hydrophobic phase of an aqueous emulsion may comprise reactive silicone(s) in an amount such that the reactive silicone(s) makes up at least 1, 2, 4, 8, 16, 32, or 64 wt. % of the total hydrophobic, silicone-based material. In further embodiments, the reactive silicone(s) may make up at most 50, 40, 25, 12, or 5 wt. % of the total hydrophobic, silicone-based material. In some particular embodiments, a hydroxy-functional silicone may make up at least 1, 2, 4, 8, 16, 32, or 64 wt. %, or at most 50, 40, 25, 12, or 5 wt. %, of the total hydrophobic, silicone-based material.

In various embodiments, the hydrophobic phase of an aqueous macroemulsion as disclosed herein may include less than 10, 5, 2, 1.0, 0.5, 0.2, 0.1, or 0.05 wt. % of non-silicone hydrophobic material(s). Silicone-polyether surfactant

A water-based composition in the form of an aqueous macroemulsion as disclosed herein will comprise at least 0.1 wt. % of silicone-polyether surfactant. The present investigations have revealed that such a surfactant can act as a wetting agent that significantly enhances the ability of the aqueous emulsion to wet out and spread on a surface, particularly a relatively hydrophobic surface such as that of a rubber tire. The presence of a silicone-polyether surfactant thus enhances the tendency for individual droplets of the water-based composition, upon being deposited on a hydrophobic surface e.g. by spraying, to spread and merge with each other to form an at least semi-continuous layer, from which the water can evaporate to leave behind a coalesced hydrophobic layer. In particular, the presence of a silicone-polyether surfactant can provide that the composition is self-leveling when applied to a hydrophobic surface; that is, the individual droplets may consolidate as described above, to the point that the thus-formed at least semi-continuous layer exhibits a fairly uniform thickness (except where perturbed by surface texture and so on, as discussed earlier herein). This can be the case even when the composition is applied to a vertical surface; that is, the thus-formed layer may exhibit similar thickness in upper areas of the surface as in lower areas of the surface, rather than pooling to form a thicker layer toward the bottom areas of the surface.

The present investigations have also revealed that a silicone-polyether surfactant can act as an effective emulsifier for a hydrophobic phase (in particular, a silicone-based hydrophobic phase) to be emulsified into oil-in-water micelles within a continuous aqueous phase. Silicone-polyether surfactants have been found to serve in this capacity so that a two-phase mixture of a silicone-based hydrophobic phase within a continuous aqueous phase does not necessarily need to be stabilized e.g. by rheological methods of the general type referred to earlier herein.

In other words, silicone-polyether surfactants can perform “double-duty” in serving as both a wetting agent, and as an emulsifier. In some embodiments the silicone-polyether surfactant may be substantially the only surfactant that is present in the aqueous emulsion (allowing the possibility that one or more ancillary surfactants may be present in minor amounts as discussed later herein). In various embodiments, any other surfactant(s) (besides the silicone-polyether surfactant) may be present in the aqueous emulsion at less than 2.0, 1.5, 1.0, 0.5, 0.2, or 0.1, or 0.05 wt. %. In some embodiments the silicone-polyether surfactant may be accompanied in the aqueous emulsion by one or more additional surfactants that can act in concert with the silicone-polyether surfactant, also as discussed later herein.

The present investigations have also revealed that silicone-polyether surfactants do not necessarily need to be used at high concentrations in order to achieve the advantageous results disclosed herein. (In fact, the present investigations have indicated that too much of the silicone-polyether surfactant may negatively impact the stability of the oil-in-water emulsion.) Thus in various embodiments, the silicone-polyether surfactant(s) may be present in the aqueous emulsion at less than 5.0, 4.0, 3.0, 2.0, 1.0, 0.8, or 0.6 wt. %. In further embodiments, the silicone-polyether surfactant(s) may be present at least at 0.15, 0.2, 0.3, or 0.4 wt. %. By a silicone-polyether surfactant is meant a surfactant comprising at least one hydrophobic segment comprising siloxane groups (e.g. dimethylsiloxane monomer units and derivatives thereof), and at least one hydrophilic segment comprising poly ether groups (e.g., polyethylene oxide) monomer units, and/or poly(propylene oxide) monomer units, and derivatives thereof). Poly(ethylene oxide) segments are sometimes referred to as polyethylene glycol segments, and poly(propylene oxide) segments are sometimes referred to as polypropylene glycol segments; silicone-polyethers in general are sometimes referred to as silicone polyols. The terminology of silicone-polyether surfactant, “a” silicone-polyether surfactant, and like terminology, is interpreted as “at least one”, and encompasses the use of a single type and composition of silicone-polyether surfactant, as well as mixtures of two or more types and compositions (for example, blends of two different grades of silicone-polyether surfactants that may differ e.g. in the length and/or composition of the hydrophobic segments and the hydrophilic segments). A silicone-polyether surfactant may comprise any suitable structure and arrangement. For example, such a surfactant may comprise a main polymer chain that includes hydrophilic polyether segments and hydrophobic polydimethylsiloxane segments, e.g. the main chain may be a block copolymer of hydrophilic and hydrophobic segments. In some instances, such a block copolymer may comprise hydrophilic polyether segments that bracket a central hydrophobic polydimethylsiloxane (PDMS) segment. In some embodiments, a silicone-polyether surfactant may comprise a branched, graft, or rake arrangement, e.g. in which hydrophilic polyether segments are present as pendant groups from a main polymer chain of e.g. PDMS. Some silicone-polyether surfactants may comprise a trisiloxane structure comprising a hydrophobic PDMS segment comprised of three siloxane monomer units, with at least one (e.g. the center) siloxane monomer unit comprising a pendant group bearing a hydrophilic polyether segment. It is noted in passing that while polydimethylsiloxane (PDMS) is used for brevity of description herein, a variety of derivatives and modified versions PDMS polymers are available; all references to PDMS will be understood to mean PDMS itself, as well as derivatives and modified versions thereof.

A silicone-polyether surfactant may have any suitable length and composition of the hydrophobic segment(s) and the hydrophilic segment(s). It has been found that, for the purpose of making oil-in-water macroemulsions as disclosed herein, it can be advantageous to use a silicone- polyether surfactant that is at least somewhat water soluble, in order to promote the formation of an oil- in-water macroemulsion. The hydrophobic/hydrophilic character of a surfactant can be at least generally characterized by the parameter commonly known as the hydrophilic -lipophilic balance (HLB) of the surfactant. In general, surfactants with an HLB of less than approximately 10 may tend to be waterinsoluble while surfactants with an HLB of 10 or greater may tend to be water-soluble. While surfactants with an HLB of 8 or greater are sometimes considered to be suitable for use as oil-in-water emulsifiers, in the present work, it is considered that silicone-polyether surfactants with an HLB of 10 or greater may be particularly advantageous. Thus in some embodiments, a silicone-polyether surfactant may be used that exhibits an HLB of at least 10, 11, or 12. Of course, a silicone-polyether surfactant may be used that has a somewhat lower HLB (e.g. in the 8-10 range), for example if the silicone-polyether surfactant is used in combination with another surfactant that comprises a higher HLB, so that an overall effect of promoting an oil-in-water emulsion is achieved.

As noted above, in some embodiments a silicone-polyether surfactant may comprise polyether groups that are polyethylene oxide) monomer units. In some embodiments the polyether groups of a silicone-polyether surfactant may include at least some polypropylene oxide) monomer units. In some embodiments, a polyether group may comprise a copolymer of polypropylene oxide) monomer units and poly(ethylene oxide) monomer units. In various embodiments, a terminal end of a polyether group may be e.g. a hydroxyl group; or the terminal end may be e.g. endcapped with any moiety as desired, as long as the desired behavior of the surfactant is retained.

Silicone-polyether surfactants that may be suitable for the present uses include, but are not limited to: the products available from Evonik Industries AG, Hanau, Germany, under the trade designations TEGOPREN 5840 and TEGOPREN 6922; the products available from Dow Inc., Midland, MI, under the trade designations DOWSIL Q2-5212, DOWSIL Q2-5211, and XIAMETER OFX 5211; and the products available from Siltech Corporation, Toronto, CA, under the trade designations SILSURF A008, SILSURF A004, AND SILSURF C208. Other silicone-polyether surfactants that may be suitable include various products available from Momentive, Inc. under the trade designation SIL WET (e.g. SIL WET L-77 and SIL WET L-7200). It is noted in passing that some silicone-polyether surfactants may comprise a small amount of inactive material (e.g. water). For example, TEGOPREN 5840 is listed as having 75 % active ingredients. All of the weight percentages of silicone-polyether surfactants (as well as any other surfactants) disclosed herein will be understood to be based on the actual active ingredients in the surfactant as supplied.

As mentioned above, in some embodiments a water-based aqueous macroemulsion as disclosed herein may comprise one or more additional surfactants in addition to the above-described silicone- polyether surfactant. By an additional surfactant is specifically meant a surfactant (or, a package of surfactants) that, in total, is present in the aqueous macroemulsion at a weight percent of at least 0.2 wt. %. Such an additional surfactant may be present e.g. in a case (discussed later herein) in which a premade silicone emulsion (comprising additional surfactant used in formulating the premade silicone emulsion) is incorporated into the herein-disclosed aqueous emulsion. In various embodiments, any such additional surfactant may be present at no more than 4.0, 2.0, 1.5, 1.0, or 0.5 wt. %.

In some embodiments one or more ancillary surfactants may be present in addition to in the silicone-polyether surfactant (and any additional surfactant, if present). The terminology of an ancillary surfactant denotes any surfactant that may be present in the aqueous emulsion in a very small amount due to its presence in some component (e.g. a water-soluble thickener, fragrance, biocide, colorant, or any such ingredient) that is present at a relatively low level in the aqueous emulsion. Any such ancillary surfactant will be present at less than 0.2 wt. %; in many cases, any such ancillary surfactant, if present, may be present in an extremely small amount, e.g. less than 0.1 or 0.05 wt. %. Given the possibility of, e.g., an ancillary surfactant being present, any disclosure in the present application with respect to a proviso (negative limitation), and/or with respect to a composition that “consists essentially of’ or similar language, will be understood to admit the possible presence of low levels (e.g., less than 2.0, 1.0, 0.5, 0.2, 0.1, or 0.05 wt. %, on an individual basis) of any of various minor components (e.g. biocide, fragrance, pH adjuster, and so on), as well as the possible presence of ancillary surfactant derived from such minor components. Such language will however preclude the presence of any additional major components (e.g., a solvent other than water, a hydrophobic material other than the hydrophobic, silicone-based material, and/or a major amount (e.g., 1.0 wt. % or more)) of a surfactant other than the silicone-polyether surfactant.

Any additional or ancillary surfactant that is present in the aqueous emulsion may comprise any suitable composition, structure and arrangement. Such a surfactant may be chosen from any suitable category, e.g. nonionic or ionic (e.g. cationic, anionic, amphoteric, or zwitterionic), or combination thereof.

Preparation of composition

An aqueous emulsion as disclosed herein may be generated in any suitable manner, as long as an oil-in-water macroemulsion is formed rather than e.g. a microemulsion, a rheologically-stabilized dispersion, or a water-in-oil emulsion. (Ordinary artisans will appreciate that the presence of an oil-in- water macroemulsion may be ascertained in any of various ways, e.g. by zeta potential measurements.) In general, such a macroemulsion may be generated by combining appropriate amounts of hydrophobic silicone-based material, water, and silicone-polyether surfactant.

In some embodiments, it has been found convenient to prepare such an emulsion by preparing an emulsion concentrate and then adding sufficient water to bring the composition to its final configuration. Thus for example to make a macroemulsion comprising 20 wt. % hydrophobic silicone- based material and 0.50 % silicone-polyether surfactant, the balance being primarily water (ignoring for now the presence of ingredients such as thickeners, biocides, fragrances, colorants and so on), the hydrophobic silicone-based material and the silicone-polyether surfactant may be combined with a small amount of water. (For example, a ratio of hydrophobic silicone-based material to water of e.g. 5:1, or even 8:1 or higher, may be used.) The combination can be subjected to mixing e.g. with a laboratory propeller-stirrer mixer equipped with e.g. a marine-style blade, a turbine-style blade, or dispersion blade, operating at e.g. 1000-2000 RPM or more. Other mixers that may be used include e.g. a rotator-stator mixer or homogenizer, a pressure-plate (e.g. Gaulin-type) homogenizer, and the like.

The presence of a suitable silicone-polyether surfactant will provide that such mixing will cause an oil-in-water macroemulsion to be formed even at a high ratio of hydrophobic silicone-based material to water (in general accordance with the “rule of thumb” known in the colloidal chemistry arts as the Bancroft rule). This mixture, which may exhibit a very high viscosity (e.g. upwards of 20000 or even 30000 cSt), will be referred to as an emulsion concentrate. It is believed that in such a concentrate, the parcels of hydrophobic silicone material (i.e., the “oil” parcels) may already be generally in their final form (e.g., at their final size) as in the final product. The proper amount of make-up water can then be added to the emulsion concentrate and then blended until uniform. The thus-formed aqueous macroemulsion can then be further processed as desired (e.g. ingredients such as thickeners, fragrances, and so on, may be added).

In some embodiments, a hydrophobic, silicone-based material may be obtained in the form of a premade silicone emulsion. A premade silicone emulsion is defined as an macroemulsion comprising a second, hydrophobic phase that is silicone-based and that is indefinitely stable and that is incorporated into the herein-disclosed aqueous macroemulsion in the form of an already -existing emulsion (e.g., as a long-term shelf-stable silicone emulsion as obtained from a vendor). This can be contrasted with, e.g., starting with a neat silicone fluid and emulsifying it in the manner described above. One representative example of a premade silicone emulsion that is suitable for use for in some compositions disclosed herein is the product available from Dow Inc. under the trade designation XIAMETER MEM-1785, which is described by the supplier as being an emulsion that comprises 60 % (solids) silicone content. This particular product (described by the supplier as comprising dimethiconol (-OH terminated PDMS fluid) silicones) is also believed to be an example of a product that comprises -OH groups at least at terminal ends of at least some of the PDMS polymer chains. (An exemplary water-based composition that includes such a premade silicone emulsion is presented in Working Example 3.)

Such a premade silicone emulsion will be expected to include “additional” surfactant (used in formulating the premade silicone emulsion) in the general manner discussed earlier herein. In some embodiments, a surfactant that is incorporated into the aqueous emulsion by virtue of being present in a premade silicone emulsion, may be a silicone-polyether surfactant. In such a case, this surfactant will be counted toward the total amount of silicone-polyether surfactant in the final aqueous dispersion. By way of a specific example, an aqueous emulsion that comprises 0.3 wt. % silicone-polyether surfactant that is added when making the aqueous emulsion, and that includes a premade silicone emulsion that adds 0.2 wt. % silicone-polyether surfactant to the aqueous emulsion, will comprise a total of 0.5 wt. % silicone-polyether surfactant.

It is noted however that any such surfactant that is present in a premade silicone emulsion does not necessarily have to be a silicone-polyether surfactant. For example, the above-mentioned XIAMETER MEM-1785 Emulsion is listed by the supplier as comprising an anionic surfactant in the form of TEA-dodecylbenzenesulfonate. For an aqueous emulsion as disclosed herein that includes a premade silicone emulsion with an additional surfactant, it is considered that the silicone-polyether surfactant (even if added after the premade emulsion is diluted with makeup water) will act in concert with the additional surfactant to maintain the aqueous macroemulsion in its emulsified form. In some embodiments, an aqueous emulsion as disclosed herein may include a premade silicone emulsion and may include additional silicone-based material (e.g. one or more neat silicone fluids) that becomes emulsified as it is mixed with the premade silicone emulsion (and, e.g. additional water, and so on) under conditions appropriate to cause the desired emulsification. Viscosity and water-soluble thickener

An aqueous emulsion, once formulated in the general manner disclosed above, can be further processed, further ingredients added, and so on. In some embodiments, a water soluble thickener can be incorporated into (or, in more general terms, can be present in) the aqueous emulsion. This can, for example, set the viscosity of the aqueous emulsion, as packaged in a container as a sprayable composition, in a range that is low enough to allow the composition to be sprayed and to allow the droplets that are spray -deposited onto a surface to spread and merge. However, the viscosity should be high enough to ensure that the spray -deposited droplets (before or after merging to form a layer) do not unacceptably run off of the surface on which they are deposited so that the resulting layer of hydrophobic material is too thin to provide e.g. a gloss-enhancing function. This last factor is particularly important since the vast majority of e.g. tire-glossing treatments are applied, e.g. by spraying, with the tire in a vertically upright condition.

In general, a viscosity range of from approximately 200 to 2000 centiStokes (cSt) has been found to be suitable. Thus in some embodiments, an aqueous emulsion as disclosed herein will exhibit a viscosity of at least 200, 300, or 400 cSt. In further embodiments, an aqueous emulsion will exhibit a viscosity of at most 2000, 1500, 1200, 800, 700, or 600 cSt. All such measurements will be at room temperature (e.g. 21 C), and are performed at low-shear conditions (e.g. by using a Brookfield viscometer equipped with spindle RV-1, operating at 10 RPM). It will be appreciated that such measurements characterize the viscosity under low shear (to produce data sometimes referred to as static or quasi-static viscosity values). In observational, non-quantitative assessments, at least some of the aqueous emulsions disclosed herein appear to exhibit behavior that is somewhat shear-thinning (e.g. thixotropic). This is advantageous from the standpoint of allowing them to be dispensed through a spray nozzle while ensuring that, once deposited onto a surface, the droplets are able to flow enough to spread and merge, but do not tend to run off a vertical surface to an unacceptable extent.

It is noted that some formulations have been observed to exhibit a tendency for the viscosity to increase somewhat over time (e.g. over a few days). The above numbers refer to the final viscosity of the formulation after any such period of stabilization (in other words, they refer to the viscosity of the formulation in its final, as-used condition). Thus for example, a formulation that exhibits a viscosity of e.g. 150 cSt as initially made but that increases to a final value of e.g. 400 cSt over a few days time, will be considered to fall within the above-recited range of 200-2000 cSt.

It is emphasized that the use of a water-soluble thickener for the purposes disclosed herein is distinguished from the incorporation of a water-soluble thickener into an oil-in-water dispersion in order to Theologically stabilize the oil droplets of the dispersion via the effect of extended networks or rheological structures that are formed by the water-soluble thickener in the water phase of the dispersion. That is, while a viscosity increase that is caused by a water-soluble thickener in a herein- disclosed aqueous macroemulsion may, in some cases, provide a further enhancement of the stability of the macroemulsion, the composition is nevertheless a macroemulsion whose fundamental characteristic is stabilization of the oil-in-water micelles of the macroemulsion by the silicone-poly ether surfactant (whether alone or in combination with an additional surfactant).

Any suitable water soluble thickener may be used. (As usual, terminology such as water soluble thickener, a water soluble thickener, and so on, encompass the use of one or more types and compositions of such items, e.g. in combination). In some embodiments, such a water soluble thickener may comprise an anionic polymer. In some embodiments, an anionic polymer (or, a potentially -anionic polymer) may be structured and arranged so that its ionization state is dependent on a physicochemical condition, e.g. pH. For example, the product available from DOW, Inc. (Midland, MI) under the trade designation ACUSOL 820 is an acrylic polymer (believed to be based on acrylic acid and/or derivatives thereof) that, as supplied, is at a relatively low pH (2.5). Under this condition the polymer is present as a low-viscosity premade emulsion (as formulated by the supplier) at approximately 30 % actives/solids in water. (This thickener may thus be expected to contribute a small amount of an ancillary surfactant to the aqueous macroemulsion in the manner described earlier herein.)

Increasing the pH to a suitably alkaline value (e.g. 8-9) will cause the polymer chains to become significantly deprotonated, with the result that their water-solubility increases significantly and the former emulsion becomes a relatively clear solution with a much higher viscosity. It will be appreciated that many polymers of this general type exist, and may be employed for the purposes herein as long as the conditions can be established that place the polymer into a state (e.g. a solubilized state) in which it can thicken an aqueous phase. It will thus be appreciated that a water-soluble thickener of this general type can be added to a mixture in a “latent” state (e.g. with the pH held at a low value) with conditions being altered at an appropriate time e.g. by addition of a suitable base, so that the thickener is “activated” to impart the final, desired viscosity.

Variations of the above-discussed arrangements are possible. In some embodiments, a water- soluble thickener (in an as-received, e.g. undiluted form) may be added to an aqueous phase of an already -formed aqueous macroemulsion. In particular embodiments a water-soluble thickener may be added at this stage in a latent state after which the thickener is “activated” e.g. by increasing the pH. An exemplary approach of this general type is presented in Working Example 1. In some embodiments, a water-soluble thickener may be diluted into water to obtain a mixture that is then combined with a premade silicone emulsion to form the final aqueous macroemulsion, after which the thickener is then activated. In a further variation, a water-soluble thickener may be diluted into water, activated, and then combined with a premade silicone emulsion to form the final aqueous macroemulsion. An exemplary approach of this general type is presented in Working Example 2.

In general, various anionic polymers that, under suitable conditions, can exert a thickening effect, include e.g. those comprising units of acrylic acid, methacrylic acids, salts of acrylic acid and/or methacrylic acids, and so on. Any such anionic polymer may be a homopolymer, copolymer, and so on. Suitable specific polymers include e.g. polyacrylic acid, sodium polyacrylate, and derivatives, copolymers, and so on, of any such materials. Other anionic polymers that may be used include e.g. anionic alginates, derivatives thereof, and similar material. Other potentially useful anionic polymers, monomers and/or monomer units are disclosed in U.S. Patent 8512863 and in U.S. Patent Application Publication US 2006/0276371, both of which are incorporated by reference herein for the specific purpose of including the anionic materials disclosed therein, into the present document. Any anionic polymer as used herein may comprise monomer units derived from anionic monomers and/or from monomers that, after polymerization, may be rendered anionic. In general, an anionic polymer may comprise anionic moieties in the polymer backbone and/or in side groups or substituents, and may be anionic as made, or may be modified to become anionic while already in a polymeric state. Particular materials that may be useful are available under trade designations such as CARBOPOL, NOVEMER, and ALCOGUM. It is emphasized that any such polymer need not necessarily be e.g. pH -activatable in the general manner of the ACUSOL 820.

The effects disclosed herein are not considered to be necessarily dependent on any particular type or category of thickener. Thus in some embodiments a water-soluble thickener may rely on a cationic polymer. In some embodiments, a cationic polymer for use in the present arrangements may contain cationic nitrogen-containing moieties, e.g. quaternary ammonium or cationic protonated amino moieties. Thus in some embodiments, a cationic polymer that is used as a thickener may be, or include, a polyquaternium material, i.e. a polymer that includes quaternary ammonium moieties. Numerous polyquaternium materials are available (e.g. polyquaternium- 1 through polyquatemium-47). One particularly useful cationic polymer of this type is polyquatemium-6, also known as polydiallyldimethylammonium chloride or polyDADMAC. Other cationic polymers that may be used include e.g. polyethylenimine, and cationically-modified guar gum. In some embodiments, a water- soluble thickener as disclosed herein may be, or include a non-ionic polymer.

Any such thickening polymer may be synthetic or naturally -derived; a non-limiting list of such polymers includes hydroxyethyl cellulose, polyacrylamide, polyvinylpryolidone, polyvinyl alcohol, and so on. Thus in some embodiments, a water-soluble thickener as disclosed herein may be a naturally- derived gum or a cellulosic material, such as e.g. alginate gum, xanthan gum, guar gum, or a modified cellulose such as hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and like materials. In some embodiments, minerals such as bentonite clay, laponites, and the like, may be used.

Any such water-soluble thickener may be used at a concentration, and under conditions (e.g. pH, pKa, ionization conditions, charge state, etc.) that are appropriate to achieve the desired overall viscosity of the aqueous macroemulsion (e.g. from 200 to 800 cSt) in view of the thickening power of the particular thickener under the conditions used. With some thickeners, a large quantity of the thickener may not necessarily be required. (For example, as shown in the Working Examples herein, in some embodiments ACUSOL 820 need only be present in the aqueous formulation at around e.g. 0.18 wt. %.) Thus in various embodiments, a water-soluble thickener may be present in the aqueous macroemulsion at at least 0.05, 0.10, 0.15, 0.20, 0.30, 0.40, or 0.50 wt. %. Any such number will be based on the actual active thickener. For example, ACUSOL 820 is supplied as a 30 % solids emulsion; the addition of 0.6 wt. % of this emulsion to an aqueous macroemulsion as disclosed herein, will result in the ACUSOL 820 water-soluble thickener being present at 0.18 wt. %. In further embodiments, a water-soluble thickener may be present in the aqueous macroemulsion at no more than 2.0, 1.5, 1.0, 0.80, 0.70, 0.50, or 0.30 wt. %.

In some embodiments, an aqueous emulsion as disclosed herein will include less than 1.0, 0.5, 0.2, 0.1, 0.5, 0.02, or 0.01 wt. %, in total of any thickening polymer that is crosslinked. In some embodiments, an aqueous emulsion as disclosed herein may comprise any suitable amount of any thickening polymer that is water-soluble (meaning that the thickening polymer is soluble in water to at least 100 mg/L at room temperature) while comprising less than 1.0, 0.50, 0.20, 0.1, 0.05, 0.02, or 0.01, wt. % (in total) of any thickener or thickeners that are water-swellable but are not water-soluble.

As noted herein, in some embodiments (e.g. if an anionic polymer is a polyacrylic acid or a polyacrylic acid-derived polymer) it may be necessary to increase the pH of the mixture to ensure that the anionic groups (e.g. COOH / COO" / H ⁺ moieties) of the polymer are substantially deprotonated, as discussed elsewhere herein. Thus, in some instances a pH-adjusting (e.g. basic) material may be present, in any suitable amount. In some embodiments, such a pH-adjusting material may exhibit buffering capacity e.g. to ensure that any later-added components do not cause the pH to deviate from the desired range. An exemplary, representative pH-adjusting material is triethanolamine, although any suitable material (or combination thereof) may be used. In various embodiments, a pH-adjusting material may be present at least at 0.1, 0.5, 0.8, 1.0, or 1.5 wt. % of the composition. In further embodiments, a pH- adjusting material may be present at most at 5.0, 3.0, 2.0, 1.6, 1.0, or 1.2 wt. % of the composition.

An aqueous macroemulsion as disclosed herein may include any other ingredients for any desired purpose. Such ingredients may include e.g. fragrances, biocides, preservatives, colorants, UV- stabilizers, UV-absorbers and the like, and so on. It is expected that such ingredients, at the level at which they are typically employed, are not likely to have a significant effect on the ability of the surfactant(s) to stabilize the oil-in-water micelles, nor on the ability of the water-soluble thickener to viscosity of the overall aqueous compositions (with the exception of a pH adjuster used in combination with a pH sensitive water-soluble thickener). Such ingredients will thus be termed minor ingredients of the water-based composition; in many embodiments any such minor ingredient will be present at less than 2.0, 1.5, 1.0, 0.8, 0.6, 0.4, or 0.2 wt. % of the aqueous composition. In some embodiments, the water-based composition may comprise some level of organic solvent, e.g. one or more of glycol ethers, alcohols, and so on. However, in some embodiments, any such solvent will be held to a very low level, e.g. less than 2.0, 1.0, 0.8, 0.6, 0.4, 0.2, 0.1, or 0.05 wt. %. As noted, the herein-disclosed composition (aqueous macroemulsion) is a water-based composition, defined earlier herein as meaning that the composition comprises at least 50 wt. % water. In various embodiments, the composition may comprise at least 60, 70, 75, 80, 84, or 88 wt. % water. Packaging of composition

An aqueous water-based composition as described herein may be packaged in any suitable manner for use by an end-user. As noted earlier herein, in some embodiments the composition may be packaged in a trigger-actuated spray container (e.g. bottle) of the general type disclosed in Figs. 1 and 2. The spray head of the container, if adjustable, may be adjusted so that the composition is atomized so as to be emitted as a relatively fine spray of droplets rather than e.g. as a continuous, narrow stream. Typically, the water-based composition, being an aqueous macroemulsion, will exhibit a somewhat milky appearance, although this may not be visible unless the container is transparent. The aqueous emulsion is expected to be sufficiently stable to allow the product to be shipped, warehoused, inventoried, sold, and used by an end user e.g. on an intermittent basis for up to months or one or more years. In some embodiments it is possible to package the composition in a pressurized container along with a propellant (i.e., to provide the composition in an aerosol spray can); however, it is expected that in many embodiments, the composition will be packaged and used in the absence of any propellant.

Dispensing of composition

In many embodiments, the composition can be dispensed onto a surface to be treated, by spraying. It will be appreciated that in many embodiments, a composition as disclosed herein can be applied in a “no-touch” manner, e.g. by spraying the composition onto the desired surface (e.g. of a tire) and simply waiting for a few minutes. That is, the tendency of the applied droplets of aqueous emulsion to spread and coalesce to form a self-leveling layer, can reduce or eliminate any need to e.g. rub, buff, or otherwise use a hand-held applicator to spread the deposited aqueous emulsion on the surface to achieve a uniform coating thickness. Nevertheless, in some embodiments, an end user may spray (or otherwise deposit) the aqueous emulsion onto an applicator (e.g. in the form of a pad or wipe) that is moved about a surface to transfer the aqueous emulsion to the surface. Thus in some embodiments, the composition may be configured for use in such manner. It is however expected that in many embodiments, use of the composition will involve direct spraying of the composition onto a surface to be treated.

If desired, a user may pre-rinse or pre-clean an item (e.g. a rubber tire) to remove dust and debris prior to applying the aqueous composition. Such a pre-rinse is often performed using a garden hose. Slightly better results may result if any gross quantities of excess water left behind by such a prerinse is removed (e.g., by letting the item drip for a few minutes) before application of the aqueous composition. However, the present investigations have indicated that the herein-disclosed compositions are not significantly affected by a nominal amount of residual dampness and/or liquid water present on the surface to be treated. Similarly, the performance of the composition does not seem to be significantly affected by the conditions of drying (e.g., whether or not the composition is applied to a surface in hot weather while the surface is exposed to direct sunlight). It seems that only a relatively short time (e.g. from tens of seconds up to a minute, depending e.g. on the viscosity) are required for the spray -applied droplets to merge and form a layer of the aqueous emulsion, with the water evaporating from the layer to form the final, e.g. gloss-imparting layer. Thus, the performance of the herein-disclosed composition is not found to be particularly sensitive to the drying conditions that are present.

One envisioned use for the herein-disclosed compositions is the treatment of rubber tires to establish, or re-establish, a shiny, glossy appearance of the surface of the tires that is highly desired by some individuals. (Such tire-treatment products are often referred to as tire shines.) Such a tire may be e.g. a tire of a motor vehicle (e.g. an automobile, truck, sport-utility vehicle, recreational vehicle, and so on) or of a non-motorized vehicle or entity (e.g. a trailer or the like). Such tires are often comprised of natural rubber or synthetic rubber (e.g. silicone-butadiene rubber (SBR), butyl rubber, etc.) that is highly crosslinked e.g. by vulcanization, and that may contain various reinforcing fillers such as carbon black, fumed silica, and so on.

One advantageous characteristic is that the herein-disclosed emulsions are typically sufficiently opaque that, even when present as a thin layer on a surface, they exhibit an easily visible milky -white appearance that can be particularly noticeable against the black surface of a rubber tire. This color can assist the user in ascertaining that the desired area of a tire has been adequately covered with the composition. Evaporation of the water and coalescence of the silicone-based parcels of material causes this milky-white appearance to disappear. That is, the layer now exhibits a shiny, glossy appearance, that is transparent so that the black color of the rubber tire can be seen therethrough. The change is quite noticeable and enables an end user to discern that the applied layer has substantially dried. This can provide that, e.g., a user does not drive an automobile with a freshly-applied, insufficiently-dried tire treatment so that some of the tire-treatment material is slung off the tire due to the centrifugal forces arising from the tire rotation.

It is noted in this regard that some tire treatments in the art may be susceptible to being slung off a rotating tire, even after the treatment has dried completely. The present investigations have found that silicone-based materials that comprise reactive groups (e.g. hydroxyl and/or amino groups) can, at least in some instances, exhibit increased resistance to such phenomena. It has also been found that the presence of silicone-based materials with reactive groups may allow the composition, after its transformation into a hydrophobic layer on a tire, to be more resistant to being dislodged by subsequent water exposure. Without wishing to be limited by theory or mechanism, it is postulated that the surface of rubber tires may comprise various moieties that, while they do not necessarily have a large effect on the surface energy of the rubber (which tends to remain strongly hydrophobic), may nevertheless provide molecular anchor points for reactive groups of certain silicone-based compounds. Such moieties might be e.g. oxidized double-bonds of natural or synthetic rubber, might be vulcanization residues of such a rubber, might be on the surface of fumed silica or carbon black filler particles that may be present in the rubber, and so on.

A hydrophobic layer as formed by the deposition and water-evaporation of an aqueous emulsion as disclosed herein may, in many embodiments, serve primarily to provide an attractive visual appearance. For example, it may impart a glossy or shiny appearance to a tire as noted above. Such a layer may not necessarily be as robust, or provide as strong a physically-protective effect, as that provided by a material (e.g., car wax or the like) that is configured to form a physically-protective film. A hydrophobic layer as disclosed herein is thus distinguished from such entities as automotive clear coats and similar protective layers. In general, the aqueous emulsions disclosed herein are distinguished from compositions that are configured to clean a surface and/or to apply a protective layer that provides robust physical protection (e.g. abrasion resistance) to a surface for long periods of time (e.g. for one or more months). As such, the aqueous emulsions disclosed herein are distinguished from compositions such as car washing compositions, car waxing compositions, and the like. In particular embodiments, a herein-disclosed aqueous composition will comprise less than 1.0, 0.5, 0.2, 0.1, or 0.05 % (on an individual basis) of any detergent, builder, bleach, enzyme, or the like, that is present for the purpose of having a cleaning or debris-removal effect.

Working Examples

Materials

The materials listed in Table 1 were obtained.

Table 1

¹ Available from a variety of sources, e.g. XIAMETER PMX-200 from Dow Chemical

² Silicone material believed to be PDMS fluid

³ Silicone material believed to include OH-functional PDMS (dimethiconol) fluid

⁴ Available from a variety of sources

All ingredients listed as “x” % actives are believed to be wt. % actives in water, with the exception of XIAMETER OFX-0531, which is listed by the supplier as 50 wt. % actives in solvent. Procedures

Viscosity measurements were performed on a Brookfield D V-I viscometer, using spindle RVO 1 set at 10RPM rotational speed.

Gloss measurements were performed using a BYK micro-TRI-gloss meter measured at 80 degree angles. Gloss measurements were performed on flat SBR coupons before and after treating the surface.

Working Example Group 1

The following is a representative example reported on abasis of 100 grams of aqueous emulsion produced. In fact, numerous Working Example samples with the following general composition, of various batch sizes and with variations in composition, were made and evaluated. To make a 100 gram sample of the aqueous emulsion, a small portion (2.5 g) of the total water was mixed with 0.5 g of TEGOPREN 5840 (which, at 75 % actives, contained approximately 0.38 g of silicone-polyether surfactant). Using a laboratory propeller-stirrer equipped with a nominal 2 inch diameter, 3 -bladed, marine-style propeller, running at approximately 2000 RPM, 20 g of 350 cSt PDMS fluid (100 % actives) was slowly added to the TEGOPREN/water mixture to emulsify the PDMS fluid in the TEGOPREN/water mixture. This resulting emulsion increased in viscosity to a yogurt-like consistency with an opaque milky white. The emulsion was mixed for a few minutes until no further changes in appearance or viscosity were evident. It was estimated that the viscosity of the emulsion was in the range of 20000-30000 cSt and that the micelle size was in the range of 200 nm. After this, the remaining portion of water (approximately 78 g) and biocide (0.1g) was added and blended with stirring via the above-described propeller-stirrer. The addition of this make-up water caused the emulsion to become water-thin, but milky in color. To this emulsion, 0.60 g of ACUSOL 820 was added and blended (noting that ACUSOL 820 is 30 % actives, thus the actual amount of polyacrylate water-soluble thickener that was added was approximately 0.18 g). 0.48 g of triethanolamine was added to increase the pH to a range (estimated to be a pH of 8-9) that deprotonated the water-soluble thickener. This caused the viscosity of the aqueous emulsion to increase significantly. 0.2 g of fragrance was added and the aqueous emulsion was further blended to thoroughly mix the fragrance into the aqueous emulsion.

The above procedure produced an aqueous emulsion with a viscosity (determined within a few minutes of making the formulation, and reported in centiPoise) of approximately 1000 cP and of the general composition shown in Table 2. Table 2

As noted, the above is a representative sample; a variety of Working Example Group 1 samples were made, of various batch sizes, with and without biocide and fragrance, etc. All percentages are in weight percent of active ingredient in the final aqueous emulsion. The total level of water includes both water added to the emulsion, and small amounts of water in various raw materials as supplied, e.g. in the TEGOPREN and in the ACUSOL.

The water-based compositions, in the form of aqueous emulsions, of various samples of Working Example Group 1 were packaged in conventional trigger-actuated spray bottles, from which the compositions were easily sprayable onto a surface. Various such samples were spray -deposited onto the sidewalls of representative automobile tires (including tires from OHTSU and Michelin). The tires were dry when the samples were applied. Typically, about six sprays per tire were applied, with each spray being qualitatively estimated to dispense approximately 3 g of the composition. The spray- deposited droplets of aqueous emulsion rapidly merged and consolidated on the tire surface (within one minute) to form a continuous-appearing layer with a milky-white appearance that was easily visible against the black tire surface. The thus-formed layer of aqueous emulsion was then allowed to dry for a few minutes, during which time the milky -white color faded and was replaced by a glossy, transparent sheen.

Some of above-described Working Example samples were compared to Comparative Examples in which similar tires were subjected to treatment with a commercially available tire shine. The commercially available tire shine had a roughly similar percentage of hydrophobic silicone-containing material (approximately 20 wt. %) but was solvent-based rather than water-based. The Working Example samples, despite being water based, were found to wet and spread on the tire surface at least as quickly and as thoroughly as the commercial, solvent-based tire shine. Upon drying of the Working Example samples and the Comparative Example samples, it was observed that the Working Example samples consistently exhibited a more shiny, glossy and darker appearance than the Comparative Example samples. A typical result is shown in Fig. 3, in which a Working Example Group 1 sample was applied to the left portion (as viewed) of the tire and a Comparative Example sample was applied to the right portion of the tire (with a small, central portion that is approximately aligned with the post against which the tire is leaning, having no sample applied to it). The superior results that were achieved by the Working Example sample are readily apparent.

Working Example Group 2

The following is a representative example reported on abasis of 100 grams of aqueous emulsion produced. In fact, numerous Working Example samples with the following general composition, but of various batch sizes and with variations in composition, were made and evaluated. To make a 100 gram sample of the aqueous emulsion, approximately 72 g water and 0.1 g biocide/preservative was added to a vessel. To this, 1.0 g of ACUSOL 820 was added and blended (noting that ACUSOL 820 is 30 % actives, thus the actual amount of polyacrylate water-soluble thickener that was added was approximately 0.30 g). 0.80 g of triethanolamine was added to increase the pH to a range (estimated to be a pH of 8-9) that deprotonated the water-soluble thickener. This caused the viscosity of the mixture to increase significantly. 25.0 g of premade silicone emulsion (from CHT Group) was then slowly added while mixing with a laboratory propeller-stirrer. (The premade silicone emulsion was believed to be 60 % actives, thus the actual hydrophobic, silicone-based material from this premade silicone emulsion that was present in the final formulation was at a level of approximately 15.0 wt. %.) 0.50 g of TEGOPREN 5840 (which, at 75 % actives, contained approximately 0.38 g of silicone-polyether surfactant) was then added, followed by 0.20 g of fragrance, and the mixture was blended until uniform. The result was an aqueous emulsion that was very similar in appearance to the above-described aqueous emulsions of Working Example Group 1, with a viscosity (again, measured within a few minutes) in the range of approximately 300 cP and of the general composition shown in Table 3.

Table 3 As noted, the above is a representative sample; a variety of samples were made, of various batch sizes, with and without biocide and fragrance, etc. All percentages are in weight percent of active ingredient in the final aqueous emulsion. The total level of water includes both water added to the emulsion, and water contained in various raw materials as received, e.g. in the premade silicone emulsion, the TEGOPREN and the ACUSOL.

The water-based compositions, in the form of aqueous emulsions, of various samples of Working Example Group 2 were packaged in a conventional trigger-actuated spray bottle, from which the compositions were easily sprayable onto a surface. Various such samples were spray -deposited onto the sidewalls of representative automobile tires in similar manner as described above. The behavior of the samples of Working Example Group 2 was quite similar to those of the samples of Working Example Group 1.

Working Example Group 3

Numerous varieties and modifications of the above formulations were formulated. For example, a number of samples were made in similar manner to Working Example Groups 1 and 2, but which were formulated with a blend of the above type of silicones along with one or more silicones bearing reactive groups. For example, one Representative Example sample (again on a basis of 100 g. total batch weight), included 16.0 g of a first premade silicone emulsion (from CHT Group) at 60 % solids, so that the silicone material (believed to be a non-reactive PDMS fluid) from this first premade emulsion was present in the final composition at 9.6 wt. %. The sample also included 8.0 g of a second premade emulsion, XIAMETER MEM-1785. This second premade emulsion comprised a silicone material believed to be OH-functional PDMS (dimethiconol) fluid. The XIAMETER premade emulsion was at 60 % solids so that the OH-functional PDMS (dimethiconol) fluid was present in the final composition at 4.8 wt. %.

The sample also included a small amount (less than 1.0 weight percent in total) of a third premade emulsion that included XIAMETER OFX-0531, which is believed to be an aminomethoxy polydimethylsiloxane. This third premade emulsion also included DOWSIL 2-1912, which is a blend of PDMS fluid and silicone resin. These ingredients were present in the third premade emulsion at levels such that, in the final composition, the aminomethoxy polydimethylsiloxane from the OFX-0531 was present at approximately 0.05 wt. % and the PDMS fluid/silicone resin blend from the DOWSIL 2-1912 was present at approximately 0.22 wt. %. (The specific ratio of PDMS fluid to silicone resin blend in the DOWSIL 2-1912 is not known.)

This sample comprised TEGOPREN silicone-polyether surfactant at approximately 0.38 wt. % and comprised ACUSOL 820 of polyacrylate water-soluble thickener at approximately 0.24 wt. %.

The Working Example Group 3 samples were thus similar to those of Working Example Groups 1 and 2 except that the hydrophobic, silicone-based materials included a significant amount of silicone that included reactive groups. The specific representative example described above comprised hydroxyl-functional PDMS (at approximately 4.8 wt. %) and smaller amounts of aminomethoxy polydimethylsiloxane (at approximately 0.05 wt. %) and silicone resin. (As noted above, the actual amount of silicone resin that is in DOWSIL 2-1912 is unknown; if DOWSIL 2-1912 is e.g. 50 % by weight of silicone resin, the silicone resin would be in the final composition at approximately 0.11 wt. %.) Numerous variations and modifications were formulated, including samples with hydroxyl- functional PDMS but without any aminofunctional silicone and without any silicone resin.

The water-based compositions, in the form of aqueous emulsions, of various samples of Working Example Group 3 were packaged in conventional trigger-actuated spray bottles, from which the compositions were easily sprayable onto a surface. Various such samples were spray -deposited onto the sidewalls of representative automobile tires in similar manner as described above. The deposition and drying behavior, and final appearance, of the samples of Working Example Group 3 were quite similar to those of the samples of Working Example Group 1 and 2.

Water resistance and gloss retention

It was noted that many of the samples of Working Example Group 3 appeared to exhibit enhanced resistance to water. This was assessed by spray -treating a portion of an automobile tire with a Working Example Group 3 sample, and spraying another portion of the tire with the commercial, solvent-based tire shine discussed above in Working Example Group 1. The tire was then subjected to a water rinse and to a gentle washing procedure using a commercially available car wash composition applied using a microfiber wash mitt. After this procedure, the portion of the tire that had been treated with the commercial, solvent-based tire shine exhibited very little gloss, while the portion that had been treated with the Working Example sample exhibited gloss that was somewhat diminished, but that was noticeably superior to that exhibited by the commercial tire shine.

Further experiments were also done using styrene-butadiene mbber (SBR) in the form of flat coupons. Gloss values of these Working-Example-Group-3 -treated SBR coupons were obtained and were compared to the gloss of SBR coupons treated with the above-mentioned commercial tire shine. The Comparative Example coupons treated with commercial tire shine exhibited an initial gloss that was almost 2.5 times as high as that of the coupons treated with the Working Example samples. This was not unexpected in view of the fact that the commercial tire shine contained approximately twice the level of hydrophobic, silicone-containing materials as these particular Working Example samples contained and also in view of the fact that these particular Working Example samples did not include thickener and thus exhibited significant runoff from the SBR coupons (which were propped up vertically for sample application, in order to best simulate actual conditions under which such formulations are typically applied to tires).

However, even a single rinse cycle (consisting of rinsing with a water-spray hose followed by drying with pressurized air) caused the gloss of the Comparative Example coupons to drop sharply (by half), while the gloss of the Working Example coupons was essentially unchanged through three rinse cycles. After four to five rinse cycles, the gloss of the Comparative Example coupons had dropped to around 25 % of its initial value, while the gloss of the Working Example coupons was holding at about 80 % of its initial value (and thus was appreciably higher than the gloss of the Comparative Example coupons after this number of rinse cycles).

As noted, numerous variations and modifications within the general Working Example Group 3 concept (using at least some silicone with reactive groups) were formulated and evaluated. It was found that using hydroxyl-functionalized silicone as the only functionalized silicone (e.g., using XIAMETER MEM-1785 in combination with a non-functionalized silicone, in the absence of aminofunctionalized silicone and in the absence of silicone resin) still provided excellent results in terms of resistance to water, as well as in overall performance.

The foregoing Examples have been provided for clarity of understanding only, and no unnecessary limitations are to be understood therefrom. The tests and test results described in the Examples are intended to be illustrative rather than predictive, and variations in the testing procedure can be expected to yield different results. All quantitative values in the Examples are understood to be approximate in view of the commonly known tolerances involved in the procedures used.

It will be apparent to those skilled in the art that the specific exemplary embodiments, elements, structures, features, details, arrangements, configurations, etc., that are disclosed herein can be modified and/or combined in numerous ways. It is emphasized that any embodiment disclosed herein may be used in combination with any other embodiment or embodiments disclosed herein, as long as the embodiments are compatible. While a number of exemplary combinations are presented herein, it is emphasized that all such combinations are envisioned and are only prohibited in the specific instance of a combination that is incompatible.

In summary, numerous variations and combinations are contemplated as being within the bounds of the conceived invention, not merely those representative designs that were chosen to serve as exemplary illustrations. Thus, the scope of the present invention should not be limited to the specific illustrative structures described herein, but rather extends at least to the structures described by the language of the claims, and the equivalents of those structures. Any of the elements that are positively recited in this specification as alternatives (e.g., any ingredient or component that is described as possibly being present but not necessarily being required to be present) may be explicitly included in the claims or excluded from the claims, in any combination as desired. Any of the elements or combinations of elements that are recited in this specification in open-ended language (e.g., comprise and derivatives thereof), are considered to additionally be recited in closed-ended language (e.g., consist and derivatives thereof) and in partially closed-ended language (e.g., consist essentially, and derivatives thereof). Although various theories and possible mechanisms have been discussed herein, in no event should such discussions serve to limit the claimable subject matter. To the extent that there is any conflict or discrepancy between this specification as written and the disclosure in any document that is incorporated by reference herein but to which no priority is claimed, this specification as written will control.