WO1994005731A9

WO1994005731A9 - Solvent-free water-based emulsion polishes

Info

Publication number: WO1994005731A9
Application number: PCT/US1993/007949
Authority: WO
Filing date: 1993-08-24
Publication date: 1994-06-09

Abstract

Solvent-free, oil-in-water emulsion polishes, especially useful as automotive polishes, with application, buffability and durability characteristics comparable to solvent-based polishes are described which are substantially free of added organic solvents and conventional surfactants. These emulsion compositions comprise 0.05-25 % of a polymeric silicone wax, 0.1-25 % of a polyorganosiloxane resin, an effective amount, preferably from 0.05-5 %, of a polymeric electrostatic emulsifier such as an acrylates/C10-C30 alkyl acrylate cross polymer which takes the place of conventional surfactants with the balance comprising water.

Description

SOLVENT-FREE WATER-BASED EMULSION POLISHES

Technical Field

This invention relates to an aqueous oil-in-water emulsion polish composition, especially useful for automobiles, which is substantially free of added organic solvents and water-sensitive surfactants which is based upon a combination of a polymeric silicone wax, a silicone resin and a specific type of polymeric electrostatic emulsifier to obtain a polish composition with buffability, durability and appearance (e.g., film gloss) characteristics of the same order as conventional organic solvent-based polishes.

Background Art As the world becomes more ecologically conscious of the potential environmental harm done by volatile organic solvent-based products which release organic solvents into the atmosphere, there is a greater desire to obtain essentially solvent-free compositions to replace such products. Unfortunately, the substitution of water-based compositions for solvent-based compositions in products often sacrifices favorable properties or increases the cost of such products because expensive materials or methods of manufacturing water-based products are required.

This is true in the field of polish products, especially four outdoor use such as automobile polishes, where water- based products tend to be harder to apply and bμff out to a high shine because they tend to dry faster than organic solvent-based polishes, especially on hot days and in the sun. They may also be less durable than their organic solvent-based counterparts due to the need for water- sensitive surfactants to disperse or emulsify the ingredients into water which tend to remain in polish left behind eventually contribute to loss of the film. Emulsion polishes can also have stability problems and thus a significant amount of surfactant must usually be added to retain product stability. Durability on weathering and against the action of detergents can be helped by the addition of amino-

SUBSTITUTE SHEET functional silicone polymers which tend to associate with the paint film as are used in conventional organic solvent-based auto compositions, but these ingredients increase the cost of the product. Many of the ingredients used to form a durable polish film on the surface of an automobile such as waxes are difficult to disperse in water due to their desirable hydrophobic properties which are used to form water-repellent polish films.

Many different ingredients have been used in polish compositions in the past. Various types of water-based emulsion products have also been proposed for use in replacing organic solvent-based polishes.

U.S. Pat. No. 2,626,870 to Cooke et al. teaches an automobile wax emulsion of the oil-in-water type containing small amounts of silicone oils in the dispersed phase. These compositions contain added organic solvents in the amount of from about 3% to 25% by weight to dissolve the wax before it is dispersed in water. From about 0.2% to 4% by weight of "emulsifying agents" are employed which are exemplified by gum tragacanth, gum arabic, bentonite, locust bean gum, starch, albumen, karaya gum, Irish moss, water-colloidable cellulose and the like. Some of the "emulsifying agents" taught are polymers, but all are water-sensitive. Additionally, water-soluble wetting agents such as anionic or nonionic surfactants can also be used in amounts of less than 1%. The silicone oils are taught as being polydimethylsiloxanes although the methyl groups may be substituted or replaced by other organic or inorganic groups or by single atoms. While these polishes are water-based, they contain significant amounts of added organic solvents and water-sensitive surfactants and emulsifying agents.

U.S. Pat. No. 4,347,333 to Lohr et al. teaches emulsion hard surface coating compositions useful as auto polishes which have excellent detergent resistance as well as good gloss and buff properties. They contain an organic solvent as well as silicone fluids, an acrylic polymer which is soluble in the solvent, surfactants, water, and optionally waxes and abrasives. Thus, these compositions require both added organic solvent to dissolve the acrylic polymer and a surfactant such as an anionic or nonionic surfactant.

U.S. Pat. No. 3,429,842 to Wolstoncroft teaches an aqueous polish formulation containing an emulsifiable polyolefin wax, an acrylic interpolymer, an alkali-soluble resin, a leveling agent containing tributoxyethyl phosphate, a hydrolytically stable polysiloxane-oxyalkylene block copolymer and diethylene glycol monoethyl ether. In addition to the ether solvent, other liquid hydrocarbon solvents can be present to dissolve the polyethylene wax. The acrylic interpolymer and polyolefin wax are the principal constituents of the polish film left behind. The acrylic interpolymer is in the form of an acrylic latex and may contain up to 10% of acrylic acid groups to "substantially aid the emulsifiability of the wax made therefrom". The alkali soluble resin present is insoluble in water, but is soluble in a basic solution such as an ammonia solution or an alkali metal hydroxide solution. The alkali soluble resin is included to permit the dried films to be removed from a substrate such as floor tile.

U.S. Pat. No. 3,393,078 to Lockhart et al. teaches a water-emulsion polish composition which contains an effective amount of an emulsifier as well as 20-55% of volatile aliphatic hydrocarbon liquid as an organic solvent for the waxes and liquid silicone polymers present.

U.S. Pat. Nos. 3,544,498 and 3,576,779, both to Holdstock et al., teach aqueous detergent resistant polishes which contain amino-functional organopolysiloxanes to improve the rub-out, gloss and detergent resistance of the polishes. To form the polishes, conventional emulsifiers such as cationic, anionic or nonionic surfactants are added in amounts of 0.5-5% as well as organic solvents in amounts of 10-60%.

U.S. Pat. No. 4,398,953 to van der Linde teaches automobile waxes with improved water beading ability composed of montan wax, an emulsifier, silicone oil, amino-functional organopolysiloxanes, finely-divided abrasive, water, volatile aliphatic hydrocarbon solvent and, optionally, pigment. The solvent is present in an amount of 30-75% and the emulsifier is an effective amount of morpholine and tall oil fatty acid such that the morpholine reacts with the acid groups in the fatty acid and the ontan wax to form emulsifiers.

U.S. Pat. No. 4,509,981 to Sanders et al. teaches coating compositions which contain 1-60% of a mixture of two different silicone fluids, one being amino-functional and the other being a linear or cyclic organopolysiloxane, along with 2-10% of a nonionic emulsifying agent, an ultraviolet radiation absorbing agent, and water. Use of organic solvent is not taught although the emulsifiers used are water- sensitive.

U.S. Pat. No. 4,265,663 to Gilicinski et al. teaches wax formulations containing liquid poly(alpha-olefin) polymers such as VYBAR® 825 for use in automobile polishes. The silicones are added as emulsions and the formulations can also contain silicones, thickeners such as CARBOPOL® 934 as well as waxes added as emulsion and emulsifiers. The use of 6-20% hydrocarbon organic solvent is also taught.

Other examples of patents showing the state-of-the-art in emulsion polishes are U.S. Pat. Nos. 2,523,281 to Currie; 2,839,482 to Geen et al. ; 3,028,350 to Hirsch; 3,929,492 to Chapman et al.; 3,931,079 to Wise et al.; 4,600,436 to Traver et al.; 4,936,914 to Hurley et al.; and 4,997,478. U.S. Pat. No. 5,043,012 to Shinohara et al. teaches a solvent-based glazing agent for automobile finishes which has long-lasting water repellency, but essentially includes no water. U.S. Pat. No. 4,113,677 to Svedas et al. teaches a polish composition containing organic solvent which is intended to be diluted with hot water for use in imparting a high and deep luster to an automobile surface which is water-resistant and requires little buffing. U.S. Pat. No. 4,317,755 to Gregory teaches water-based self-polishing compositions for use on floors, metal parts and the like which contains a hydrocarbon organic solvent of a certain solubility parameter which has been emulsified with a compatible surfactant. U.S. Pat. No. 4,354,871 to Sutton teaches an aqueous emulsion cleaner-polish formulation which is used to treat furniture surfaces. The compositions contain a low level of organic hydrocarbon solvent along with an alpha-olefin of from 10 to 18 carbon atoms to take over some of the cleaning power of the organic solvent which it replaces in addition to acting as a leveling agent..

Thus, there is still a need for a water-based emulsion polish which is as free of organic solvents and water- sensitive surfactants as possible, but still possesses good durability, ease of application and buffability as well as good emulsion stability.

Summary Disclosure of the Invention

One object of the present invention is to provide an oil-in-water emulsion polish composition which has substantially, and preferably, no added organic solvent or water-sensitive surfactants which compositions are particularly useful as automobile polishes. Another object of the present invention is^' to provide water-based emulsion polish compositions which possess good ease of application and buffability as well as polish film appearance characteristics such as gloss which are comparable or better than conventional polishes containing organic solvents. Yet another object of the present invention is to provide a water-based emulsion polish composition with good durability without any need for the use of hydrocarbon solvents or expensive amino-functional polyorganosiloxanes. These and other objects of the present invention are provided by a water-based oil-in-water emulsion polish composition comprising

A. from about 0.01% to 25% by weight of the total composition of a polymeric silicone wax, and more preferably from about 0.05% to 3%, and most preferably, from about 1% to 1.5%;

B. from about 0.1% to 25% by weight of the total composition of a polyorganosiloxane resin, and more preferably from about 0.1% to 5%; C. an effective amount, more preferably from about 0.01% to 5% of the total composition; and most preferably from about 0.05% to 0.5%, of a polymeric electrostatic emulsifier for forming oil-in-water emulsions which is a modified polymer, preferably lightly cross-linked, having a major portion of a monoolefinically unsaturated carboxylic acid monomer or its anhydride of 3 to 6 carbon atoms and a minor portion of a long chain acrylate or methacrylate monomer which polymer is neutralized with an effective amoun of a base and is capable of dispersing (A) and (B) within

D. water comprising the balance of the composition to form an oil-in-water emulsion wherein the composition is substantially free of any added organic solvents and water- sensitive surfactants. Additionally, such polish compositions can preferably contain organic waxes to improve polish buffability and durability in amounts of from about 0.05% to 25% and hydrocarbon resins to improve film durability, buffability and film appearance characteristics in amounts of from about 0.01% to 20%.

Best Mode for Carrying Out the Invention The oil-in-water¹ emulsion polish compositions of the present invention require three ingredients in addition to tap or deionized water which forms the balance of the composition. Deionized water or low mineral content, soft tap water is preferred. The percentages given herein are based upon non-volatile solids (actives) content unless otherwise specified.

The first required ingredient is from about 0.05% to 25% percent by weight of the total composition of a polymeric silicone wax composition which is a viscous liquid to a waxy solid at room temperature (25° C), but has a melting point of no more than about 100°C. Such waxes are known to those of ordinary skill in the art and are composed of copolymers of dimethylsiloxy units [(CH₃)2SiO] and methylalkylsiloxy [CH₃RSiO] units or homopolymers of methylalkylsiloxy units [CH₃RSiO] where the alkyl or R group contains from about 8 to 30 carbon atoms. These copolymers and homopolymers are typically endblocked with trimethylsiloxy units t (^CH ₃) ₃ ^si°ι/2] • Such waxes are commercially available from Th. Goldschmidt AG Che ische Fabriken of Essen, Germany, Wacker-Chemie GmbH of Burghausen, Germany, and the General Electric Company, Silicone Products Division of Waterford, New York, USA. A presently preferred silicone polymer wax is sold by Th. Goldschmidt AG under the ABIL®-Wax 9810 (also sold by Th. Goldschmidt under the designation TEGOPREN® 6846) which is a high molecular weight silicone wax described as a polysiloxane polyalkylene copolymer which is a trimethylsiloxy endblocked homopolymer of CH₃RSiO units having a white, waxy appearance at 25°C. with a melting point of 64+2°C, a specific gravity of 0.83+0.01 gram/cubic centimeter ("g/cm³) at 70°C. , a flash point (DIN 51758) of greater than 150°C. and an actives (non-volatile solids) content of 100%. At 10% concentration at 90°C, this wax is insoluble in water and glycerol, but is soluble in mineral oil, isopropyl myristate and sunflower seed oil. Other types of such silicone waxes are available from Th. Goldschmidt under the designations ABIL®-Wax 9800 (TEGOPREN® 6800) and ABIL®-Wax 9801 (TEGOPREN® 6801) . Another preferred silicone wax is one available from Wacker-Chemie under the designation "SLM 50553/1" or "Wacker Wax W 23" which is a white, wax¬ like, non-soapable methyl-substituted siloxane having a viscosity at 50°C. of approximately 300 mPa.s, and a melting point of 35°-45°C.

These polymeric silicone waxes may be emulsified in water using small amounts of conventional surfactants to improve the ease of making the emulsion polish compositions of the present invention without greatly decreasing the durability of the resulting polish compositions due to the small amount of surfactant added by the use of the emulsions instead of the neat polymeric silicone wax. Wacker Chemie sells an aqueous milky oil-in-water emulsion of a polymeric silicone wax at 35% non-volatile solids content using a nonionic surfactant as the emulsifier under the designation "SLM 23032" or "Fluid Emulsion E 32" having an emulsion viscosity of 7 mm²/second at 25°C. and a particle size of about 300 nanometers.

More preferably, from about 0.05% to 25% by weight of the silicone wax is used. This ingredient is used to provide good buffability to the polish compositions of the present invention as well as to retain the surface protective properties of any additional organic waxes which may be added to such compositions. The silicone waxes also tend to help in improving the long term durability of the polish films. If too little silicone wax is used, the buffability of the polish composition suffers while the use of too much silicone wax adds unnecessary expense to the polish compositions. More preferably, from about 0.05% to 3% by weight of the silicone wax is used, and most preferably, from about 1% to 1.5%.

The degree of buffability provided by the compositions of the present invention is surprising. Conventional water- based emulsion polishes typically require the addition of glycerol or other humectants to prevent the water-based emulsion film from drying out too quickly and becoming difficult to buff to a high shine. Besides a decrease in product cost, there is an important advantage afforded by the elimination of the need for water-sensitive humectants. The long term durability of the polish film left by our polish compositions is improved since water standing on the polish film can wet the humectants which in turn can act to release the film from the polished surface. The second required ingredient is from about 0.1% to about 25% by weight of a polyorganosiloxane resin which is used to impart durability to the polish film left on a substrate after application of the emulsion polish composition. Polyorganosiloxane resins are well known products which are available from a number of manufacturers throughout the world such as Wacker-Chemie GmbH of Burghausen, Germany, Dow Corning Corporation of Midland, Michigan, USA, and the General Electric Company, Silicone Products Division, Waterford, NY, USA. Such resins are typically characterized by being organic solvent soluble solids, typically brittle solids, at 25°C. Such resins are composed of a combination of trimethylsiloxy units [ (CH₃)₃Si0₁/ ] ' dimethylsiloxy units [(CH₃)2SiO] and silica units [(SiO. /2)] which can be expressed by the general formula

^((CH₃)₃ ^Si⁰ _1/2⁾a^(Si^θ4_/2⁾b^((CH₃ ⁾ ₂ ^Si^θ2/2⁾c

where the numbers and ratios of the units present are such as to give the desired resinous properties to the polymers. Some presently preferred silicone resins are sold by Wacker Chemie under the designations "Wacker Release Agent TPR" and "Wacker Release Agent VP 1038" which are described by the manufacturer as corresponding to the above formula wherein a+b is from 20% to 50% by weight of the resin, c is from 50% to 80% by weight of the resin and the ratio of a to b is from 6:10 to 8:10. The manufacturer describes Release Agent TPR as a colorless liquid with a melting point of less than -35°C. , a density of 1.02 g/cm³ at 25°C. , a viscosity of 250-400 mPa.s at 25°C. and a flashpoint (DIN 51758) of greater than 165°C. The manufacturer describes Release Agent VP 1038 in the same manner as for Release Agent TPR, but lists the viscosity as being 1000-3000 mPa.s at 25°C. Since the silicone resins are typically solids, Wacker-Chemie includes an amount of dimethicone fluid in Release Agent VP 1038 and in Release Agent TPR to make the products easier to use because they are then in liquid form. The Release Agent VP 1038 is said to contain a higher amount of resin than the Release Agent TPR and thus the viscosity of the former is higher than the latter product.

Since solid or hydrophobic liquid resin products can be difficult to disperse in water without the use of solvents, Wacker Chemie also provides an aqueous emulsion version of its Release Agent TPR under the designation "SLM 55072/1" or "Fluid Emulsion E 37" as a 35% non-volatile solids content aqueous emulsion having a pH of 7.5 made using a small amount of both an anionic surfactant and a nonionic surfactant. As with the polymeric silicone waxes, an emulsion form is more preferred. More preferably, from about 0.1% to 5% by weight of the silicone resin is used. This ingredient is used to provide durability as well as good buffability and application characteristics to the polish films obtained from the polish compositions of the present invention. If too little silicone wax is used, the durability, buffability and application characteristics of the polish composition suffers while the use of too much silicone resin adds unnecessary expense to the polish compositions. Most preferably, from about 0.05% to 3% by weight of the silicone resin is used. The third required ingredient is an effective amount of a polymeric electrostatic emulsifier for forming oil-in-wate emulsions which is capable of dispersing the polymeric silicone wax and the silicone resin within the water present in the composition. Additionally, application properties an buffability are improved by the use of the polymeric electrostatic emulsifier as compared with emulsion polish compositions made with conventional surfactants and thickening agents. More preferably, from about 0.05% to about 5% by weight of the polymeric electrostatic emulsifier is used. The polymeric electrostatic emulsifier must have a combination of hydrophilic groups which provide compatibilit with the water and hydrophobic groups such as long chain alkyl (8 or more carbon atoms) groups that enable the polymeric electrostatic emulsifier to associate with the less hydrophilic or substantially hydrophobic ingredients to form an emulsion. The hydrophilic groups present are preferably carboxyl groups which can be neutralized to a salt form by the addition of a base to render them strongly hydrophilic. Thus, the polymeric electrostatic emulsifier is modified polymer, preferably lightly cross-linked, having a major portion of a monoolefinically unsaturated carboxylic acid monomer or its anhydride of 3 to 6 carbon atoms and a minor portion of a long chain aerylate or methacrylate monomer. A preferred polymeric electrostatic emulsifier possessing such characteristics is the class of polymeric electrostatic emulsifier referred to as "electrostatic emulsifiers" sold as the CARBOPOL® 1600 series of products by The BFGoodrich Company, Specialty Polymers & Chemicals Division, Brecksville, Ohio, USA and under the PEMULEN® trademark in Europe by the same company. The manufacturer describes these polymeric electrostatic emulsifiers as being predominantly high molecular weight polyacrylic acid polymers which have a large water-loving (hydrophilic) portion and a smaller oil-loving (oleophilic or hydrophobic) portion which permits these polymers to act as primary emulsifiers in oil- in-water emulsions. The Cosmetics, Toiletry and Fragrance Association ("CTFA") designation for these polymers is Acrylates/C₁o-C₃o alkyl acrylate cross polymer. The 1600 series of CARBOPOL® emulsifiers include CARBOPOL® 1610 having a typical viscosity of 18,000 centipoise (18 Pa.s) at 1% concentration in water pH of 7 at room temperature (25°C); CARBOPOL® 1621 (also designated PEMULEN® TR-1) having a typical viscosity of 5,000 centipoise (5 Pa.s) at 1% concentration in water pH of 7 at room temperature (25°C); CARBOPOL® 1622 (also designated PEMULEN® TR-2) which is said to have outstanding emulsifying ability over a broad range of oil/water concentrations with minimal thickening effect and contains the highest level of hydrophobic groups of the four 1600 series products noted here; and CARBOPOL® 1631 which is said to be the most ion-resistant of the four 1600 series polymers noted here and contains mineral spirits which makes this product undesirable for use in the present invention. PEMULEN® TR-1 (CARBOPOL® 1621) and PEMULEN® TR-2 (CARBOPOL® 1622) are presently preferred for use in the present invention. These electrostatic emulsifiers differ from other polyacrylic acid thickening polymers such as the well known "900" series of CARBOPOL® resins sold by BFGoodrich for use as thickeners because of the presence of the hydrophobic groups as noted in column 9, lines 50-65 of U.S. Pat. No. 5,004,598 noted below.

These polymeric electrostatic emulsifiers appear to be described in BFGoodrich's U.S. Pat. Nos. 5,004,598 to Lochhead et al. ; 4,923,940 to Hsu; and 4,758,641 to Hsu which are hereby incorporated by reference to further teach such polymeric electrostatic emulsifiers. These patents characterize such polymers being composed of from 50-99% by weight of the total monomers, more preferably 80-99%, and most preferably, 90-98% by weight of one or more of the carboxylic monomers noted above such as acrylic acid, methacrylic acid and maleic anhydride; from 1-50% by weight of the total monomers, preferably 1-20%, and most preferably, 2-10% by weight of one or more acrylate esters or methacrylate esters such as decyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, and melissyl acrylate and the corresponding methacrylates; and, optionally, but preferably, a small amount, up to about 5%, more preferably 0.1-2%, of a cross-linking agent having two or more unsaturated groups such as 0.1-1.4% allyl pentaerythritol; 0.1-0.8% allyl acrylate; 0.1-1.4% allyl sucrose and 0.4-2.5% trimethylol propane diallylether. Cross-linking of the polymers is said to provide improved ability for the copolymers to swell. A specific example of one such polymer is given in Example 1 of the '598 Patent as being the polymerization product of 250.28 grams of acrylic acid, 5.72 grams of stearyl methacrylate and 0.858 grams of allyl pentaerythritol. An effective amount, from about 80% to 100% of the stoichiometric amount, of carboxylic acid present in the polymeric electrostatic emulsifier are neutralized to render the emulsifier more hydrophilic. Such neutralization can be done with an alkaline neutralizing agent such as an organic base such as a ino alcohols such as triethanolamine, 2-amino- 2-methyl-l-propanol ("AMP"),' and 2-amino-2-methyl-l,3- propanediol and organic amines of from 2 to 22 carbon atoms such as triethylamine and laurylamine, or inorganic bases such as ammonium hydroxide, sodium hydroxide and the like. Volatile neutralizing agents will contribute to longer polish film stability since the neutralizing agent can evaporate away and leave the polymer emulsifier less sensitive to water after the polish film has dried on a substrate. AMP is a presently preferred neutralizing agent. This ingredient is used to take the place of added surfactants that would normally be used in emulsion polish compositions to disperse the hydrophobic ingredients in the water. Conventional surfactants can result in decreased durability upon exposure to water and detergents and can also contribute to a loss of film gloss on aging of the polymeric film. If too little electrostatic polymeric electrostatic emulsifier is used, the stability of the emulsion polish composition suffers while the use of too much electrostatic polymer emulsifier may undesirably thicken the composition, render the resulting polish films more sensitive to the effects of water and detergents, and add unnecessary expense to the polish compositions. Most preferably, from about 0.05% to 0.5% by weight of the polymeric electrostatic emulsifier is used. An optional, but preferred additional ingredient is a conventional wax of the type commonly used in polish compositions. Hard waxes such as carnauba wax contribute to the formation of high gloss polymeric films while soft waxes such as paraffin wax can improve the buffability of the polish compositions. Other examples of waxes which may be useful in the emulsion polish compositions of the present invention are synthetic and naturally-derived waxes such as polyethylene waxes, modified polyethylene waxes such as maleinized and acrylated polyethylene waxes, oxidized polyolefin waxes, micro-crystalline waxes, oxidized micro- crystalline waxes, ontan wax, bees wax, hydrogenated castor oil and the like. Such waxes are included in the compositions of the present invention in amounts of from about 0.1% to 30% of the total composition and more preferably, from about 0.1% to 18%.

Yet another optional, but preferred ingredient is a poly(alpha-olefin) polymer which is used to further improve the durability and buffability of the emulsion polish compositions of the present invention. These well known hydrocarbon polymers are ethylene derived hydrocarbon polymers made from 1-alkenes having from about 5 to 20 carbon atoms per molecule which are described in U.S. Pat. No. 2,937,129. They are commercially available from the Petrolite Specialty Polymers Group of Tulsa, Oklahoma, USA under the trademark VYBAR®. Two such products which are presently preferred for use in the present invention are VYBAR® 825 a liquid having a viscosity of 6.4 Pa.s at 0°C. (ASTM D-2669) and 0.53 Pa.s at 37.8°C. which is described in U.S. Pat. No. 4,265,663 to Gilicinski et al. noted above which states that this product is described in Example 3 of J . S . Pat. No. 2,937,129 and VYBAR® 103 which is a solid at room temperature having a molecular weight of 2800, a melting point of 72°C. and a viscosity at 98.9°C. of 0.36 Pa.s. Such polymers are included in the compositions of the present invention in amounts of from about 0.1% to 20% of the total composition and more preferably, from about 0.1% to 5%. If desired, abrasives of the type commonly used in conventional polish formulations can be included in amounts of from about 0.1% to 20% of the total composition. Examples of such abrasives are amorphous silica, diatomaceous earth, aluminum silicate such as calcined aluminum silicate and aluminum oxide such as hydrated alumina. Increasing amounts of abrasive tend to reduce the durability of the polish films obtained from the emulsion polishes of the present invention, thus lower levels of abrasives such as from about 0.5% to

3.5% are more preferred if abrasives are used.

In addition to the above silicone polymers, non-volatile polydimethylsiloxane polymers such as dimethicone of viscosities from about 50 to 10,000 centistokes (0.00005 to 0.01 m /s) in viscosity at 25°C. can be included in the compositions of the present invention as further polish film forming agents. Further additional minor amounts of compatible, conventional polish composition additives can be used in amounts of no more than about one percent of the total emulsion polish composition such as preservatives, ultraviolet light absorbing agents, slip agents such as polytetrafluoroethylene additives and thickening agents such lightly cross-linked polyacrylic acid polymers such as CARBOPOL® 980 which bear the CTFA designation of "Carbomer" resins. Thickening agents are desirable when abrasives are used since they assist in suspending the abrasives within the emulsion polish composition.

Industrial Applicability The emulsion polish compositions of the present invention are typically in two ways depending upon the nature of the ingredients being used. The first method is employed where the ingredients are substantially in non-emulsion form. The hydrophobic ingredients such as the polymeric silicone wax, the polyorganosiloxane resin, and any other waxes and hydrocarbon polymers are charged to a melting vessel (i.e., a stirrer-equipped, preferably an anchor stirrer, vessel capable of heating the contents placed inside) and liquefied while stirring with the application of heat up to about 100°C. The actual temperature used depends upon the melting point of the ingredients. The water is charged to a separate mixing vessel (i.e., a stirrer-equipped vessel capable of heating the contents placed inside which further contains a homogenizer) and heated to 85°C followed by the addition of any abrasive and ultraviolet light absorbing agent with stirring. The homogenizer is then turned on and the abrasive is homogenized into the water, typically for about 15 minutes, while the temperature is kept at about 85°-90°C. The contents of the melting vessel is cooled to 85°C. and the polymeric electrostatic emulsifier is then added to the melting vessel with stirring while keeping the temperature at 85°C. The liquefied mixture from the melting vessel is then slowly added to the mixing vessel with vigorous stirring. After completion of the addition, the heating of the mixing vessel is discontinued and the contents of the mixing vessel are allowed to stir for at least 10 minutes until the contents are well mixed. Approximately 85% of total amount of the neutralizing agent specified for the polymeric electrostatic emulsifier is then added to the stirring contents of the mixing vessel and the contents are allowed to stir for at least an additional ten minutes until the contents are homogeneous. Any preservative to be used is then added and allowed to stir into the contents until homogeneous. if desired, the composition may be subjected to the action of a homogenizer to further ensure complete formation of an emulsion. If a thickener such as CARBOPOL® 980 is to be added, the temperature of the contents of the mixing vessel is adjusted to 55°-50°C. and then the thickener is added to the stirring contents, preferably as an aqueous solution of the thickener. The contents are rapidly cooled to 25°-30°C. with stirring and the stirring is continued for at least 30 minutes until the contents are homogeneous. The contents are adjusted to the desired final pH value using the remaining neutralizing agent (typically from about pH 7 to 9.5) and allowed to stir until homogeneous to complete the formation of the emulsion polish composition of the present invention.

As noted, the hydrophobic ingredients may be difficult to disperse and thus such ingredients may advantageously be added in the form of aqueous emulsions although this does introduce small amounts of less desirable conventional surfactants into the emulsion polish compositions of the present invention. In this case, the second method of making the compositions involves either obtaining the emulsified ingredients directly from the manufacturer or separately dispersing ingredients such as waxes together as is described in the following Examples. Any hydrophobic ingredients

(e.g., silicone resin or wax, hydrocarbon polymer or wax) which are not in aqueous emulsion form are charged to a melting vessel and heated with stirring to about 100°C. until the contents are liquefied. Separately, the water is charged to a mixing vessel, heated to about 85°-90°C. and stirring is started. Any abrasive may be added to the water as described above for the first method. The contents of the melting vessel are cooled to 85°-90°C. The polymeric electrostatic emulsifier is then added to'the stirring contents of the melting vessel and allowed to mix into the contents at a temperature of 85°C. The contents of the melting vessel are slowly added to the mixing vessel with vigorous stirring. Heating is then discontinued and the contents of the mixing vessel are allowed to stir for at least an additional 10 minutes until homogeneous. Approximately 85% of total amount of the neutralizing agent specified for the emulsion composition is then added to the stirring contents of the mixing vessel and the contents are allowed to stir for at least an additional ten minutes until the contents are homogeneous. Any preservatives and other additives are then added to the contents of the mixing vessel and stirring is continued for at least 10 minutes until the contents are homogeneous. All aqueous emulsions of the silicone wax, silicone resin or any emulsions of the other waxes and hydrocarbon polymers are then added sequentially with stirring. The contents are stirred for at least 30 minutes and cooled to 25°-30°C. The contents is adjusted to the desired final pH value using the remaining neutralizing agent (typically from about pH 7 to 9.5) to complete the formation of the emulsion polish composition of the present invention. If desired, the composition may be subjected to homogenization to further insure the formation of good emulsions.

The emulsion polish compositions of the present invention can take the form of liquids, gels or pastes depending upon the intended use for the product. They are especially useful as automobile polishes although they may also find use for protecting the surfaces of plastic or painted objects such as cabinets, furniture as well as for metallic substrates such as chrome and aluminum. The following Examples are provided to show various aspects of the present invention without departing from the scope and spirit of the invention. Unless otherwise indicated, all parts and percentages used in the Examples are by weight. In the Examples, the viscosities reported were run at 20°C. on a Brookfield Viscometer Model No. LVT using a #3 spindle at 30 rpm. The non-volatile solids reported were determined using 2 grams of material placed in an oven at 145°C for 30 minutes.

Example 1

The following emulsion polish composition was made to illustrate a liquid auto polish composition for use on surfaces coated with non-metallic paints.

Deionized Water

Wacker Release Agent VP 1038

Goldschmidt ABIL®-Wax 9810 Silicone Wax

Petrolite VYBAR® 825 polymer Petrolite VYBAR® 103 polymer

BFGoodrich PEMULEN® TR-2 polymeric emulsifi

Carnauba Wax, Light North Country, Type 3

Hoechst Wax VPEA¹

Hoechst Wax E² Paraffin Wax 54°/57°C.

SATINTONE® No. I³

BODOXIN® preservative⁴

2-Amino-2-Methyl-l-Propanol (90% in water)

1. Montanic acid ester wax with added acrylic groups from Hoechst Celanese Corporation OF Charlotte, North Carolina, USA. 2. Montanic acid ester wax from Hoechst Celanese Corporation.

3. Calcined aluminum silicate from Engelhard Industries of Edison, New Jersey, USA.

4. Preservative (1,6-dihydroxy-2,5-dioxahexane dihydroxymethylenurea) from Bode Chemie GmbH & Company of Hamburg, Germany.

This liquid polish composition, useful as an automobile polish, is made by charging the following into a melting vessel: VP 1038 Silicone Resin; ABIL®-Wax 9810 Silicone Wax, VYBAR® 825 and 103 polymers; Carnauba Wax; Hoechst Wax VPEA and E; and Paraffin Wax. While stirring the contents of the melting vessel, the contents are heated to 100°C. In a separate mixing vessel equipped with a stirrer, a heating means, and a homogenizer, tap water of 85°C. is charged, the stirrer is started and the temperature is adjusted to 85°- 90°C. The SATINTONE® No. 1 abrasive mixed into the contents of the mixing vessel and the homogenizer is turned on for about 15 minutes to disperse the abrasive into the water while the temperature is maintained at 85°-90°C. The temperature of the contents of the melting vessel is cooled to 85°-90°C. The PEMULEN® TR-2 polymeric electrostatic emulsifier is added to the melting vessel with stirring while the temperature of the contents is kept at no higher than 85°C. to avoid clumping of the polymeric electrostatic emulsifier.

The contents of the melting vessel are then slowly added to the mixing vessel with vigorous stirring. After the addition is complete, the heating is discontinued and the contents are stirred for 10 minutes. Then 85% of the total amount of neutralizing agent (2-Amino-2-Methyl-l-Propanol (90% in water) - 0.23%) is added to the stirring contents of the mixing vessel and stirring is continued for an additional 10 minutes. The BODOXIN® preservative is then added to the stirring contents of the mixing vessel and the contents are stirred for 10 minutes after completion of the addition. The contents are then cooled to 25°-30°C. and pumped into a storage tank equipped with a stirrer where that final product is adjusted to a pH of from 7.2 to 7.7 using the remainder of the neutralizing agent. The resulting product is a white viscous opaque liquid emulsion polish composition having a viscosity of 2800-3300 centipoise (2.8-3.3 Pa.s) at 20°C. with a non-volatile content of 23.00-24.00%. It is useful for polishing automobile finishes and possesses a degree of buffability and durability comparable to solvent-based polish compositions

Example 2 This Example illustrates a liquid emulsion polish composition of the present invention which is especially formulated for use on automobiles with metallic paints since it has a milder and less abrasive grade of calcined aluminum silicate in a lesser amount than in Example 1 above.

% bv Weight Deionized Water 76.88

Wacker Release Agent VP 1038 2.50

Goldschmidt ABIL®-Wax 9810 Silicone Wax 1.00 Petrolite VYBAR® 825 1.00

Petrolite VYBAR® 103 2.50

BFGoodrich PEMULEN® TR-2 polymeric emulsifier 0.25 Carnauba Wax, Light North Country, Type 3 0.25 Hoechst Wax VPEA 0.25 Hoechst Wax E 5.00

Paraffin Wax 54°/57°C. 9.50

SATINTONE® No. 5¹ 0.50

BODOXIN® preservative 0.10

2-Amino-2-Methyl-l-Propanol (90% in water) 0.27 100.00

Calcined aluminum silicate from Engelhard Industries of Edison, New Jersey, USA. This emulsion polish composition is prepared in the sam manner as was described for Example 1 above. The final pH o the emulsion polish composition is from 7.2 to 7.7 and the viscosity at 20°C. is from 2800-3300 centipoise (2.8-3.3 Pa.s) with a non-volatile content of 23.00-24.00%.

Example 3

This is an example of a thickened emulsion polish composition of the present invention which is useful as a pre-softened paste automotive polish composition for use on surfaces coated with non-metallic paints.

% bv Weight Deionized Water 59.83

Wacker Release Agent TPR 2.50 Goldschmidt ABIL®-Wax 9810 Silicone Wax 1.00 Petrolite VYBAR® 825 ' 3.00

Dimethicone, 10,000 centistokes (0.01 m²/sec) 2.50 BFGoodrich PEMULEN® TR-2 0.20

Carnauba Wax, Light North Country, Type 3 0.25 Hoechst Wax VPEA 0.25

Hoechst Wax E 5.00

Paraffin Wax 54°/57°C. 9.50

SATINTONE® No. 1 3.00

BODOXIN® preservative 0.10 Givaudan GIVSORB® UV2 (Formamidine) ¹ 0.02

2-Amino-2-Methyl-l-Propanol (90% in water) 0.85 CARBOPOL® 980 Solution² 12.00

100.00

1. N-(p-ethoxycarbonylphenyl)-N'-methyl-N'-phenyl formamidine ultraviolet light absorber from Givaudan Corporation of Clifton, New Jersey, USA. 2. As used in this Example and later Examples, this

Solution was composed of a dispersion of 97.97% tap water, 2.00% of CARBOPOL® 980 and 0.03% of KATHON® 886 MW, a preservative (5-chloro-2-methyl-4-isothiazolin-3- one) from Rohm and Haas Company of Philadelphia, Pennsylvania, USA. This emulsion polish composition is prepared in the same manner as described in Example 1 except the GIVSORB® UV2 ultraviolet absorbing agent is added at the same time as is the SATINTONE® No. 1 abrasive. An additional change is that the CARBOPOL® 980 Solution is prepared prior to making the emulsion polish composition. After the BODOXIN® preservative is added, the contents of the mixing tank are cooled to 55°- 50°C. and the CARBOPOL® 980 Solution is then charged to the mixing vessel with stirring. The contents of the mixing tank are then rapidly cooled to 25°-30°C. and a homogeneous paste is formed. The pH of the stirring contents of the mixing tank are then adjusted to a pH of 9.00-9.50 with the remaining amount of the 2-Amino-2-Methyl-l-Propanol (90% in water) . The resulting emulsion polish composition is stirred for an additional 30 minutes and a final check of the pH and viscosity is made. The resulting product is a compact white paste emulsion polish'composition having a non-volatile content of 27.40-28.40%.

Example 4

This is an example of a thickened emulsion polish composition of the present invention which is useful as a pre-softened paste automotive polish composition for use on surfaces coated with metallic paints. % bv Weight

Deionized Water 61.83

Wacker Release Agent TPR 2.50

Goldschmidt ABIL®-Wax 9810 Silicone Wax 1.00 Petrolite VYBAR® 825 3.00 Dimethicone, 10,000 centistokes (0.01 m /sec) 2.50 BFGoodrich PEMULEN® TR-2 0.20

Carnauba Wax, Light North Country, Type 3 0.25 Hoechst Wax VPEA 0.25

Hoechst Wax E 5.00 Paraffin Wax 54°/57°C. 9.50

SATINTONE® No. 5 1.00

BODOXIN® preservative 0.10

Givaudan GIVSORB® UV2 (Formamidine)¹ 0.02

2-Amino-2-Methyl-l-Propanol (90% in water) 0.85 CARBOPOL® 980 Solution² 12.00

100.00

This emulsion polish composition is made in the same manner as described for Example 3. The resulting composition is a compact white paste having a pH of 9.0-9.5 and a non¬ volatile content of 27.40-28.40%.

Example 5 This is an example of an abrasive-free emulsion polish composition of the present invention which is useful as an automotive polish composition, particularly for use on new automobile surfaces. It is also an example of how compositions of the present invention can be prepared using pre-emulsified ingredients such as a silicone wax emulsion, a silicone resin emulsion and a wax emulsion.

The wax emulsion,' designated "Wax Emulsion A", has the following formula:

% bv Weight

Deionized Water 79.95

BODOXIN® preservative 0.05

Hoechst Wax VPEA 4.00

Hoechst Wax KSL 9.60 Carnauba Wax, Light North Country, Type 3 4.00

Hoechst Emulsifier 4106¹ 2.40

100.00

1. Nonionic surfactant mixture of alkyl ethoxylates from Hoechst AG of Frankfurt, Germany.

To make Wax Emulsion A, Hoechst Wax VPEA; Hoechst Wax KSL; and the Carnauba Wax are added to a melting vessel and heated to 105°-110°C. with stirring. The Hoechst Emulsifier 4106 is then added to the contents of the melting vessel and stirred well into the contents using a propeller mixer. The water is charged to a mixing vessel and heated to 96°C. The contents of the melting vessel are slowly charged at 105°-110°C. into the water in the mixing vessel with stirring. Stirring is continued for a further 10 minutes before the contents of the mixing vessel are cooled with good stirring to a temperature of 30°C. The contents of the mixing vessel are then filtered and the BODOXIN® preservative is then added to the filtered product and allowed to stir into the product for 10 minutes. The product is a milky white emulsion having a pH of 9.00-9.50 with a non-volatile content of 19.50-20.50%.

The emulsion polish composition has the following formulation:

Tap Water

Wacker Release Agent TPR Wacker SLM 50553/1 (Wax W 23) Silicone Wax

Petrolite VYBAR® 825 ' 0.20

Wacker SLM 55072/1 TPR Resin Emulsion

(Fluid Emulsion E 37) (35%) 3.00

BFGoodrich PEMULEN® TR-1 0.10 Du Pont ZONYL® FSN-100 (100%)! 0.01

Wacker SLM 23032 Silicone Wax Emulsion

(Fluid Emulsion E 32) (35%) 1.00

Hoechst Wax E 0.60

BODOXIN® preservative 0.10 2-Amino-2-Methyl-l-Propanol (90% in water) 0.27

Wax Emulsion A 7.00

100.00

1. Nonionic fluorocarbon surfactant from E. I. Du Pont De Nemours & Company of Wilmington, Delaware, USA.

To make the emulsion polish composition, the Wacker TPR Silicone Resin; Petrolite VYBAR® 825; Hoechst Wax E and Wacker SLM 50553/1 (Wax W 23) Silicone Wax are charged into a melting vessel and heated with stirring to 100°C. The water is charged to a mixing vessel and is heated with stirring to 85°-90°C. The contents of the melting vessel are cooled to 85°-90°C. The PEMULEN® TR-1 is added to the melting vessel and the contents are kept at 85°C. and stirred until the PEMULEN® TR-1 is well dispersed. The contents of the melting vessel are then slowly charged to the mixing vessel with vigorous stirring. When the addition is complete, the heating is discontinued and the contents of the mixing vessel are allowed to stir at least another 10 minutes until the contents are homogeneous. Then 85% of the total 2-Amino-2- Methyl-1-Propanol (90% in water) is added to the contents of the melting vessel and allowed to stir into the contents for 10 minutes. The contents of the mixing vessel are then cooled to 25°-30°C. The BEDOUIN® preservative and the Du

Pont ZONYL® FSN-100 (100%) are then added to the contents of the mixing vessel with stirring. The stirring is continued for 10 minutes. The Wacker SLM 55072/1 TPR Resin Emulsion (Fluid Emulsion E 37) , Wacker SLM 23032 Silicone Wax Emulsion (Fluid Emulsion E 32) and the Wax Emulsion A are then charged to the mixing vessel with stirring. The remainder of the 2- Amino-2-Methyl-l-Propanol (90% in water) is used to adjust the pH of the resulting emulsion polish composition to 9.00- 9.50. The stirring is continued for 30 minutes to obtain a homogeneous emulsion polish composition. The viscosity at 20°C is from 150-500 centipoise (0.15-0.50 Pa.s) with a non¬ volatile content of from 4.10-4.16%.

Example 6

In this Example, an independent testing firm evaluated emulsion polish compositions of the present invention of Examples 1-5 versus commercially available solvent-based automobile polish compositions using test protocols published by the Industrieverband Putz Pflegemittel of Germany, an independent automobile association. The test scoring and results of the evaluation are described below. The results show that the emulsion polish compositions of Examples 1-5 are comparable to commercial solvent-based automobile polish compositions. TEST SCORING APPLIED

TO TABLES I-III

SCORE RATING ABBREVIATION USED IN TEXT

0.00-1.50 Very Poor

1.51-2.50 Poor

2.51-3.50 Satisfactory

3.51-4.50 Good +

4.51-5.00 Very Good ++

TABLE I

ATTRIBUTES B

Overall Performance

Convenience of Use

Polishing

Appearance

Color Depth

Gloss

Resistance to Grip

Protection

(3.27) (3.13) (4.40) (3.58) (3.36) (4.39)

A = Dauerschutz Politur from S. C. Johnson GmbH, 5657

Haan 1, Germany B = Rex Hochglanz Politur from Erdal Rex, Mainz, Germany C = Polish Composition of Example 1 D = Dauerschutz Politur Metallic from S. C. Johnson GmbH,

5657 Haan 1, Germany E = Hochglanz Politur Metallic from Erdal Rex, Mainz, Germany F = Polish Composition of Example 2 TABLE II

ATTRIBUTES B D

Overall Performance + + + + + 3.87 3.79 3.94 3.80 4.14

Convenience of Use + + + + +

Polishing + + 0 + 0

Appearance + + + +

Color Depth + + + + +

Gloss + + + + +

Resistance to Grip ++ ++ + ++ +

Protection 0 0 + 0 ++ (3.27) C3.14) (4.16) (3.05) (4.58)

A = Autopudding from S. C. Johnson GmbH, 5657 Haan 1, Germany

B = Armor-All Polish 'N' Wax from Armor All, Irvine,

California

C = Polish Composition of Example 3

D = Autopudding Metallic from S. C. Johnson GmbH, 5657

Haan 1, Germany

E = Polish Composition of Example 4

TABLE III

ATTRIBUTES B D

A = Dauerschutz Hartwachε from S. C. Johnson GmbH, 5657 Haan 1, Germany

B = Sonax Hart Wax from Hoffmann, Neuburg, Germany C = Rex Dauerwachs from Erdal Rex, Mainz, Germany D = Polish Composition of Example 5

Claims

• That which we claim is:

1. A water-based oil-in-water emulsion polish composition comprising

A. from about 0.05% to 25% by weight of the total composition of a polymeric silicone wax;

B. . from about 0.1% to 30% by weight of the total composition of a polyorganosiloxane resin;

C. an effective amount of a polymeric electrostatic emulsifier for forming oil-in-water emulsions which is a modified polymer having a major portion of a monoolefinically unsaturated carboxylic acid monomer or its anhydride of 3 to 6 carbon atoms and a minor portion of a long chain acrylate or methacrylate monomer which polymer is neutralized with an effective amount of a base and is capable of dispersing (A) and (B) within

D. water comprising the balance of the composition to form an oil-in-water emulsion wherein the composition is substantially free of any added organic solvents and water- sensitive surfactants.

2. The composition as claimed in Claim 1 wherein the composition contains from about 0.05% to 5% by weight of a polymeric electrostatic emulsifier which is an acrylates/Cιo~ C Q alkyl acrylate cross polymer.

3. The composition as claimed in Claim 1 wherein the silicone resin is of the formula

^((CH3⁾ ₃ ^Si⁰ _1/2⁾a^(Si^θ4_/2⁾b^((CH₃ ⁾2^Si^θ2/2⁾c wherein a+b is from 20% to 50% by weight of the resin, c is from 50% to 80% by weight of the resin and the ratio of a to b is from 6:10 to 8:10.

4. The composition as claimed in Claim 1 wherein the silicone wax is a trimethylsiloxy-endblocked polymer selected from the group consisting of a copolymer of (CH₃)₂SiO units and CH₃RSiO units and a homopoly er of CH RSiO units wherein the polymer is a waxy solid at 25°C. having a melting point of no more than 100°C. wherein R is an alkyl group of from about 8 to 30 carbon atoms.

5. The composition as claimed in Claim 1 wherein the composition further contains from about 0.1% to 30% by weight of the total composition of at least one synthetic or naturally-derived wax other than a silicone wax.

6. The composition as claimed in Claim 1 wherein the composition further contains from about 0.1% to 20% by weight of the total composition of a poly(alpha-olefin) polymer derived from the polymerization of at least one 1-alkene of from about 5 to 20 carbon atoms per molecule.

7. A water-based oil-in-water emulsion polish composition comprising A. from about 0.05% to 3% by weight of the total composition of a polymeric silicone wax;

B. from about 0.1% to 5% by weight of the total composition of a polyorganosiloxane resin;

C. from about 0.05% to 5% of a polymeric electrostatic emulsifier for forming oil-in-water emulsions which is a lightly cross-linked modified polymer having a major portion of a monoolefinically unsaturated carboxylic acid monomer or its anhydride of 3 to 6 carbon atoms and a minor portion of a long chain acrylate or methacrylate monomer which polymer is neutralized with an effective amount of a base and is capable of dispersing (A) and (B) within

8. The composition as claimed in Claim 7 wherein the polymeric electrostatic emulsifier is an acrylates/Cιo~^c ₃o alkyl acrylate cross polymer.

9. The composition as claimed in Claim 8 wherein the silicone resin is of the formula

(^(CH₃ ⁾ ₃ ^Si⁰ _1/2 ⁾a^(Si^θ4_/2 ⁾b^{(( H}3⁾2^Si^θ2/2⁾c wherein a+b is from 20% to 50% by weight of the resin, c is from 50% to 80% by weight of the resin and the ratio of a to b is from 6:10 to 8:10.

10. The composition as claimed in Claim 9 wherein the silicone wax is a trimethylsiloxy-endblocked polymer selected from the group consisting of a copolymer of (CH₃)2SiO units and CH₃RSiO units and a homopolymer of CH₃RSiO units wherein the polymer is a waxy solid at 25°C. having a melting point of no more than 100°C. wherein R is an alkyl group of from about 8 to 30 carbon atoms.

11. The composition as claimed in Claim 10 wherein the composition further contains from about 0.1% to 30% by weight of the total composition of at least one synthetic or naturally-derived wax other than a silicone wax.

12. The composition as claimed in Claim 11 wherein the composition further contains from about 0.1% to 20% by weight of the total composition of a poly(alpha-olefin) polymer derived from the polymerization of at least one 1-alkene of from about 5 to 20 carbon atoms per molecule.