Automotive protective compositions with improved vertical adhesion and their use

Abstract

A sprayable automotive protectant composition comprising: (a) 0.1% to 5% by weight of a nonionic surfactant comprising an alcohol ethoxylate, (b) 0.1% to 5% by weight of an anionic surfactant comprising a sulfonate surfactant, (c) 5 wt% to 15 wt% of a polyorganosiloxane having a pure viscosity of 10 mm 2 / s (cSt) up to 1 000 000 mm 2 / s (cSt), (d) 0.05% to 0.3% rheology modifier selected from the group consisting of acrylic polymers, methacrylic polymers, acrylamide polymers, acrylic and acrylamide copolymers, methacrylic and acrylamide copolymers and mixtures thereof, (e) 65% to 95% water and (f) sodium benzoate, wherein the automotive protectant is an emulsion in which the polyorganosiloxane is present with a particle size in the range of 10 nm to 1000 nm and the automotive protectant has a viscosity of greater than 4 Pas (4000 cps) and less than 6 Pas (6000 cps) and has a vertical adhesion parameter of between 2.54 cm flow per 2 minutes and 17.78 cm flow per 2 minutes at a temperature of 25°C and wherein the ratio of nonionic surfactant to anionic surfactant is 1:1 to 3:2.

Description

BACKGROUND OF THE INVENTIONField of the invention

[0001] The present invention relates to a sprayable automotive protectant composition having advantageous surface adhesion and application properties and its use.

[0002] These surface adhesion and application properties are measured and quantified as the vertical adhesion of a composition. A composition with a very high vertical adhesion parameter, greater than 7, will sag very quickly from a vertical surface, making it difficult to obtain uniform coverage with a composition on vertical, inclined, or angled surfaces, which are common on automotive surfaces. A very low vertical adhesion parameter, less than 1, means the composition has very strong surface adhesion to vertical surfaces and will not sag. If it has a very low vertical adhesion parameter, this may not be beneficial because the composition may not be sprayable, may not spread easily, or may not be easily applied to surfaces, and uniform coverage may not be obtained.

[0003] The present invention generally relates to a protectant composition comprising a sprayable aqueous silicone emulsion containing at least one surfactant and a rheology modifier, a silicone, and water. The composition has a vertical adhesion parameter between 1 and about 7 at a temperature of about 25°C. The present application also describes a method for cleaning, providing shine, and / or protecting an interior automotive surface by applying the composition of the invention directly to a soiled or cleaned surface and then spreading the composition over the surface with a substrate. The substrate may be a nonwoven material comprising cellulosic fibers, modified cellulosic materials, synthetic fibers, or a mixture of cellulose or modified cellulose and synthetic fibers.The synthetic fibers are selected from the group consisting of polyethylene, polypropylene, and polyethylene terephthalate (PET), and any mixture or combination thereof. In an alternative embodiment, the composition can be applied to an automotive surface using a pre-coated wiper or substrate coated with a protectant composition.

[0004] The present invention relates to sprayable silicone-containing protectant compositions used to enhance the gloss and contribute to the protection of automotive surfaces. More particularly, the present invention relates to protectant compositions that are aqueous silicone emulsions that provide a uniform gloss and protection to surfaces without dripping or running. Furthermore, the protectant composition of the present invention typically contains less silicone, yet still provides a gloss comparable to or higher than other prior art and / or commercially available formulations. Description of the related art

[0005] Silicone-based automotive protectants are now established products on the market. The term "automotive protectants" refers to products applied to vinyl, leather, plastics, rubber, and other interior and exterior surfaces of cars, trucks, and other vehicles to enhance the shine of such surfaces. These protectants also serve to protect such surfaces from the damaging effects of UV rays, sunlight, heat, moisture, etc. Although they are described as "automotive protectants," the term "automotive" should not be construed as limiting the use of these compositions, which can be used on boats, trains, airplanes, patio furniture, indoor furniture, etc., as well as for a variety of interior applications.

[0006] The protectant can be sprayed directly onto the surface to be treated, or it can first be sprayed onto a cloth, pad, or the like and then applied to the intended surface. Evaporation of the aqueous continuous phase leaves an organopolysiloxane coating that can, in some cases, penetrate polymer substrates, ameliorating the loss of plasticizers from such surfaces due to exposure to sun and heat. The protectants are also often formulated with UV absorbers, and the net effect is not only to restore the vehicle or other product to a glossy appearance, but also to generally extend the life of leather and vinyl surfaces to which the protectant has been applied.

[0007] While lotion- and paste-type protectants exist, these have not achieved the acceptance of sprayable formulations, not only because they are more difficult to apply to the surface, but also because of their tendency to leave a buildup of protectant at seams, crevices, and on highly textured surfaces, such as leather-like vinyl. Examples of such paste- and lotion-type protectants are provided by US Pat. No. 5,433,890, which discloses protectants containing both an amino-functional organopolysiloxane and a polydimethylsiloxane, a film-forming polymer to increase abrasion resistance, and morpholine, which is necessary to activate the film-forming polymer. These protectants must be left on the surface for a considerable period of time before the excess is wiped off, and maximum effectiveness is achievable only with a second coating.The disadvantages of such preparations are easy to see.

[0008] Published Canadian application CA 1176828 A discloses paste-type polishes based on an organopolysiloxane emulsion containing a silicone-soluble UV absorber. These polishes have a high organopolysiloxane content, greater than 20 percent by weight based on the weight of solids, and an organic thickener that provides the paste-like character of the polish and serves to keep the high level of silicone solids evenly dispersed. However, these compositions are not sprayable and therefore suffer from the disadvantages of other pastes, creams, and lotions. In addition, they contain a high proportion of relatively expensive organopolysiloxane.

[0009] US 2005 / 250668 A1 describes rheologically stabilized silicone dispersions. The active ingredients of automotive protectants include silicones, which are usually organopolysiloxanes. Organopolysiloxanes are relatively expensive, and a typical protectant can contain from 20% to 40% by weight of organopolysiloxane as an aqueous emulsion. Despite the relatively high amount of organopolysiloxane, studies show that only a relatively small amount, i.e., 10% to 20%, of what is applied actually ends up on the substrate. It would be desirable to be able to reduce the amount of organopolysiloxane in automotive protectants without reducing performance, or to obtain increased performance with the same level of active ingredient. Even with the same organopolysiloxane content, improved performance can allow for lower application rates, resulting in greater cost-effectiveness for the buyer.

[0010] Two patents, US 6,221,433 B1 and US 6,206,956 B1 to Muntz et al., describe siloxane automotive protectant compositions containing about 10% to 20% by weight organopolysiloxane and having comparable or improved gloss performance to comparative examples containing 20% ​​to 40% by weight organopolysiloxane. The siloxane automotive protectants described in the Muntz patents require the viscosity of the emulsion to be less than about 4 Pas (4000 cP) to maintain their sprayability. Although these protectant formulations are an improvement over previous protectants, it is still possible to reduce the amount of siloxane in the formulation to levels of less than 10% to achieve cost savings while maintaining good gloss performance.In addition, these formulations described by Muntz have a viscosity of less than 4 Pas (4000 cps) and do not show good vertical adhesion and tend to drip and run off surfaces.

[0011] Therefore, there is a need in the art for improved protectant compositions and methods of using these protectants that provide good gloss and protection of automotive surfaces with low levels of silicone and provide improved application and better vertical adhesion properties so that they can be applied evenly to surfaces without dripping and running. SUMMARY OF THE INVENTION

[0012] In accordance with the above objects and those mentioned and apparent hereinafter, one aspect of the present invention is a sprayable automotive protectant composition comprising: (a) 0.1% to 5% by weight of a nonionic surfactant comprising an alcohol ethoxylate, (b) 0.1% to 5% by weight of an anionic surfactant comprising a sulfonate surfactant, (c) 5 wt% to 15 wt% of a polyorganosiloxane having a pure viscosity of 10 mm 2 / s (cSt) up to 1 000 000 mm 2 / s (cSt), (d) 0.05% to 0.3% rheology modifier selected from the group consisting of acrylic polymers, methacrylic polymers, acrylamide polymers, acrylic and acrylamide copolymers, methacrylic and acrylamide copolymers and mixtures thereof, (e) 65% to 95% water, wherein the automotive protectant is an emulsion in which the polyorganosiloxane is present with a particle size in the range of 10 nm to 1000 nm and the automotive protectant has a viscosity of more than 4 Pas (4000 cps) and less than 6 Pas (6000 cps) and has a vertical adhesion parameter of between 2.54 cm flow per 2 minutes and 17.78 cm flow per 2 minutes at a temperature of 25°C and wherein the ratio of nonionic surfactant to anionic surfactant is 1:1 to 3:2 and (f) Sodium benzoate.

[0013] In one embodiment of the present invention, the cleaning concentrate of the present invention adheres to a wetted vertical surface of an automobile without excessively running, dripping, or flowing, as measured by the vertical adhesion parameter.

[0014] In a further embodiment of the present invention, there is provided a protectant composition according to the claims, which contains at least one surfactant and a rheology modifier, which has a vertical adhesion parameter between 1 and about 7 at a temperature of about 25°C and optionally contains a solvent and optionally contains a source of alkalinity.

[0015] In yet another embodiment of the present invention, there is provided a protectant composition according to the claims, comprising at least one surfactant, at least one silicone and a rheology modifier, having a vertical adhesion parameter between 1 and about 7 at a temperature of about 25°C and optionally comprising a source of alkalinity.

[0016] Also described is a method for protecting an automotive surface by spraying the protectant composition of the invention, which has a vertical adhesion parameter between 1 and about 7 at a temperature of about 25°C, directly onto a clean automotive surface, followed by spreading the compositions of the invention to provide uniform gloss and protection. A method is also described for applying the protectant composition to a soiled surface and spreading the protectant formulation onto the substrate surface to clean and protect the surface.

[0017] Described is a kit that uses the automotive protectant of the invention, a dispensing package, and instructions for applying the protectant directly to a cleaned or soiled automotive surface, for example, a vehicle cleaning kit that uses a spray gun or aerosol atomizer that enables the uniform application of the protectant composition to a surface and has a vertical adhesion parameter between 1 and about 7 at a temperature of about 25°C.

[0018] Also described is a method for protecting an automotive surface, comprising the steps of: (a) spraying the automotive surface with a protectant composition having a vertical adhesion parameter between 1 and about 7 at a temperature of about 25°C, the protectant composition comprising: (i) a mixture of nonionic and anionic surfactants, (ii) a polyorganosiloxane, (iii) and (iv) a rheology modifier, and (b) distributing the protectant composition over the automotive surface.

[0019] In one disclosure, the vehicle cleaning kit instructions include step-by-step instructions for a method of use whereby the compositions of the invention are applied directionally to a soiled surface, followed by a cleaning step wherein the concentrated cleaning agent is distributed over the surface so that it acts on the soil, followed by a rinsing step with water to remove the cleaning concentrate and the soil.

[0020] Further features and advantages of the present invention will become apparent to those skilled in the art in view of the following detailed description of suitable embodiments when considered in conjunction with the appended claims. DETAILED DESCRIPTION

[0021] Before describing the present invention in detail, it should be understood that this invention is not limited to the particular systems or process parameters illustrated, which may, of course, vary. It should be understood that the terminology used herein is for the purpose of describing particular embodiments of the invention only and is not intended to limit the scope of the invention in any way.

[0022] It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include the plural referent unless the content clearly dictates otherwise. For example, a reference to a "surfactant" includes two or more such surfactants.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. While a variety of methods and materials similar or identical to those described herein may be used in the practice of the present invention, exemplary materials and methods are described herein.

[0024] In the application, effective amounts are typically the amounts listed as the ranges or levels of ingredients in the descriptions that follow. Unless otherwise stated, amounts expressed as percentages ("%") are weight percents based on the weight of the total composition. Compositions are usually expressed as weight percents equivalent to 100% active ingredient (based on the weight of the active ingredient), and thus, the weight of carrier or solvent is not included in the stated percentages.

[0025] As used herein, the term "polymer" generally includes, but is not limited to, homopolymers, copolymers, such as block, graft, random, and alternating copolymers, terpolymers, etc., and mixtures and modifications thereof. Furthermore, unless otherwise specifically limited, the term "polymer" is intended to include all possible geometric configurations of the molecule. These configurations include, but are not limited to, isotactic, syndiotactic, and random symmetries.

[0026] The term “protective composition” as used herein is intended to mean and include a formulation comprising at least one surfactant and at least one silicone component.

[0027] The term "surfactant" or "surfactant," as used herein, is intended to mean and include a substance or compound that reduces surface tension when dissolved in water or aqueous solutions, or reduces the interfacial tension between two liquids or between a liquid and a solid. The term "surfactant" or "surfactant" thus includes anionic, cationic, nonionic, zwitterionic, and / or amphoteric agents.

[0028] The term "viscosity" as used herein, unless otherwise stated, is the viscosity of a liquid component of the invention as expressed as kinematic viscosity in centipoise (cps) measured at 25°C (77°F). composition

[0029] The compositions of the invention comprise combinations of, among others, a surfactant, a rheology modifier, and a silicone, which are combined to provide a protectant composition having suitable substantivity on a vertical surface defined by a vertical adhesion parameter such that the compositions of the invention, when applied to a vertical surface, do not excessively sag, drip, or flow from the point of application. The compositions of the invention contain at least one silicone component that imparts gloss and brilliance to the surface and contain at least one rheology modifier that contributes to thickening and desirable rheological properties that provide the compositions with a vertical adhesion parameter between 1 and about 7 at a temperature of about 25°C. Surfactant

[0030] The compositions of the present invention contain two surfactants. The compositions of the present invention may contain multiple surfactants selected from anionic, nonionic, cationic, ampholytic, amphoteric, and zwitterionic surfactants, and mixtures thereof. A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes and species of these surfactants is given in U.S. Pat. No. 3,929,678 to Laughlin and Heuring. A list of suitable cationic surfactants is given in U.S. Pat. No. 4,259,217 to Murphy. Where present, ampholytic, amphoteric, and zwitterionic surfactants are used in combination with one or more anionic and nonionic surfactants.

[0031] The automotive protective agent composition includes: 0.1 wt% to 5 wt% of a nonionic surfactant comprising an alcohol ethoxylate 0.1% to 5% by weight of an anionic surfactant comprising a sulfonate surfactant,

[0032] The composition may comprise an anionic surfactant. Essentially any anionic surfactant suitable for detergent purposes may be comprised in the composition of the invention. These may be salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts, such as mono-, di-, and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate, and sarcosinate surfactants. Anionic surfactants may comprise a sulfonate or sulfate surfactant. Anionic surfactants may comprise an alkyl sulfate, a straight or branched alkylbenzenesulfonate, or an alkyl diphenyl oxide disulfonate, as described herein. Preferred anionic surfactants include, but are not limited to, secondary alkanesulfonate sodium salt surfactants, such as HOSTAPUR ® SAS 30, HOSTAPUR ®SAS 60, both marketed by Clariant Functional Chemicals, and alkoxylate sulfate surfactant, such as TRITON™ W30, marketed by the Dow Chemical Company.

[0033] Other anionic surfactants include isethionates, such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters (for example, saturated and unsaturated C12-C18 monoesters) of sulfosuccinate, diesters (for example, saturated and unsaturated C6-C14 diesters) of sulfosuccinate, and N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil. Anionic sulfate surfactants suitable for use according to the invention include:straight and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty acid oleoylglycerol sulfates, alkylphenol ethylene oxide ether sulfates, C5-C17 acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl)glucamine sulfates, and alkyl polysaccharide sulfates, such as alkyl polyglucoside sulfates (the nonionic, non-sulfated compounds being described here). Alkyl sulfate surfactants can be selected from straight and branched primary C10-C18 alkyl sulfates, branched-chain C11-C15 alkyl sulfates, or straight-chain C12-C14 alkyl sulfates.

[0034] Alkyl ethoxysulfate surfactants can be selected from the group consisting of C10-C18 alkyl sulfates ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. The alkyl ethoxysulfate surfactants can be a C11-C18 or a C11-C15 alkyl sulfate ethoxylated with 0.5 to 7 or 1 to 5 moles of ethylene oxide per molecule. In one aspect of the invention, mixtures of the alkyl sulfate and / or sulfonate and the alkyl ethoxysulfate surfactants are used. Such mixtures are disclosed in PCT Patent Application No. WO 93 / 18124.

[0035] Anionic sulfonate surfactants suitable for use in the present invention are the salts of linear C5-C20 alkylbenzenesulfonates, alkyl ester sulfonates, primary or secondary C6-C22 alkanesulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty acid oleoyl glycerol sulfonates, and any mixtures thereof. Suitable anionic carboxylate surfactants include the alkyl ethoxycarboxylates, the alkyl polyethoxypolycarboxylate surfactants, and the soaps ("alkyl carboxyls"), especially certain secondary soaps, as described herein. Suitable alkyl ethoxycarboxylates include those having the formula RO(CH2CH2O) x CH2COO - M +wherein R is a C6 to C18 alkyl group, x is in the range from 0 to 10 and the ethoxylate distribution is such that, by weight, the amount of substance wherein x is 0 is less than 20% and M is a cation. Suitable alkylpolyethoxypolycarboxylate surfactants include those having the formula RO-(CHR 1 -CHR 2 -O)-R 3 , wherein R is a C6 to C18 alkyl group, x ranges from 1 to 25, R 1 and R 2 are selected from the group consisting of hydrogen, methyl acid residue, succinic acid residue, hydroxysuccinic acid residue and mixtures thereof, and R 3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 C atoms and mixtures thereof.

[0036] Suitable soap surfactants are secondary soap surfactants containing a carboxyl group bonded to a secondary carbon atom. Secondary soap surfactants suitable for use in the present invention are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid, and 2-pentyl-1-heptanoic acid. Certain soaps may also be added as suds suppressors.

[0037] Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON(R 1 )CH-)COOM, where R is a straight or branched C5-C17 alkyl or alkenyl group, R 1 is a C1-C4 alkyl group and M is an alkali metal ion. Examples are myristyl and oleoylmethyl sarcosinates in the form of their sodium salts.

[0038] Essentially, all alkoxylated nonionic surfactants are suitable here, e.g., ethoxylated and propoxylated nonionic surfactants. Alkoxylated surfactants can be selected from the classes of nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, nonionic ethoxylated / propoxylated fatty alcohols, nonionic ethoxylate / propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide / ethylenediamine adducts. Preferred nonionic surfactants include, but are not limited to, nonionic polyglycol ether surfactants, such as TMN-6 TERGITOL. ® , which is from SIGMA-ALDRICH ® supplied, ethoxylated non-ionic lauryl alcohol surfactants, such as the SURFONIC ®L 12 series supplied by Huntsman Performance Products and ethoxylated straight nonionic primary alcohol surfactants such as the SURFONIC ® L-series, especially SURFONIC ® SPF 23-9, both supplied by Huntsman Performance Products.

[0039] The condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxide, particularly ethylene oxide and / or propylene oxide, are suitable for use according to the invention. The alkyl chain of the aliphatic alcohol can be either straight or branched, primary or secondary, and generally contains 6 to 22 carbon atoms. Also suitable are the condensation products of alcohols containing an alkyl group with 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol.

[0040] Polyhydroxy fatty acid amides suitable for use according to the invention are those having the structural formula R 2 CONR 1 Z, where R1 represents H, C1-C4 hydrocarbon radical, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or a mixture thereof, for example C1-C4 alkyl or C1 or C2 alkyl, and R 2 is a C5-C31 hydrocarbon radical, for example straight-chain C5-C19 alkyl or alkenyl, or straight-chain C9-C17 alkyl or alkenyl, or straight-chain C11-C17 alkyl or alkenyl, or a mixture thereof, and Z is a polyhydroxyhydrocarbon radical having a straight hydrocarbon chain with at least 3 hydroxyl groups directly attached to the chain, or an alkoxylated (e.g., ethoxylated or propoxylated) derivative thereof. Z can derive from a reducing sugar in a reductive amination reaction; for example, Z is glycidyl.

[0041] Suitable fatty acid amide surfactants include those with the formula: R 1 CON(R 2 )2, where R 1 an alkyl group having 7 to 21 or 9 to 17 carbon atoms and R2 each selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl and -(C2H4O) x H, where x is in the range 1 to 3.

[0042] Suitable alkyl polysaccharides for use in the present invention are disclosed in U.S. Pat. No. 4,565,647 to Llenado and have a hydrophobic group containing 6 to 30 carbon atoms and a hydrophilic polysaccharide, e.g., a polyglycoside, group having 1.3 to 10 saccharide units. Alkyl polyglycosides may have the formula: R 2 O(C n H 2n O) t (glycosyl) x , where R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain 10 to 18 carbon atoms, n is 2 or 3; t ranges from 0 to 10, and x ranges from 1, 3 to 8. The glycosyl may be derived from glucose.

[0043] Suitable amphoteric surfactants for use according to the invention include amine oxide surfactants and alkylamphocarboxylic acids. Suitable amine oxides include the compounds of the formula R 3 (OR 4 ) x NO(R 5 )2, where R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof having 8 to 26 carbon atoms, R 4 is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof, x ranges from 0 to 5, alternatively from 0 to 3 and R 5 each is an alkyl or hydroxyalkyl group having 1 to 3 ethylene oxide groups or a polyethylene oxide group having 1 to 3 ethylene oxide groups. Suitable amine oxides are C10-C18 alkyldimethylamine oxide and C10-C18 acylamidoalkyldimethylamine oxide. A suitable example of an alkylamphodicarboxylic acid is Miranol™ C2M Conc., manufactured by Miranol, Inc., Dayton, NJ.

[0044] Zwitterionic surfactants may also be included in the compositions of the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use in the invention.

[0045] Suitable betaines are the compounds with the formula R(R 1 )2N + R 2 COO - , where R is a C6-C18 hydrocarbon group, R 1 each is usually C1-C3 alkyl and R 2is a C1-C5 hydrocarbon group. Suitable betaines are C12-C18 dimethylammonium hexanoate and the C10-C18 acylamidopropane (or ethane) dimethyl (or diethyl ether) betaines. Complex betaine surfactants are also suitable for use according to the invention.

[0046] Suitable cationic surfactants that can be used here include quaternary ammonium surfactants. The quaternary ammonium surfactant can be a mono-C6-C16 or a C6-C10 N-alkyl or alkenylammonium surfactant, with the remaining N positions substituted by methyl, hydroxyethyl, or hydroxypropyl groups. Monoalkoxylated and bisalkoxylated amine surfactants are also suitable.

[0047] Another suitable group of cationic surfactants that can be used in the compositions of the invention are cationic ester surfactants. The cationic ester surfactant is a compound with surface-active properties that comprises at least one ester (i.e., -COO-) bond and at least one cationically charged group. Suitable cationic ester surfactants, including choline ester surfactants, are disclosed, for example, in U.S. Patent Nos. 4,228,042, 4,239,660, and 4,260,529. The ester bond and the cationically charged group may be separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e., with a chain length of three atoms), or from three to eight atoms, or from three to five atoms, or three atoms.The atoms comprising the spacer group chain are selected from the group consisting of carbon, nitrogen, and oxygen atoms, as well as any mixtures thereof, provided that each nitrogen or oxygen atom in that chain forms only one bond with carbon atoms in the chain. Thus, spacer groups containing, for example, -OO- (i.e., peroxide), -NN-, and -NO- bonds are excluded, while spacer groups with, for example, -CH2-O-, CH2-, and -CH2-NH-CH2- linkages are included. The spacer group chain may comprise only carbon atoms, or the chain may be a hydrocarbon chain.

[0048] The composition according to the invention may comprise cationic monoalkoxylated amine surfactants, for example of the general formula: R 1 R 2 R 3 N + ApR 4 X - , where R 1an alkyl or alkenyl group containing from about 6 to about 18 carbon atoms, or from 6 to about 16 carbon atoms, or from about 6 to about 14 carbon atoms; R 2 and R 3 are each independently alkyl groups having one to about three carbon atoms, for example methyl; for example R 2 and R 3 both are methyl groups; R 4 is selected from hydrogen, methyl and ethyl; X - is an anion such as chloride, bromide, methylsulfate, sulfate or the like, so that electrical neutrality is provided; A is an alkoxy group, especially an ethoxy, propoxy or butoxy group, and p ranges from 0 to about 30, or from 2 to about 15, or from 2 to about 8. The ApR 4 -group in the formula can have p = 1 and is a hydroxyalkyl group with no more than 6 C atoms, where the -OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 C atoms. Suitable ApR4 -groups are -CH2CH2-OH, -CH2CH2CH2-OH, -CH2CH(CH3)-OH and -CH(CH3)CH2-OH. Suitable R 1 -groups are straight alkyl groups, for example straight R 1 -groups with 8 to 14 carbon atoms.

[0049] Suitable cationic monoalkoxylated amine surfactants for use according to the invention have the formula R 1 (CH3)(CH3)N + (CH2CH2O) 2-5 HX - , where R 1 a C10-C18 hydrocarbon radical and mixtures thereof, especially C10-C14 alkyl or C10 and C12 alkyl, and X is any suitable anion for charge balance, for example chloride or bromide. As mentioned, compounds of the above type include those in which the ethoxy (CH2CH2O-) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2O-] and [CH2CH(CH3)O-] units (i-Pr) or n-propoxy units (Pr) or mixtures of EO and / or Pr and / or i-Pr units.

[0050] The cationic bisalkoxylated amine surfactant may have the general formula: R 1 R 2 N + ApR 3 A'qR 4 X - , where R 1 is an alkyl or alkenyl group containing from about 8 to about 18 carbon atoms, or from 10 to about 16 carbon atoms, or from about 10 to about 14 carbon atoms; R 2 is an alkyl group having one to three carbon atoms, for example methyl; R 3 and R 4 can vary independently and are selected from hydrogen, methyl and ethyl; X -is an anion, such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C1-C4 alkoxy, for example, ethoxy (i.e., -CH2CH2O-), propoxy, butoxy, and mixtures thereof; p ranges from 1 to about 30, or from 1 to about 4, and q ranges from 1 to about 30, or from 1 to about 4, or p and q are both 1.

[0051] Suitable cationic bisalkoxylated amine surfactants for use according to the invention have the formula R 1 CH3N + (CH2CH2OH)(CH2CH2OH) X - , where R 1 represents a C10-C18 hydrocarbon radical and mixtures thereof or C10, C12, C14 alkyl and mixtures thereof; X - is any anion that provides charge balance, for example chloride. Regarding the general structure of cationic bisalkoxylated amines given above, since in an exemplary compound R1 originates from the (coconut) fatty acids of the C12-C14 alkyl fraction, R 2 is methyl and ApR 3 and A'qR 4 are each monoethoxy.

[0052] Further cationic bisalkoxylated amine surfactants suitable according to the invention include compounds of the formula: R 1 R 2 N + -(CH2CH2O) p H-(CH2CH2O) q HX - , where R 1 represents a C10-C18 hydrocarbon radical or C10-C14 alkyl; p is independently 1 to about 3 and q is 1 to about 3; R 2 represents C1-C3 alkyl, for example methyl, and X - is an anion, for example chloride or bromide. Other compounds of the above type include those in which the ethoxy (CH2CH2O-) units (EO) are replaced by butoxy (Bu), isopropoxy [CH(CH3)CH2O-] and [CH2CH(CH3)O-] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and / or Pr and / or i-Pr units.

[0053] The compositions of the invention may contain a fluorosurfactant selected from nonionic fluorosurfactants, cationic fluorosurfactants, and mixtures thereof that are soluble or dispersible in the aqueous compositions taught herein, occasionally compositions that do not contain other detersive surfactants or other organic solvents, or both. Suitable nonionic fluorosurfactant compounds can be found among the substances currently commercially available under the trade name Fluorad. ® (ex. 3M Corp.). Examples of fluorosurfactants include those sold as Fluorad ® FC-740, which is generally described as fluorinated alkyl esters, Fluorad ® FC-430, which is generally described as fluorinated alkyl esters, Fluorad ® FC-431, which is generally described as fluorinated alkyl esters, and Fluorad ®FC-170-C, which is generally described as fluorinated alkyl polyoxyethylene ethanols.

[0054] Suitable non-ionic fluorosurfactant compounds include those believed to conform to the following formulation: C n F 2n+1 SO2N(C2H5)(CH2CH2O) x CH3, where: n has a value of 1-12 or of 4-12 or 8; x has a value of 4-18 or of 4-10 or 7; which is described as a non-ionic fluorinated alkyl alkoxylate and is known as Fluorad ® FC-171 (ex. 3M Corp., formerly Minnesota Mining and Manufacturing Co.).

[0055] Furthermore, suitable non-ionic fluorosurfactant compounds are also among the substances sold under the trade name ZONYL ® (DuPont Performance Chemicals). These include, for example, ZONYL ® FSO and ZONYL ® FSN. These compounds have the following formula: RfCH2CH2O(CH2CH2O) x H, where Rf stands for CF3(CF2CF2) y At ZONYL ® FSO is x 0 to about 15 and y is 1 to about 7. For ZONYL ® FSN is x 0 to about 25 and y is 1 to about 9.

[0056] An example of a suitable cationic fluorosurfactant compound has the following structure: C n F 2n+1 SO2NHC3H6N + (CH3)3I - , where n ~ 8. This cationic fluorosurfactant is available under the trade name Fluorad ® FC-135 is available from 3M. Another example of a suitable cationic fluorosurfactant is CF3-(CF2) n -(CH2) m SCH2CHOH-CH2-N + R1R2R3C1 - , where: n is 5-9 and m is 2 and R1, R 2 and R 3 represent -CH3. This cationic fluorosurfactant is available under the trade name ZONYL ® FSD available (available from DuPont, as 2-hydroxy-3-((gamma-omega-perfluoro-C 6-20-alkyl)thio)-N,N,N-trimethyl-1-propylammonium chloride). Other cationic fluorosurfactants suitable for use in the present invention are also described in EP 866,115 to Leach and Niwata.

[0057] According to the invention, the composition contains a mixture of anionic and nonionic surfactants. In this embodiment of the invention, it is preferred that the ratio of nonionic surfactant to anionic surfactant is about 1:1 to about 3:2. In this invention, the nonionic surfactant is selected from alkoxylated surfactants, namely nonionic ethoxylated alcohols. The anionic surfactant is a sulfonate surfactant, and more preferably an alkylsulfonate surfactant. According to the invention, the anionic surfactant is present at a level of about 0.1% to about 5% by weight of the composition, and the nonionic surfactant is present at a level of about 0.1% to about 5% by weight of the composition.In one embodiment, there is more than one nonionic surfactant combined at a level of less than 5% by weight based on the weight of the composition. In another embodiment, there may be more than one anionic surfactant combined at a level of less than 5% by weight based on the weight of the composition. In one embodiment, the percentage ratio of nonionic to anionic surfactant(s) is about 50% to 50%, in another embodiment, it is 55% to 45%, and in yet another embodiment, it is about 60% to 40%.

[0058] The surfactant may be present in the compositions of the invention at a level of from about 0.01% to 20% by weight, or from about 0.1% to 10% by weight, or from about 0.1% to 5% by weight. Rheology modifiers

[0059] The compositions according to the invention contain at least one rheology modifier that contributes to both the thickening and the rheological structure of the cleaning concentrate and contributes to the desirable vertical adhesion properties of the invention. The at least one rheology modifier can be selected from the group consisting of organic polymers, natural polymers, inorganic thickeners, and their derivatives. Mixtures of the rheology modifiers can also be used as appropriate.

[0060] According to the invention, at least one rheology modifier selected from the group consisting of acrylic polymers, methacrylic polymers, acrylamide polymers, acrylic and acrylamide copolymers, methacrylic and acrylamide copolymers and mixtures thereof is used.

[0061] In general, any suitable organic polymer can be used as a rheology modifier, whereby this organic polymer generally relates to the class of synthetic or artificially produced polymers. The compositions according to the invention can employ water-soluble or water-dispersible polymers. The compositions according to the invention can employ non-ionic (neutral and / or non-ionizable), anionic and / or cationic polymers and mixtures thereof. Suitable anionic polymers include those having ionizable groups that are at least partially anionic in solution, ie, carry a negative charge in solution, or that can be at least partially or completely neutralized, so that they are at least partially or completely anionic in solution. Suitable cationic polymers include polymers that are ionizable (ie, can be protonated) and those having permanent cationic groups, ie,which carry a permanent positive charge in solution. The compositions of the invention can employ hydrophilic polymers, hydrophobic polymers, or polymers that possess both properties due to the presence of hydrophilic and hydrophobic monomer units. Suitable hydrophilic polymers are those that are attracted to and absorbed onto surfaces without covalent bonds. Examples of suitable polymers include polymers and copolymers of N,N-dialkylacrylamide, acrylamide, and certain monomers containing substituted and / or unsubstituted quaternary ammonium groups and / or amphoteric groups that promote substantivity to surfaces, together with comonomers that promote the adsorption of water, such as acrylic acid and other acrylate salts, sulfonates, betaines, and ethylene oxides.Water-soluble or water-dispersible cationic polymers may be suitable due to their charge-dissipating, antistatic, surface-lubricating, and potential plasticizing benefits.

[0062] With regard to the synthesis of a water-soluble or water-dispersible cationic copolymer, the level of the first monomer, which has a permanent cationic charge or is capable of forming a cationic charge upon protonation, is typically between 3 and 80 mol%, or alternatively between 10 and 60 mol%, based on the copolymer. The level of the second monomer, which is an acidic monomer capable of forming an anionic charge in the composition, when present, is typically between 3 and 80 mol%, or alternatively between 10 and 60 mol%, based on the copolymer. The level of the third monomer, which has an uncharged hydrophilic group, when present, is usually between 3 and 80 mol%, or alternatively between 10 and 60 mol%, based on the copolymer.When present, the level of the uncharged hydrophobic monomer is less than about 50 mol%, or alternatively, less than 10 mol%, based on the copolymer. The molar ratio of the first monomer to the second monomer is typically in the range of 19:1 to 1:10, or alternatively, ranges from 9:1 to 1:6. The molar ratio of the first monomer to the third monomer is typically in the range of 4:1 to 1:4, or alternatively, ranges from 2:1 to 1:2.

[0063] The average molecular weight of the copolymer is typically in the range of about 5,000 to about 10,000,000, the appropriate molecular weight range depending on the polymer composition, with the proviso that the molecular weight is selected such that the copolymer is at least 0.01 wt.% water-soluble or water-dispersible in distilled water at 25°C.

[0064] Examples of permanently cationic monomers include, but are not limited to, quaternary ammonium salts of substituted acrylamide, methacrylamide, acrylate and methacrylate, such as trimethylammonium ethyl methacrylate, trimethylammonium propyl methacrylamide, trimethylammonium ethyl methacrylate, trimethylammonium propyl methacrylamide, 2-vinyl-N-alkyl quaternary pyridinium, 4-vinyl-N-alkyl quaternary pyridinium, 4-vinylbenzyltrialkylammonium, 2-vinylpiperidinium, 4-vinylpiperidinium, 3-alkyl-1-vinylimidazolium, diallyldimethylammonium, and the class of ionenes of internal cationic monomers as described by D.R. Berger in Cationic Surfactants, Organic Chemistry, edited by J.M. Richmond, Marcel Dekker, New York, 1990, ISBN 0-8247-8381-6, described.This class includes co-polyethyleneimine, co-polyethoxylated ethyleneimine, and co-polyquaternized ethoxylated ethyleneimine, co-poly[(dimethylimino)trimethylene(dimethylimino)hexamethylene disalt], co-poly[(diethylimino)trimethylene(dimethylimino)trimethylene disalt], co-poly[(dimethylimino)-2-hydroxypropyl salt], co-polyquarternium-2, co-polyquarternium-17, and co-polyquarternium-18, as described in the International Cosmetic Ingredient Dictionary, 5th edition, edited by J.A. Wenninger and G.N. McEwen. Other cationic monomers include those containing cationic sulfonium salts, such as co-poly-1-[3-methyl-4-(vinylbenzyloxy)phenyl]tetrahydrothiophenium chloride. Particularly suitable monomers are mono- and di-quaternary derivatives of methacrylamide. The counterion of the cationic comonomer can be selected from, for example, chloride, bromide, iodide, hydroxide, phosphate, sulfate, hydrosulfate, ethyl sulfate, methyl sulfate, formate, and acetate.

[0065] Examples of monomers that are cationic upon protonation include, but are not limited to, acrylamide, N,N-dimethylacrylamide, N,N-diisopropylacrylamide, N-vinylimidazole, N-vinylpyrrolidone, ethyleneimine, dimethylaminohydroxypropyldiethylenetriamine, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, dimethylaminoethyl acrylate, dimethylaminopropylacrylamide, 2-vinylpyridine, 4-vinylpyridine, 2-vinylpiperidine, 4-vinylpiperidine, vinylamine, diallylamine, methyldiallylamine, vinyloxazolidone; vinylmethyoxazolidone and vinylcaprolactam.

[0066] Monomers that are cationic upon protonation typically contain a positive charge over a portion of the pH range 2-11. Such suitable monomers are also illustrated in Water-Soluble Synthetic Polymers: Properties and Behavior, Volume II, by P. Molyneux, CRC Press, Boca Raton, 1983, ISBN 0-8493-6136. Additional monomers can be found in the International Cosmetic Ingredient Dictionary, 5th edition, edited by J.A. Wenninger and G.N. McEwen, The Cosmetic, Toiletry, and Fragrance Association, Washington DC, 1993, ISBN 1-882621-06-9. A third source for such monomers can be found in Encyclopedia of Polymers and Thickeners for Cosmetics by R.Y. Lochhead and W.R. Fron, Cosmetics & Toiletries, Vol. 108, May 1993, pp. 95-135.

[0067] Examples of acidic monomers that can form an anionic charge in the composition include, but are not limited to, acrylic acid, methacrylic acid, ethacrylic acid, dimethylacrylic acid, maleic anhydride, succinic anhydride, vinylsulfonate, cyanoacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylideneacetic acid, propylidineacetic acid, crotonic acid, fumaric acid, itaconic acid, sorbic acid, angelic acid, cinnamic acid, styrylacrylic acid, citraconic acid, glutaconic acid, aconitic acid, phenylacrylic acid, acryloxypropionic acid, citraconic acid, vinylbenzoic acid, N-vinylsuccinamidic acid, mesaconic acid, methacroylalanine, acryloylhydroxyglycine, sulfoethyl methacrylate, sulfopropyl acrylate, and sulfoethyl acrylate.Exemplary acid monomers also include styrenesulfonic acid, 2-methacryloyloxymethane-1-sulfonic acid, 3-methacryloyloxypropane-1-sulfonic acid, 3-(vinyloxy)propane-1-sulfonic acid, ethylenesulfonic acid, vinylsulfuric acid, 4-vinylphenylsulfuric acid, ethylenephosphonic acid, and vinylphosphoric acid. Suitable monomers include acrylic acid, methacrylic acid, and maleic acid. Copolymers suitable for this invention may contain the above acidic monomers and their alkali metal, alkaline earth metal, and ammonium salts.

[0068] Examples of monomers with an uncharged hydrophilic group include, but are not limited to, vinyl alcohol, vinyl acetate, vinyl methyl ether, vinyl ethyl ether, ethylene oxide, and propylene oxide. Also suitable are hydrophilic esters of monomers, such as hydroxyalkyl acrylate esters, alcohol ethoxylate esters, alkyl polyglycoside esters, and polyethylene glycol esters of acrylic acid and methacrylic acid.

[0069] Finally, examples of uncharged hydrophobic monomers include, but are not limited to, C1-C4 alkyl esters of acrylic acid and methacrylic acid.

[0070] Suitable copolymers are prepared by copolymerizing the desired monomers. Conventional polymerization techniques may be employed. Illustrative techniques include, for example, solution, suspension, dispersion, or emulsion polymerization. An exemplary preparation method is by precipitation or inverse suspension polymerization of the copolymer from a polymerization medium in which the monomers are dispersed in a suitable solvent. The monomers employed in preparing the copolymers may be water-soluble or sufficiently soluble in the polymerization media to form a homogeneous solution. They readily undergo polymerization to form polymers that are water-dispersible or water-soluble. Exemplary copolymers include acrylamide, methacrylamide, and substituted acrylamides and methacrylamides, acrylic and methacrylic acid, and esters thereof.Suitable synthesis methods for these copolymers are described, for example, in Kirk-Othmer, Encyclopedia of Chemical Technology, Volume 1, Fourth Edition, John Wiley & Sons.

[0071] They may also contain other polymers. Other examples of polymers that provide benefits with regard to film formation and stain prevention are polymers containing hydrophilic amine oxide groups. Polymers containing other hydrophilic groups, such as a sulfonate, pyrrolidone, and / or carboxylate groups, may also be used. Examples of desirable polysulfonate polymers include polyvinylsulfonate and polystyrenesulfonate, such as those sold by Monomer-Polymer Dajac (1675 Bustleton Pike, Feasterville, Pa. 19053). A typical formula is as follows: [CH(C6H4SO3Na)-CH2]1-CH(C6H5)-CH2, where n is a number that provides the appropriate molecular weight, as disclosed below.

[0072] Typical molecular weights range from about 10,000 to about 1,000,000, or alternatively, from about 200,000 to about 700,000. Exemplary polymers containing pyrrolidone functionalities include polyvinylpyrrolidone, quaternized pyrrolidone derivatives (such as Gafquat 755N from International Specialty Products), and copolymers containing pyrrolidone, such as polyvinylpyrrolidone / dimethylaminoethyl methacrylate (available from ISP) and polyvinylpyrrolidone / acrylate (available from BASF). Other substances can also provide substantivity and hydrophilicity, including cationic substances that also contain hydrophilic groups and polymers containing multiple ether linkages. Cationic substances include cationic sugar and / or starch derivatives, and typical block copolymer detergent surfactants based on mixtures of polypropylene oxide and ethylene oxide are examples of polyether substances. However, polyether substances are less substantivizing.

[0073] Also suitable are polymers comprising water-soluble amine oxide units. It is believed that the partial positive charge of the amine oxide group may act to adhere the polymer to the surface of the surface substrate, allowing water to "drain" more easily. To the extent that polymer anchoring promotes better "layer formation," higher molecular weight substances are suitable. Increased molecular weight improves the efficiency and effectiveness of the amine oxide-based polymer. Suitable polymers may have one or more monomer units containing at least one N-oxide group. At least about 10%, suitably more than about 50%, more suitably more than about 90%, of the monomers constituting the polymers contain an amine oxide group.These polymers can be described by the following general formula: P(B), where P is selected from homopolymerizable and copolymerizable units which combine to form the polymer backbone, suitably vinyl units, for example C(R)2=C(R)2, where each R is H, C1-C12, alternatively C1-C4 alkyl(ene), C6-C12 aryl(ene) and / or B; B is a unit selected from substituted and unsubstituted, straight and cyclic C1-C12 alkyl, C1-C12 alkylene, heterocyclic C1-C12, aromatic C6-C12 groups, and where at least one of the B units has at least one amine oxide group; u ranges from a number providing at least about 10% monomers having an amine oxide group to about 90%; and t is a number such that the average molecular weight of the polymer ranges from about 2,000 to about 500,000, alternatively from about 5,000 to about 250,000, and also alternatively from about 7,500 to about 200,000.Exemplary polymers include, but are not limited to, poly(4-vinylpyridine N-oxide) polymers (PVNO), wherein the average molecular weight of the polymer ranges from about 2,000 to about 500,000, alternatively from about 5,000 to about 400,000, and also alternatively from about 7,500 to about 300,000. Generally, higher molecular weight polymers are suitable. Often, higher molecular weight polymers allow the use of lower levels of polymer, which can be advantageous in the surface cleaner applications of the compositions of the invention. Lower molecular weights of the exemplary polyamine oxide polymers of the invention are due to the fact that these higher molecular weight polymers are more difficult to prepare.

[0074] Some non-limiting examples of homopolymers and copolymers that can be used as water-soluble polymers according to the invention are: adipic acid / dimethylaminohydroxypropyldiethylenetriamine copolymer; adipic acid / epoxypropyldiethylenetriamine copolymer; polyvinyl alcohol; methacryloylethylbetaine / methacrylate copolymer, ethyl acrylate / methyl methacrylate / methacrylic acid / acrylic acid copolymer; polyamine resins and polyquaternary amine resins; poly(ethenylformamide); poly(vinylamine) hydrochloride; poly(vinyl alcohol-co-vinylamine); poly(vinyl alcohol-co-vinylamine); poly(vinyl alcohol-co-vinylamine); poly(vinyl alcohol-co-vinylamine hydrochloride) and poly(vinyl alcohol-co-vinylamine hydrochloride).Alternatively, the copolymer and / or homopolymers are selected from the group consisting of adipic acid / dimethylaminohydroxypropyldiethylenetriamine copolymer, poly(vinylpyrrolidone / dimethylaminoethyl methacrylate); polyvinyl alcohol; ethyl acrylate / methyl methacrylate / ethacrylic acid / acrylic acid copolymer; methacryloylethyl betaine / methacrylate copolymer; polyquaternary amine resins; poly(ethenylformamide), poly(vinylamine) hydrochloride; poly(vinyl alcohol-co-vinylamine); poly(vinyl alcohol-co-vinylamine); poly(vinyl alcohol-co-vinylamine); poly(vinyl alcohol-co-vinylamine hydrochloride) and poly(vinyl alcohol-co-vinylamine hydrochloride).

[0075] Suitable polymers can be selected from the group consisting of copolymers of hydrophilic monomers. The polymer can be linear random or block copolymers and mixtures thereof. The term "hydrophilic" is used herein in accordance with its standard meaning as having at least some affinity for water. As used herein with reference to monomer units and polymer substances, including copolymers, "hydrophilic" means substantially water-soluble and / or substantially water-dispersible. In this regard, "substantially water-soluble" or "substantially water-dispersible" shall refer to a substance that is soluble and / or dispersible in distilled (or equivalent) water at 25°C at a concentration of about 0.0001 wt% or more.The terms "soluble", "solubility", "dispersible" and the like, for the purposes of the invention, correspond to the maximum concentration of monomer or polymer, as applicable, that can dissolve or be dispersed in water and / or other solvents or mixtures thereof and form a homogeneous solution, as understood by one of skill in the art.

[0076] Non-limiting examples of suitable hydrophilic monomers are unsaturated organic mono- and polycarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and their half-esters, itaconic acid; unsaturated alcohols, such as vinyl alcohol, allyl alcohol; polar vinyl heterocycles, such as vinylcaprolactam, vinylpyridine, vinylimidazole; vinylamine; vinylsulfonate; unsaturated amides, such as acrylamides, e.g., N,N-dimethylacrylamide, Nt-butylacrylamide; hydroxyethyl methacrylate; dimethylaminoethyl methacrylate; salts of the above-listed acids and amines, and the like, and mixtures thereof. Some exemplary hydrophilic monomers are acrylic acid, methacrylic acid, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, Nt-butylacrylamide, dimethylaminoethyl methacrylate, and mixtures thereof.

[0077] Polycarboxylate polymers are those prepared by polymerizing monomers, at least some of which contain carboxylic acid functionality. Common monomers are acrylic acid, maleic acid, ethylene, vinylpyrrolidone, methacrylic acid, methacryloylethylbetaine, etc. Exemplary polymers for substantivity are those with higher molecular weights. For example, polyacrylic acid with molecular weights below about 10,000 is not particularly substantivizing and therefore does not typically provide the hydrophilicity for three rewettings of a treated surface with the compositions of the invention, although molecular weights down to about 1,000 may provide some results at higher levels. Generally, the polymers should have molecular weights greater than about 10,000. It has also been found that higher molecular weight polymers, e.g.Those with molecular weights greater than about 10,000,000 are extremely difficult to formulate and are less effective at providing stain prevention benefits than lower molecular weight polymers. Accordingly, the molecular weight, particularly for polyacrylates, should typically range from about 1,000 to about 10,000,000, alternatively from about 5,000 to about 5,000,000, alternatively from about 10,000 to about 2,500,000, and also suitably from about 20,000 to about 1,000,000.

[0078] Non-limiting examples of polymers for use in the present invention include the following: Poly(vinylpyrrolidone / acrylic acid) sold under the name "Acrylidone" ® marketed by ISP, and poly(acrylic acid), which is sold under the name "Accumer" ® sold by Rohm & Haas. Other suitable substances include sulfonated polystyrene polymers sold under the name Versaflex ®distributed by the National Starch and Chemical Company, primarily Versaflex 7000.

[0079] Suitable polymers can be selected from the group consisting of water-soluble and water-dispersible polyacrylate polymers and copolymers containing at least one acrylate monomer, water-swellable and alkali-swellable polyacrylate polymers and copolymers containing at least one acrylate monomer, non-linear polyacrylate polymers crosslinked with at least one polyalkenyl polyether monomer, film-forming and water-swellable insoluble polyacrylate polymers, hydrophobically modified crosslinked polyacrylate polymers and copolymers containing at least one hydrophobic monomer, water-dispersible associative and non-associative polyacrylate polymers and copolymers containing at least one acrylate monomer, and mixtures thereof. Examples of hydrophobically modified alkali-soluble acrylic polymer emulsions are sold under the name ACUSOL. ®Distributed by Rohm and Haas. Suitable polymers, copolymers, or their derivatives are also selected from polyvinyl alcohols, polyvinylpyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyamino acids or peptides, polyamides, polyacrylamide, copolymers of maleic acid / acrylic acid, polysaccharides, including starch and gelatin, natural gums such as xanthan gum and carrageenan. Exemplary polymers are also selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, and polymethacrylates. Also suitable are polymers selected from polyvinyl alcohols, polyvinyl alcohol copolymers, hydroxypropyl methylcellulose (HPMC), xanthan gum and starch.The polymer may have any weight average molecular weight from about 1000 to 1 000 000 or even from 10 000 to 300 000 or even from 15 000 to 200 000 or even from 20 000 to 150 000.

[0080] Also suitable are polymer blend compositions, for example blends containing a hydrolytically degradable and water-soluble polymer blend, such as polylactide and polyvinyl alcohol, obtained by blending polylactide and polyvinyl alcohol and typically comprising 1-35 wt% polylactide and from about 65 wt% to 99 wt% polyvinyl alcohol if the substance is to be water-dispersible or water-soluble.

[0081] In general, natural polymers and derivatized natural polymers can be used as rheology modifiers. Some non-limiting examples of natural polymers and derivatized natural polymers suitable for use in the present invention include polysaccharide polymers, including substituted cellulose substances such as carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, succinoglycan, and naturally occurring polysaccharide polymers such as xanthan gum, guar gum, locust bean gum, tragacanth gum, carrageenan gum, or derivatives thereof. Also suitable are polypeptides and proteins such as, but not limited to, gelatin and its derivatives, peptin, peptone, and the like, as well as polysaccharide and peptide copolymers such as peptidoglycans and the like.

[0082] Also suitable for use as rheology modifiers are inorganic thickeners, typically in the form of finely divided additives, including colloids and nanoparticles. Examples of such inorganic thickeners include, but are not limited to, substances such as natural clays, silicas, zeolites, finely divided metal oxides, finely divided inorganic minerals, and nanoparticulate forms of such substances, and mixtures thereof. Also included are derivatized inorganic thickeners such as fumed silica, silanized silica, and hydrophobized silica, and the like. Examples of metal oxides include, but are not limited to, oxides of alkali metals, alkaline earth metals, and transition metals from Groups IIA, IVB, VB, VIIB, VIII, IB, IIB, IIA, and IVA of the Periodic Table. silicone

[0083] The protectant composition comprises about 5% to about 15% by weight of the composition. The composition of the invention requires at least one organopolysiloxane fluid. These fluids are also commonly referred to as "silicone oils" or "silicones" and are distinguished from silicone elastomers and resins, which are more highly crosslinked than silicone oils. The silicone of the composition is an organopolydimethylsiloxane, which has a pure viscosity of about 10 mm 2 / s (cSt) to about 1 000 000 mm 2 / s (cSt) and preferably of about 50 mm 2 / s (cSt) to about 100 000 mm 2 / s (cSt). The protectant composition forms a sprayable, aqueous organopolysiloxane emulsion. In one embodiment, the silicone component of the composition may contain a mixture of both high- and low-viscosity organopolysiloxanes.

[0084] Generally speaking, the organopolysiloxanes are those that can be easily dispersed to form aqueous emulsions and are resistant to gelation in the aqueous composition. Preferred are polydimethylsiloxanes end-masked with dimethylsilanolyl groups or, more preferably, trimethylsilyl groups. Polydimethylsiloxanes that are lightly or moderately branched are also preferred. Another category of preferred organopolysiloxanes are aminoalkyl-functional and polyaminopolyalkyl-functional polydimethylsiloxanes with terminal, pendant, or both terminal and pendant aminoalkyl or polyaminopolyalkyl groups. Mixtures of different organopolysiloxanes can also be used, in particular mixtures of organopolysiloxanes with different viscosities, for example, mixtures of low- and high-viscosity siloxanes, for example, mixtures of siloxanes with viscosities in the range of 10 mm2 / s (cSt) up to 10 000 mm 2 / s (cSt) and 1000 mm 2 / s (cSt) up to 1 000 000 mm 2 / s (cSt), with the siloxane in the latter range having a higher viscosity than that in the former. In addition to polydimethylsiloxanes, resinous organopolysiloxanes can be added in smaller amounts to increase resistance.

[0085] The organopolysiloxanes are used in the form of an aqueous emulsion, preferably with a relatively small particle size, for example in the range of 10 nm to 1000 nm, more preferably in the range of 100 nm to 800 nm and most preferably in the range of 200 nm to 450 nm.

[0086] Suitable silicone fluids include those based on organopolysiloxanes, which are selected from the class of polymers with the following general formula: (RnSiO ((4-n) / 2)) m (I), where n is between 0 and 3, m is 2 or more, and R is alkyl or aryl, as defined in Silicone Compounds Register and Review, 5th ed., R. Anderson, G. L. Larson, and C. Smith, Eds., Hüls America Inc., Piscataway, NJ, p. 247 (1991). The value of m can be up to one million or more, but is more commonly a value between about 5 and 1000, representing free-flowing fluids with good handling and performance characteristics. These exemplary silicones can be straight or branched.Various naming conventions and nomenclature substantially equivalent to this exemplary class of silicones include, but are not limited to: dialkylpolysiloxane hydrolysate; alpha-alkyl-omega-methoxypolydialkylsiloxane; polydialkylsilicone oil; poly(dialkylsiloxane); alkyl-endblocked polydialkylsiloxane; polyoxy(dialkylsilylene), alpha-(trialkylsilyl)-omega-hydroxy; poly[oxy(dialkylsilylene)], alpha-[trialkylsily-]-omega-[(trialkylsilyl)oxy], and alpha-(trialkylsilyl)poly[oxy(dialkylsilylene)]-omega-alkyl. Some additional suitable examples also include dimethicone copolyol, dimethylpolysiloxane, diethylpolysiloxane, high molecular weight dimethicone, mixed C1-C30 alkylpolysiloxane, phenyl dimethicone, dimethiconol, and mixtures thereof.

[0087] Non-limiting examples of silicones useful in the present invention are also described in U.S. Pat. No. 5,011,681 to Ciotti et al. The silicone compounds useful herein also include polyalkyl or polyarylsiloxanes. The alkyl or aryl groups substituted on the siloxane chain (R) or on the ends of the siloxane chains can have any structure, as long as the resulting silicone remains flowable at or around room temperature. Suitable R groups are hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, phenyl, methylphenyl, phenylphenyl, aryl, and aryloxy. One or more R groups on the silicon atom can be the same or different groups, or any combination thereof. Suitable silicone compounds are polydimethylsiloxane, polydiethylsiloxane, and polymethylphenylsiloxane.Polydimethylsiloxane, also known as dimethicone, is suitable and available in many forms and grades, including, for example, edible grades suitable for use in compositions intended for use in contact with food. Polyalkylsiloxanes that can be used include, for example, polydimethylsiloxanes. These silicone compounds are used, for example, by the General Electric Company in its Visca-sil. ®- and SF 96 series, and from Dow Corning in their Dow Corning 200 series. Polyalkylarylsiloxane fluids containing one or more alkyl or alkylaryl substituents may also be used and include, for example, but are not limited to, polymethylphenylsiloxanes, poly[(dimethylsiloxane) / (methylvinylsiloxane)], poly[(dimethylsiloxane) / (diphenylsiloxane)], poly[(dimethylsiloxane) / (phenylmethylsiloxane)], and poly[(dimethylsiloxane) / (diphenylsiloxane) / (methylvinylsiloxane)]. These siloxanes are available, for example, from the General Electric Company as SF 1075 methylphenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid, Rhodorsil 763 from Rhône-Poulenc, Silbione 70641 V 30 and 70641 V 200 from Rhône-Poulenc, the PK series silicones from Bayer, such as PK20, the PN and PH series silicones from Bayer, such as PN 1000 and PH 1000, and certain oils of the SF series from General Electric, such as SF 1250, SF 1265, SF 1154 and SF 1023.Higher molecular weight silicones, including silicone gums and resins, can be used in the invention and include polydiorganosiloxanes having a molecular weight between 200,000 and 5,000,000, used alone or as a mixture in a solvent selected from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, methylene chloride, pentane, dodecane, tridecane and tetradecane or mixtures thereof.

[0088] The silicones can be straight or branched and can be modified with chemical groups to provide additional properties. For example, suitable silicones also include amino-modified silicones, where R is an amine, amide, or an alkyl-, dialkyl-, or trialkyl-derivatized amine moiety. Other organopolysiloxanes can be prepared by substituting one or more of the R groups with other organic or functionalized organic groups, such as vinyl, phenyl, fluoroalkyl, perfluoroalkane, carboxylic acid derivatives, carboxyesters, and quaternary ammonium derivatives.These include mixtures of these substances, for example, but not limited to: 1) mixtures made from a chain-end hydroxylated polydimethylsiloxane (dimethiconol according to the CTFA nomenclature) and from a cyclic polydimethylsiloxane (cyclomethicone according to the CTFA nomenclature), such as the product Q2 1401 marketed by Dow Corning; 2) Mixtures made from a polydimethylsiloxane rubber with a cyclic silicone, such as General Electric's SF 1214 Silicone Fluid, which is an SE 30 rubber with a MW of 500,000 dissolved in SF 1202 Silicone Fluid (decamethylcyclopentasiloxane); 3) Mixtures of two PDMS substances of different viscosities, for example, a PDMS rubber and a PDMS oil, such as General Electric's SF 1236 and CF 1241 products. The "SF 1236" product is a mixture of an SE 30 rubber as defined above with a viscosity of 20 m. 2 / s and from an SF 96 oil with a viscosity of 5 x 10 -5 m 2 / s (15% SE 30 rubber and 85% SF 96 oil). The product "CF 1241" is a mixture of an SE 30 rubber (33%) and a PDMS (67%) with a viscosity of 10 -3 m 2 / s.

[0089] The organo-modified silicones according to the invention are silicones as defined above which contain in their general structure one or more organofunctional groups which are bonded directly to the siloxane chain or via a hydrocarbon-based radical. Examples of these are silicones containing: a) polyethyleneoxy and / or polypropylenoxy groups, optionally containing alkyl groups, such as: the product known as dimethicone copolyol, marketed by Dow Corning under the name ‘DC 1248’, and alkyl(C12)methicone copolyol, marketed by Dow Corning under the name ‘Q2 5200’, the ‘Silwet’ L 722, L 7500, L 77 and L 711 oils from General Electric, the mixture of dimethicone copolyol and cyclomethicone, such as the product marketed by Dow Corning under the trade name ‘Q2-3225C’, the product ‘Mirasil DMCO’ marketed by Rhöne-Poulenc, b) (per)fluoro groups,for example, trifluoroalkyl groups, such as those sold by General Electric under the names 'FF 150 Fluorosilicone Fluid' or by Shin Etsu under the names 'X-22-819', 'X-22-820', 'X-22-821', 'X-22-822' or 'FL 100'; c) hydroxylacylamino groups, such as those described in European patent application EP-A-0 342 834 and in particular the silicone sold by Dow Corning under the name 'Q2-8413'; d) thiol groups, such as in the silicones 'X 2-8360' by Dow Corning or 'GP 72A' and 'GP 71' by Genesee; Union Carbide or the silicone known as 'Amodimethicone' in the CTFA dictionary; f) carboxylate groups, such as the products described in European patent EP 186 507 of Chisso Corporation; g) hydroxylated groups, such as the polyorganosiloxanes containing a hydroxyalkyl function described in patent application FR-A-2,589,476, and in particular polyorganosiloxanes,containing a γ-hydroxypropyl function; h) alkoxylated groups containing at least 12 carbon atoms, such as the product ‘Silicone Copolymer F 7551’ from SWS Silicones and the products ‘Abilwax 2428’, ‘Abilwax 2434’ and ‘Abilwax 2440’ from Goldschmidt; i) acyloxyalkyl groups containing at least 12 carbon atoms, such as the polyorganosiloxanes described in patent application FR-A-2 641 185, in particular polyorganosiloxanes containing a stearoyloxypropyl function; j) quaternary ammonium groups, such as in the products ‘X2 81 08’ and ‘X2 81 09’ and the product ‘Abil K 3270’ from Goldschmidt; k) amphoteric or betaine groups, such as in the product marketed by Goldschmidt under the name "Abil B 9950"; 1) bisulfite groups, such as in the products marketed by Goldschmidt under the names "Abil S 201" and "Abil S 255".

[0090] The block copolymers having a straight polysiloxane-polyoxyalkylene block as a repeating unit used in the present invention include those having the following general formula: ([Y(R2SiO)aR'2SiYO] [CnH2nO)b])c (II), in which R and R', which may be the same or different, represent a monovalent hydrocarbon-based radical without aliphatic unsaturation, n is an integer in the range from 2 to 4, a is an integer greater than or equal to 5, in particular between 5 and 200 and very particularly between 5 and 100, b is an integer greater than or equal to 4, in particular between 4 and 200 and very particularly between 5 and 100, c is an integer greater than or equal to 4, in particular between 4 and 1000 and very particularly between 5 and 300, Y represents a divalent organic group which is bonded to the adjacent silicon atom via a carbon-silicon bond and to a polyoxyalkylene block via an oxygen atom, each siloxane block having a molecular weight between about 400 and about 10,000 and each polyoxyalkylene block having a molecular weight between about 300 and about 10 000, the siloxane blocks about 10% to 95%,based on the weight of the block copolymer, the average molecular weight of the block copolymer is at least 3000 and in particular between 5000 and 1 000 000 and most particularly between 10 000 and 200 000. R and R' are suitably selected from the group comprising alkyl radicals such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl and dodecyl, aryl radicals such as phenyl and naphthyl, arylalkyl radicals such as benzyl and phenethyl, and tolyl, xylyl and cyclohexyl radicals. Y is suitably selected from radicals including -R''¾, ¾R''¾CO¾, ¾R''¾NHCO¾, ¾R''¾NH¾CO¾NH¾R''¾NHCO or ¾R''¾OCONH¾R'''¾NHCO¾, where R'' is a divalent alkylene group such as ethylene, propylene or butylene, and R''' is a divalent alkylene group or a divalent arylene group such as ¾C6H4, ¾C6H4C6H4¾, C6H4¾CH2¾C6H4, C6H4¾C(CH3)2C6H4. More particularly, Y represents a divalent alkylene radical, more specifically,the residue ¾CH2¾CH2¾CH2¾ or the residue ¾C4H8¾. The preparation of the block copolymers used in connection with the present invention is described in European application EP 0 492 657 A1.

[0091] Also suitable for use, particularly in combination with other silicone oils, is the class of silicone wetting and / or leveling agents, which assist in the spreading and leveling of silicone oils on treated surfaces. Some of the exemplary silicones described above can serve this purpose in addition to their coating properties. Other examples also include, but are not limited to, polyalkylene oxide-modified polydimethylsiloxane available from General Electric as Silwet 7650, polyalkylene oxide-modified heptamethyltrisiloxane available as Silwet 7280 and Silwet 7608, also available from General Electric, silicone glycol copolymer surfactant available from Dow Corning as DC 57, and the Dow Corning silicone polyether surfactant designated Q2-5211. Another example from Dow Corning is a polyalkylene oxide-modified heptmethyltrisiloxane called FZ-77.Further examples also include substances with additional flow control properties, such as, but not limited to, the alkylmethylsiloxanes DC 56 available from Dow Corning and the organomodified dimethylsiloxane known as Formasil 433 available from General Electric.

[0092] Mixtures and combinations of any of the silicone oils exemplified herein, for example, silicone oils with different molecular weights, different viscosities, differently functionalized derivatives, different volatilities and / or vapor pressures, different properties and benefits, and combinations thereof, can be advantageously combined in the compositions of the invention. For example, a "lighter" polyorganosiloxane or a low-viscosity polyorganosiloxane can be combined with a "heavier" silicone oil or a higher-viscosity silicone oil and / or a silicone rubber and / or silicone elastomer for the purpose of dispersion in the compositions of the invention, where the "heavier" substances would otherwise be difficult to handle and disperse if used alone or in combinations without a "lighter" silicone included.Alternatively, depending on the end use, a volatile silicone oil can be combined with a less volatile or substantially non-volatile silicone oil. Alternatively, a silicone oil with spreading, wetting, or selective leveling properties can be combined with another silicone oil to improve the spreading and leveling of the combined silicone oil mixture, thus achieving a positive effect on the surfaces treated with the inventive compositions described herein.

[0093] The use of silicone oils in the compositions of the invention containing these and other substituted organopolysiloxanes, and combinations and mixtures thereof, is a matter of choice depending on the material to be treated and / or the environment to which the treated materials are exposed, as well as the desired surface properties to be imparted to the surface. The silicones can be premixed in their desired proportions prior to processing, mixed during the actual processing of the compositions of the invention, or incorporated into the compositions of the invention in any suitable order or manner, subject exclusively to considerations of ease of handling, transportation, mixing, and processing of the compositions of the invention.

[0094] The organopolysiloxane in the composition is believed to provide a water and water vapor resistant coating on the surface of the treated materials, thus improving their resistance to environmental stress such as water and oxygen penetration and attack by other environmental pollutants.

[0095] Organopolysiloxanes are also suitable for imparting a gloss or glossy finish to treated surfaces, resulting in improved appearance and other aesthetic benefits associated with the modification of incident light, such as refractive and diffusive contributions to specular reflections, which contribute to a perception of enhanced color and hue and a reduced perception of surface defects such as scratches, stress cracks, streaks, and other surface defects that commonly develop on surfaces with normal age and wear. Therefore, due to their restorative effect, organopolysiloxanes are useful when used on old and worn surfaces, especially elastomeric surfaces, which are most susceptible to these conditions.

[0096] The organopolysiloxane in the composition is also believed to provide a dirt- and oil-resistant coating on the surface of treated substances, such as household surfaces, including, but not limited to, stainless steel, tile, porcelain, marble, and the like, thereby improving their resistance to stains and soiling, water, and microbial growth. In one embodiment of the present invention, the organopolysiloxane comprises one or more of a silicone selected from the group consisting of polydimethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, polyalkylarylsiloxane, polyethyleneoxydialkylsiloxane, polypropyleneoxydialkylsiloxane, and polydialkylcyclosiloxane.

[0097] In suitable embodiments, the organopolysiloxane comprises 5 wt% to about 15 wt%, or 5 wt% to about 12 wt%, or alternatively 8 wt% to about 10 wt%, based on the weight of the composition of the invention.

[0098] The silicone component of the composition is used to prepare an aqueous organopolysiloxane emulsion and can be present in a concentrated or diluted organopolysiloxane emulsion. Conventional organopolysiloxane emulsions are also commercially available. For example, silicone fluid emulsions E10, E103P, E1044, E125P, E1656, E677, E60-350, E60-1000, and others are available from Wacker Silicones, Adrian, Mich., and from Wacker-Chemie GmbH, Munich, Germany. The emulsions of the invention can start from commercially available emulsions to which the remaining ingredients are added, or can be prepared by mixing and emulsifying pure organopolysiloxane with suitable surfactants and optionally including ingredients such as UV protectants, plasticizers, spreading agents, etc.Such emulsions typically contain 40 to 70 weight percent organopolysiloxane and are diluted with additional water for use. Glycols such as propylene glycol, ethylene glycol, or low molecular weight polyols such as glycerin, etc., can be added during the initial preparation of the emulsion to ensure a stable, easily dispersible emulsion concentrate.

[0099] The organopolysiloxane emulsions used herein are preferably stable, small-particle-sized emulsions. By "stable," with respect to the emulsions, we mean that the emulsions do not separate over extended periods of time, typically having a shelf life at room temperature of about 2 years or more. Shelf life can be examined by observing the particle size after storage for 1 month at 50°C. Generally, there should be less than a 20% increase in particle size over this period, more preferably less than a 10% increase. The particle size should be less than 450 nm. Stability can also be examined by centrifuge testing. Stable emulsions should exhibit less than 1 inch, more preferably less than 0.5 inch, and even more preferably less than 0.2 inch of phase separation. Most preferably, no phase separation is observed.Stable emulsions do not require any additional surfactants, thickeners, or other additives beyond those originally used in the emulsification process to keep the dispersed phase free from separation or coalescence.

[0100] The organosilicone emulsion of the invention contains a gloss-enhancing additive. It has surprisingly been discovered that gloss-enhancing additives can be selected from inorganic thickeners and water-soluble aqueous thickeners present in extremely small amounts so that the protectant remains sprayable, as that term is defined herein. Numerous thickeners in these categories have been tested and all have been found to contribute to gloss improvement. Suitable gloss-enhancing additives are preferably compositions that exhibit a slight increase in the viscosity of aqueous emulsions at low concentrations. Examples of such water-soluble additives are the various soluble polyacrylic acid and polyacrylic acid / polyacrylate copolymers, such as those sold under the trade name CARBOPOL ® available or, more precisely, CARBOPOL ®EZ-3, various polyacrylamides; associative polyethers, such as polyoxyethylene and polyoxyethylene / polyoxypropylene copolymer polyethers end-capped with C8-30 α-olefin oxides; various vegetable gums, for example, tragacanth, acacia, gum arabic, carrageenan, xanthan gum, and the like; and various cellulose ethers, for example, carboxymethylcellulose, hydroxypropylcellulose, and similar products. Among the inorganic, water-insoluble thickeners, various clay minerals, such as bentonite, and fumed silica are also suitable. Reference may be made in this context to MCCUTCHEON'S VOLUME 2: FUNCTIONAL MATERIALS, 1997 North American Edition, McCutcheon's Division, MC Publishing Co., Glen Rock, NJ. solvent

[0101] In one embodiment of the invention, the protectant composition does not contain any organic solvent. Instead of an organic solvent, the composition contains about 65% to about 95% water, or alternatively, about 70% to 85% water, or alternatively, about 75% to 85% water, by weight of the composition. In one embodiment, the composition is substantially free of organic solvents because they contribute to a smeared or hazy appearance after the composition has dried on the surface. In this embodiment, it is preferable to keep the composition free of organic solvents so that the composition forms a uniform, glossy, and clear coating on automotive surfaces.

[0102] In another embodiment of the invention, the organic solvent constitutes less than 1% of the composition, more preferably less than 0.5% of the composition, and most preferably less than 0.01 percent of the composition. In a third embodiment of the invention, the protectant composition comprises a small amount of solvent that contributes to the removal of dirt, grease, and other unwanted contaminants from the surface to be treated. The particular solvent used in the composition of the invention can be selected depending on the particular end use and, in particular, the type of surface to be treated.Furthermore, the solvent can help solubilize insoluble or poorly water-soluble excipients, such as ultraviolet (UV) absorbers, fragrances, perfumes, and the like, to prevent the separation of these ingredients in the compositions of the invention. Suitable solvents include both hydrophilic and hydrophobic compounds, generally encompassing solvents that are water-soluble, water-miscible, and water-insoluble and water-immiscible. Mixtures of any solvents can optionally be employed in the compositions of the invention.

[0103] Suitable organic solvents include, but are not limited to, monohydric alcohols and polyhydric alcohols, such as C 1-6 -alkanols and C 1-6 -diols, alkylene glycols, such as C 1-10-Alkyl ethers of alkylene glycols, glycol ethers, such as C 3-24Alkylene glycol ethers, polyalkylene glycols, short-chain carboxylic acids, short-chain esters, isoparaffinic hydrocarbons, mineral spirits, alkyl aromatics, terpenes, terpene derivatives, terpenoids, terpenoid derivatives, formaldehyde, and pyrrolidones. Alkanols include, but are not limited to, monohydric alcohols, including, for example, methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, and hexanol, and their isomers. Diols include, but are not limited to, methylene, ethylene, propylene, and butylene glycols.Alkylene glycol ethers include, but are not limited to, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol monobutyl ether, propylene glycol t-butyl ether, di- or tripolypropylene glycol methyl or ethyl or propyl or butyl ether, acetate and propionate esters of glycol ethers. Short-chain carboxylic acids include, but are not limited to, acetic acid, glycolic acid, lactic acid, and propionic acid. Short-chain esters include, but are not limited to, glycol acetate and cyclic or even volatile methylsiloxanes.Water-insoluble solvents such as isoparaffinic hydrocarbons, mineral spirits, alkyl aromatics, terpenoids, terpenoid derivatives, terpenes and terpene derivatives, can, if used, be mixed with a water-soluble solvent.

[0104] Examples of organic solvents with a vapor pressure of less than 0.1 mm Hg (20°C) include, but are not limited to, dipropylene glycol n-propyl ether, dipropylene glycol t-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-butyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, and diethylene glycol butyl ether acetate (all available from ARCO Chemical Company).

[0105] When used, the solvents are optionally present at a level of from 0.001 wt% to 10 wt%, alternatively from 0.01 wt% to 10 wt%, or alternatively from 1 wt% to 4 wt%. Alkalinity source

[0106] The composition of the invention may also contain an alkalinity source, which is believed to increase the effectiveness of the surfactant and the overall cleaning efficiency of the compositions. The alkalinity source may be a builder, a buffer, and / or a pH-adjusting agent, which may also act as a water softener, and / or a sequestering agent in the composition of the invention. The builder, buffer, and pH-adjusting agent may be used alone or in mixtures, or in combination with, or in the form of, their corresponding conjugate acids and / or conjugate bases to adjust and control the pH of the compositions of the invention.

[0107] A variety of builders or buffers may be used, including, but not limited to, phosphate silicate compounds, zeolites, alkali metal, ammonium, and substituted ammonium polyacetates, trialkali salts of nitrilotriacetic acid, carboxylates, polycarboxylates, carbonates, bicarbonates, polyphosphates, aminopolycarboxylates, polyhydroxysulfonates, and starch derivatives. Builders or buffers may also include polyacetates and polycarboxylates.The polyacetate and polycarboxylate compounds include, but are not limited to, sodium, potassium, lithium, ammonium, and substituted ammonium salts of ethylenediaminetetraacetic acid, ethylenediaminetriacetic acid, ethylenediaminetetrapropionic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, oxydisuccinic acid, iminodisuccinic acid, mellitic acid, polyacrylic acid or polymethacrylic acid and copolymers, benzenepolycarboxylic acids, gluconic acid, amidosulfonic acid, oxalic acid, phosphonic acid, organic phosphonic acids, acetic acid, and citric acid. These builders or buffers may also be present either partially or entirely in the hydrogen ion form.

[0108] The builder may include sodium and / or potassium salts of EDTA and substituted ammonium salts. The substituted ammonium salts include, but are not limited to, ammonium salts of methylamine, dimethylamine, butylamine, butylenediamine, propylamine, triethylamine, trimethylamine, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, ethylenediaminetetraacetic acid, and propanolamine.

[0109] Buffering and pH-adjusting agents, when used, include, but are not limited to, organic acids, mineral acids, alkali metal and alkaline earth metal salts of silicate, metasilicate, polysilicate, borate, hydroxide, carbonate, carbamate, phosphate, polyphosphate, pyrophosphates, triphosphates, tetraphosphates, ammonia, hydroxide, monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, triethanolamine, and 2-amino-2-methylpropanol. Suitable buffering agents for the compositions of the invention are nitrogen-containing substances. Some examples are amino acids, such as lysine, or lower alcohol amines, such as monoalkanolamine, dialkanolamine, and trialkanolamine. Examples of suitable alkanolamines include the mono-, di-, and triethanolamines.Other suitable nitrogen-containing buffering agents include tri(hydroxymethyl)aminomethane (TRIS), 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanol, disodium glutamate, N-methyldiethanolamide, 2-dimethylamino-2-methylpropanol (DMAMP), 1,3-bis(methylamine)cyclohexane, 1,3-diaminopropanol-N,N'-tetramethyl-1,3-diamino-2-propanol, N,N-bis(2-hydroxyethyl)glycine (bicine), and N-tris(hydroxymethyl)methylglycine (tricine). Other suitable buffers include ammonium carbamate, citric acid, and acetic acid. Mixtures of any of the above are also acceptable. Suitable inorganic buffers / alkalinity sources include ammonia, alkali metal carbonates, and alkali metal phosphates, e.g., sodium carbonate and sodium polyphosphate. Further buffers are described in WO 95 / 07971. Other suitable pH-adjusting agents include sodium or potassium hydroxide.

[0110] When employed, the alkalinity source, builder, buffer, or pH adjusting agent constitutes at least about 0.001% and typically about 0.01% to 5% of the composition of the invention. Alternatively, the builder, buffer, or pH adjusting agent content is about 0.01% to 2%. Excipients

[0111] The composition of the invention may contain additional optional adjuvants, such as one or more cleaning agents, cleaning aids, protectants, chelators, builders, co-solvents, co-surfactants, descaling agents, foam boosters, foam depressants, surface modifiers, pH adjusting agents, pH buffers, wetting agents, stain and soil repellents, waxes, resins, polishes, abrasives, colloid stabilizers, waxes, lubricants, odor control agents, perfumes, fragrances and fragrance release agents, brighteners, optical brighteners, ultraviolet light (UV) absorbers, UV scattering agents, excited state quenchers, antioxidants, oxygen quenchers, bleaching agents, electrolytes, dyes and / or colorants, phase stabilizers, emulsifiers, thickeners, defoamers, hydrotropes, cloud point modifiers, antimicrobials, preservatives and mixtures of that.

[0112] These one or more optional adjuvants may be used in embodiments of the compositions of the invention to impart further cleaning and protective benefits or functionality to the compositions of the invention.

[0113] When employed, these one or more optional excipients may individually comprise from 0.0001% to about 5% by weight, or from 0.001% to about 5% by weight, or alternatively from 0.01% to about 1% by weight, based on the weight of the composition of the invention. Procedure for application

[0114] The protectant compositions of the present invention are generally used to protect and / or clean the surfaces of vehicles, including, for example, but not limited to, automobiles, trucks, aircraft, motorcycles, boats, marine vessels, trailers, recreational vehicles, jet skis, snowmobiles, bicycles, tractors, and scooters. The compositions of the present invention are suitably used to treat and clean a variety of surface materials, e.g., building materials, including, but not limited to, rubber, vinyl, leather, plastics, wood, elastomers, tires, wheels, hubcaps, tarps, vehicle covers, and combinations thereof.

[0115] In one embodiment, the compositions of the invention can be applied directly to a soiled or clean automotive surface, preferably by a manual spray device or an aerosol spray device. Alternatively, in another embodiment, compositions of the invention can be applied to an applicator, including, for example, but not limited to, a sponge, cloth, towel, wet wipe, wiper, absorbent pad, foam, shami, or similar carrier, or a tool employing a combination thereof. In either application method, the vertical adhesion parameter of the compositions of the invention is sufficient to substantially hold the applied compositions in place at the desired location.In embodiments in which the compositions of the invention are first applied to an applicator and then applied to the soiled exterior surface or soiled material surface, the vertical adhesion parameter of the applied compositions of the invention is sufficient to substantially hold the applied compositions in place at the desired location. Means of useSpray dispenser

[0116] Compositions of the invention can also be sprayed directly onto the target surface and therefore packaged in a spray dispenser. The spray dispenser can be any of the manually operated devices for producing a spray of liquid droplets known in the art, e.g., spray guns, pump bottles, electric sprayers, hydraulic nozzles, ultrasonic nebulizers, high-pressure nebulizing nozzles, self-pressurized non-aerosol sprayers, and aerosol sprayers. Automatically triggered devices can also be used herein. These types of automatic devices are similar to manually triggered devices except that the propellant is replaced by a compressor.

[0117] The spray dispenser may be an aerosol dispenser. The aerosol dispenser comprises a container that can be made from any of the conventional materials used to manufacture aerosol containers. The dispenser must be capable of withstanding an internal pressure in the range of about 5 to about 120 psig, or alternatively, about 10 to about 100 psig. One important requirement regarding the dispenser is that it be provided with a valve component that allows the compositions of the invention contained in the dispenser to be dispensed in the form of a continuous stream or spray of droplets. The aerosol dispenser utilizes a pressurized, sealed container from which the composition of the invention is dispensed under pressure by a trigger / valve element. The aerosol dispenser is pressurized by introducing a gaseous component, commonly known as a propellant, into it.A more complete description of commercially available aerosol spray dispensers appears in U.S. Pat. No. 3,436,772, Stebbins, and U.S. Pat. No. 3,600,325, Kaufman et al.

[0118] Alternatively, in one embodiment, the spray dispenser may be a self-pressurized non-aerosol container having a convoluted liner and an elastomeric sleeve. This self-pressurized dispenser comprises a liner / sleeve assembly including a thin, flexible, radially expandable, convoluted plastic liner having a thickness of about 0.010 to about 0.020 inches within a substantially cylindrical elastomeric sleeve. The liner / sleeve is capable of containing a substantial amount of odor-absorbing fluid product and effecting the dispensing of that product. A more complete description of self-pressurized spray dispensers can be found in U.S. Patent Nos. 5,111,971, Winer, and 5,232,126, Winer.

[0119] In another type of aerosol spray dispenser, a barrier layer separates the composition of the invention from the propellant (usually compressed air or nitrogen), as disclosed in U.S. Pat. No. 4,260,110. Such a dispenser is available from EP Spray Systems, East Hanover, NJ.

[0120] In a further embodiment of the invention, the spray dispenser is a manually triggered non-aerosol pump-action spray dispenser. The pump-action spray dispenser comprises a container and a pumping mechanism that is securely screwed or snapped onto the container. The container comprises a vessel containing the composition of the invention to be dispensed. The pumping mechanism comprises a substantially fixed-volume pumping chamber having an opening at its inboard end. Within the pumping chamber is a pump stem having a piston on one end that reciprocates within the pumping chamber. A passage extends through the pump stem with a dispensing outlet at the outer end of the passage and an axial inlet opening at its inboard end.

[0121] The container and pump mechanism may be made from any conventional material used to manufacture pump-spray dispensers, including, but not limited to, polyethylene, polypropylene, polyethylene terephthalate, blends of polyethylene, vinyl acetate, and rubber elastomer. Other materials may include stainless steel. A more complete disclosure of commercially available dispensing devices appears in U.S. Pat. No. 4,895,279, Schultz; U.S. Pat. No. 4,735,347, Schultz et al.; and U.S. Pat. No. 4,274,560, Carter.

[0122] In yet another embodiment, the spray dispenser is a manually triggered spray gun. The spray gun comprises a container and a trigger, both of which can be made from any of the conventional materials used to make spray guns, including, but not limited to: polyethylene, polypropylene, polyacetal, polycarbonate; polyethylene terephthalate, polyvinyl chloride, polystyrene, blends of polyethylene, vinyl acetate, and rubber elastomer. Other materials can include stainless steel and glass. The spray gun does not contain a propellant gas. This is typically a spray gun that acts only on a predetermined amount of the composition of the invention itself, usually by means of a piston or collapsing bellows that displaces the composition through a nozzle to create a stream or spray of liquid.The spray gun typically includes a pumping chamber with either a piston or a bellows that can be moved by a limited stroke response to the trigger, allowing the volume of the pumping chamber to be varied. This pumping chamber or bellows chamber collects and holds the product to be dispensed.

[0123] The spray gun typically has an outlet check valve that blocks communication and fluid flow through the nozzle and responds to the pressure inside the chamber. In piston-type spray guns, when the lever is pressed, it acts on the fluid in the chamber and the spring, increasing the pressure on the fluid. In bellows-type spray guns, the pressure on the fluid increases when the bellows are compressed. The increase in fluid pressure in both spray guns acts to open the upper outlet check valve. The upper valve allows the product to be forced through the swirl chamber and out the nozzle, forming a discharge stream or pattern. An adjustable nozzle cap can be used to vary the pattern of the dispensed fluid.With the piston-operated spray gun, when the trigger is released, the spring acts on the piston, causing it to return to its original position. With the bellows-operated spray gun, the bellows acts as a spring, returning to its original position. This process creates a vacuum in the chamber. The reacting fluid causes the outlet valve to close while the inlet valve opens, drawing the product from the reservoir up into the chamber.

[0124] A complete disclosure of commercially available dispensing devices appears in U.S. Pat. No. 4,082,223 to Nozawa; U.S. Pat. No. 4,161,288 to McKinney; U.S. Pat. No. 4,434,917 to Saito et al.; U.S. Pat. No. 4,819,835 to Tasaki; and U.S. Pat. No. 5,303,867 to Peterson. A wide variety of spray guns or finger pump spray bottles are suitable for use with the compositions of the present invention. These are readily available from suppliers such as Calmar, Inc., City of Industry, Calif.; CSI (Continental Sprayers, Inc.), St. Peters, M.; Berry Plastics Corp., Evansville, Ind.; or Seaquest Dispensing, Cary, Ill.

[0125] In general, the spray dispensers are best used with compositions of the invention that, in addition to the rheological vertical adhesion properties of the invention, also exhibit a degree of shear-thinning properties. Alternatively, the opening size of the spray dispenser passages, chambers, inlet, and outlet openings can be appropriately sized, i.e., typically with an enlarged internal diameter relative to sizes suitable for thin liquids, such as water, to an extent dictated by the viscosity of the compositions of the invention, so as to provide suitable dispensing properties. RESULTS AND DISCUSSIONVertical liability parameter

[0126] The vertical adhesion parameter of a liquid substance is determined in the following manner using a sample panel made of an exemplary material selected to allow for easy testing under controlled conditions. The exemplary material is a clear, coated, black-painted metallic sample panel from ACT Laboratories Co., Hillsdale, Michigan, designated Ford F-Series APR437222. A rectangular sample panel approximately 18 inches wide by 12 inches high is divided into six vertical sections of equal dimensions to yield six approximately equivalent sections of approximately 3 inches wide by 12 inches long. The division of the six vertical sections can be accomplished using a marker, tape, or any similar means that provides visible separation of the sections solely for ease of testing.The six sections provide test replicates. During testing, the sample panel is placed upright so that its shortest dimension is perpendicular to a flat, horizontal support surface and its longest dimension is parallel to the horizontal, so that the sample panel is positioned in a generally vertical (upright) plane. The sample panel is secured in the upright position using a clamp or frame that holds it at an angle of approximately 95° with respect to the horizontal, i.e., approximately 5° from the normal to the vertical plane, and oriented such that the test surface (front surface) is tilted backward by 5° from a position normal to the plane.This position allows the liquid substance applied for the purpose of testing the vertical adhesion parameter of the liquid substance to come into contact with the slightly tilted front side of the sample panel and flow downwards and along the front side of the sample panel under the influence of gravity.

[0127] Liquid substance is prepared for application by transferring approximately 3 milliliters of the liquid substance into an appropriately sized syringe (5 or 10 milliliter volume) that is partially filled with 3 milliliters of the liquid substance and displacing air so that the liquid substance is between the syringe opening and the plunger with no intervening air gap or trapped air bubbles present. Multiple syringes may be made or the same syringe can be used for replicates with the same liquid substance. At the beginning of the test, the filled syringe containing the liquid substance is held to the top edge of one of the six sections at a point approximately 1 inch below the top edge and positioned so that the syringe opening is approximately 2 inches from the surface of the sample panel.At the same time, a) the syringe is manually depressed so that the liquid substance is completely dispensed onto the top of the test panel in a smooth motion, and b) a timer is started starting at zero to obtain the elapsed time in seconds. After exactly 120 seconds (2 minutes), a ruler with divisions to at least 0.0125 inches is used to measure the total length of the liquid substance path (the flow path), starting at the highest position at which the liquid substance at the application point has wetted the test surface and ending at the lowest position wetted by the liquid substance flowing on the test surface. The flow path is recorded to the nearest 0.0125 inches.Further repetitions of the test are repeated following the same procedure, using an aliquot of the liquid substance in each subsequent section of the sample panel, so that at least six individual flow path values ​​are generated. The average of the six individual flow path repetitions represents the vertical adhesion parameter (in units of inches of flow per 2 minutes) of the liquid substance on the sample panel.

[0128] It should be noted that selected test substances, including liquid substances, and sample panels of the selected surface material are tested at approximately 25°C. Higher or lower temperatures may result in either increased or decreased flow rates, as it is well known in the art that temperature sensitivity is associated with the temperature-dependent rheological behavior of liquids. Therefore, all tests are conducted using temperature-equilibrated test substances / materials and ambient temperatures of approximately 25°C. It was also found that rinsing or pre-wetting the sample panel surfaces with water had no significant effect on the vertical adhesion parameter measurements of the compositions of the invention.Without being bound by theory, it is assumed that the common surfaces of interest and construction materials of automotive surfaces are essentially non-absorbent and do not retain water to any significant extent, especially on partially inclined or vertically oriented surfaces. Thus, for the purpose of determining the vertical adhesion parameter, rinsing the sample panel or test materials is optional.

[0129] Thus, the vertical adhesion parameter provides a convenient and easily measured parameter that describes the overall rheological behavior of the compositions of the invention, which are characterized by their ability to adhere to a vertical surface without excessive sagging, dripping, or flowing, as defined by a vertical adhesion parameter value between 1 to about 7. The compositions of the invention have sufficient vertical adhesion properties that they exhibit a vertical adhesion parameter of at least 1. Compositions that are generally too viscous and also do not exhibit measurable flow under the conditions of the vertical adhesion test, i.e., having a vertical adhesion parameter below 1 or substantially zero, are unusable because they are generally too viscous to be easily dispensed and applied and spread over a treated surface.In contrast, compositions that are generally less viscous and also have a vertical adhesion parameter of greater than 7 were found to have insufficient adhesion to vertical surfaces. Compositions of the invention that have a vertical adhesion parameter between 1 and about 7 are also generally easier to apply without excessive sagging or dripping from the desired application area, allowing a minimal amount of the cleaning composition to be applied where needed.While the measured viscosity of the compositions of the invention and the vertical adhesion parameter are not necessarily proportional, it has generally been found that compositions of the invention include those compositions having measured viscosities between about 2 Pas (2000 centipoise (cps)) to about 20 Pas (20,000 cps) and simultaneously having a vertical adhesion parameter between 1 and about 7. EXAMPLES

[0130] Examples of suitable embodiments of the compositions according to the invention are given in Table 1. These example formulations illustrate the type of formulations encompassed by the present invention and are not an exhaustive list of possible formulations.

[0131] Viscosity measurements were also performed, and the example formulations in Table 1 had viscosities between the ranges of 4 Pas (4000 cps) and 6 Pas (6000 cps), preferably between the ranges of 4.025 Pas and 5.075 Pas (4025 and 5075 cps), more preferably between about 4.050 and 5.050 Pas (4050 and 5050 cps). The vertical adhesion ranges for the example formulations were between 1 and 7, more preferably between 1 and 5, and most preferably between 1 and 3.

[0132] In contrast, the comparative examples in Table 2 showed that the viscosity of the formulations ranged from about 0.01 to 3 Pas (10 to 3000 cps), and the vertical adhesion of these examples ranged from 1 to 7. Surprisingly, the viscosity of the tested liquid substances was found not to directly correlate with the measured vertical adhesion parameter. That is, the least viscous comparative product did not necessarily exhibit the slowest flow rate or the least desirable vertical adhesion parameter. Without wishing to be bound by theory, it is believed that the rheological contribution to the vertical adhesion properties of the compositions of the invention includes other factors, such as surface wetting, friction, and shear flow behavior, which are not readily reflected by a measured viscosity value alone.Thus, the vertical adhesion parameter represents the best measure for the compositions of the invention and best describes the protectant compositions suitable for the methods of use, methods of application, and protectant kit presented herein.

[0133] Without departing from the spirit and scope of this invention, one of ordinary skill in the art can make various changes and modifications to the invention to adapt it to various uses and conditions. As such, these changes and modifications are properly and genuinely intended to fall within the full scope of equivalence of the following claims. Table 1: Protective agent spray formulations Ingredient Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 hydrophobically modified alkali-soluble acrylic polymer 0,54% 0,21% 0,25% 0,75% 0,05% 0,03% Sodium bicarbonate 0,027% 0,027% 0,027% 0,027% 0,027% 0,027% Polydimethylsiloxan-Fluid (350 mm 2 / s(cst)) 11,93% 12,00% 8,00% 5,00% 10,00% 8,00% Triethanolamine99 (1) 0,6% 0,3% 0,31% 0,73% 0,08% 0,06% FZ-77 Superspreader (2) 0,25% 0,25% 0,25% 0,25% 0,25% 0,25% Alkanesulfonate (anionic surfactant) 0,35% 0,31% 0,45% 0,42% 0,35% 0,38% Alcohol ethoxylate (nonionic surfactants) 0,43% 0,38% 0,30% 0,42% 0,39% 0,36% Preservatives 0,24% 0,24% 0,24% 0,24% 0,24% 0,24% Defoamers 0,018% 0,018% 0,018% 0,018% 0,018% 0,018% UV absorbers 0,30% 0,30% 0,30% 0,30% 0,30% 0,30% Sodium benzoate 0,018% 0,018% 0,018% 0,018% 0,018% 0,018% demineralized water qs qs qs qs qs qs I Total 100 I 100 100 100 100 100 1. Huntsman low-freezing grade triethanolamine. 2. Silicone surfactant superspreader from Dow Corning Co. Table 2: Formulations for protective wipes Ingredient Example 1 I Example 2 Example 3 Example 4 hydrophobically modified alkali-soluble acrylic polymer 0,11% 0,09% 0,18% 0,21% Sodium bicarbonate 0,42% 0,42% 0,42% 0,42% Polydimethylsiloxan-Fluid (350 mm 2 / s (cst)) 9,24% 28,95% 18,55% 28,95% Triethanolamine 99 (1) 0,12% 0,09% 0,27% 0,30% FZ-77 Superspreader(2) 0,40% 0,40% 0,40% 0,40% Alkanesulfonate (anionic surfactant) 0,10% 0,31% 0,20% 0,31% Alcohol ethoxylate (nonionic surfactants) 0,40% 1,26% 0,81% 1,26% Preservatives 0,23% 0,29% 0,25% 0,29% Defoamers 0,01% 0,04% 0,03% 0,04% UV absorbers 0,30% 0,30% 0,30% 0,30% Sodium benzoate 0,028% 0,028% 0,028% 0,028% demineralized water qs qs qs qs In total 100 100 100 100 1. Huntsman low-freezing grade triethanolamine. 2. Silicone surfactant superspreader from Dow Corning Co. Table 3: Data of the vertical adhesion test liquid substance Viscosity (1) Pas(cps) vertical fall in inches after 9 seconds Measurement of vertical adhesion (2) Comparison product 1 (3) 1,5 (1500) 11 > 7 liquid substance Viscosity (1) Pas(cps) vertical fall in inches after 35 seconds Measurement of vertical adhesion (2) Comparison product 2 (4) 4,034 (4034) 11 > 7 liquid substance Viscosity (1) Pas(cps) vertical fall in inches after 120 seconds Measurement of vertical adhesion (2) inventive example (5) 4,512 (4512) 6,58 6,58 1. Viscosity measured in Pas (centipoise (cps)) at 25°C using an LV viscometer equipped with spindle No. 4 operating at 30 rpm. 2. Vertical adhesion parameter determined using clear coated black painted metallic test panel from ACT Laboratories Co., designated as Ford F-Series APR437222. 3. The example formulations can be found in U.S. Patent Nos. 6,206,956 and 6,221,433 to Muntz et al. Comparative Product 1 contains 0.075 wt.% active ingredients CARBOPOL ® 940. 4. The example formulations can be found in U.S. Patent Nos. 6,206,956 and 6,221,433 to Muntz et al. Comparative Product 1 contains 1.2 wt.% active ingredients CARBOPOL ® 940. 5. The example formulation according to the invention corresponds to the sample formulation found as Example 6 in Table 1 (above).

Claims

[1] A sprayable automotive protectant composition comprising: (a) 0.1% to 5% by weight of a nonionic surfactant comprising an alcohol ethoxylate, (b) 0.1% to 5% by weight of an anionic surfactant comprising a sulfonate surfactant, (c) 5 wt% to 15 wt% of a polyorganosiloxane having a pure viscosity of 10 mm 2 / s (cSt) up to 1 000 000 mm 2 / s (cSt), (d) 0.05% to 0.3% rheology modifier selected from the group consisting of acrylic polymers, methacrylic polymers, acrylamide polymers, acrylic and acrylamide copolymers, methacrylic and acrylamide copolymers and mixtures thereof, (e) 65% to 95% water and (f) sodium benzoate, wherein the automotive protectant is an emulsion in which the polyorganosiloxane is present with a particle size in the range of 10 nm to 1000 nm and the automotive protectant has a viscosity of greater than 4 Pas (4000 cps) and less than 6 Pas (6000 cps) and has a vertical adhesion parameter of between 2.54 cm flow per 2 minutes and 17.78 cm flow per 2 minutes at a temperature of 25°C and wherein the ratio of nonionic surfactant to anionic surfactant is 1:1 to 3:

2. [2] The protectant composition of claim 1, wherein the viscosity is 4.025 Pas (4025 cps) to 5.075 Pas (5075 cps). [3] The protectant composition of claim 1, wherein the protectant has a viscosity between 4.5 Pas (4500 cps) to 5.5 Pas (5500 cps). [4] The protectant composition of claim 1, further comprising a UV absorber. [5] The protective agent composition according to claim 1, wherein the composition does not contain any organic solvent. [6] Use of the automotive protectant composition according to claim 1 for application to a substrate. [7] Use according to claim 6, wherein the substrate comprises cellulose fibers and synthetic fibers. [8] The protectant composition of claim 1, further comprising a UV absorber. [9] The protectant composition of claim 1, further comprising one or more adjuvants selected from the group consisting of chelators, builders, alkalinity sources, descaling agents, foam boosters, foam suppressants, surface modifiers, pH adjusting agents, pH buffers, wetting agents, stain and soil resistant agents, waxes, resins, polishes, colloid stabilizers, waxes, lubricants, odor control agents, perfumes, fragrances and fragrance release agents, brighteners, ultraviolet light (UV) absorbers, UV scattering agents, dyes, colorants, phase stabilizers, emulsifiers, thickeners, defoamers, hydrotropes, cloud point modifiers, antimicrobial agents and preservatives.