CA2121267C - Improved fabric cleaning shampoo compositions - Google Patents

Abstract

An improved aqueous fabric cleaning shampoo composition contains a combination of (a) about 0.5-20% by weight of a fabric cleaning polymer which is a solid at 25 °C and water dispersible or water soluble upon neuturalization with an alkaline compound such as a polymer of methacrylic acid/styrene/n-butyl acrylate, (b) about 0.1-10% by weight of a specific type of wax having a melting point of at least 50 °C such as pressure-emulsified polyethylene wax and (c) about 0.05-5% by weight of a silicone betaine polymer in addition to an effective amount of at least one conventional anionic, amphoteric or zwitterionic surfactant in water at a pH of from about 7 to about 10.5. Such a fabric cleaning shampoo composition not only provides good cleaning and conditioning to fabrics, particularly synthetic fibre fabrics, such as those used in carpets as well as to upholstery and pile fabrics, but also provides soil resistance to the fabric cleaned with such a composition.

Description

W094/07980 2 1 2 1 2 6 7 PCT/USg3/~88 IMPROVED FABRIC CLEANING SHAMPOO COMPOSITIONS

Technical Field This invention relates to an improved aqueous fabric cle~ning shampoo composition containing a combination of a fabric cleaning polymer, a rpecific type of wax and a silicone betaine polymer in addition to at least one 10 conventional surfactant to provide a fabric cl~aning shampoo composition which not only provides good cl~an~ng and ¢onditioning to fabrics, particularly synthetic fibre fabrics, such as those used in carpets as well as to , ~
upholstery and pile fabrics, but also provides improved soil 15 resistance to fabrics cleaned with such a composition.

c~L~ul-~ Art Shampoo compositions for use on fabric materials such as - carpets and upholstery have existed for a number of years.
_h~- types of p~ ~ are used on fabrics that are large in size or fixed in place on furniture and thus cannot be easily removed from their current location for cl~ ng. In the case of carpets and rugs, these fabrics tend to receive high foot traffic and may get dirty rather quickly. Because, of ~; 25 their size or location, such fabrics are not cleaned very ; often and thu~ it is beneficial to provide such fabrics with soil repellent treatments. Unlike articles of clothing that can be laundered in a clothes w~chinq machine, the surfactants used to clean such fabrics cannot readily be 30 rin~-~ from the fabric with water since the carpet or upholstery is fixed in place. Therefore there has been a constant desire to provide fabric cleaning compositions that can remove soil from carpets or upholstery with a minimum amou~nt~of water to~speed drying of the fabric being cle~ngA
35~iwhile~removing as much of the surfactants as possible since they~ténd to attract soil. Excess water can also cause shrinkage and warping of carpeting and may also promote mold 'growth. It is further desirable to have the cleaning composition impart anti-soiling properties to the fabric , ~ .
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WOg4J07980 2 1 2 1 2 6 7 - 2 - PCT/US93/0~88 being cleaned to increase the time span between cleanings.
Conditioning of the fabrics as a part of the cleaning process is also desirable.
Anti-soiling or soil repellency is described as the 5 ability of a fabric such as a carpet to resist subsequent resoiling as a result of normal use such as foot traffic on carpets and ordinary use of furniture. It is a rough measure of the attraction or repulsion power of the products used to clean the fabric. Most carpeting and, often fabric furniture 10 upholstery, is treated with a soil-resisting layer during the manufacture of the fabric or shortly before it is provided to the ~G,.sumer. Examples of such treatments are the TEFLON~
carpet treatment from E. I. Du Pont De Nemours & Company of ~Wilmington, Delaware, U.S.A. that is used in carpeting ; 15 bearing the STAINMASTER~ trademark and the SCOTCHGARD~
~ cts from 3M Company of St. Paul, Minnesota, U.S.A. which are used on both carpeting and fabric upholstery. Although these ~od~cts render the fabric resistant to soiling, it is observed in many cases that the subsequent application of a 20 shampoo fabric cleaning composition actively promotes the r~h~uent rate of resoiling of the cleaned fabric.
A number of attempts to provide sh~mpoo fabric cl~nin~
compositions have been made. U.S. Pat. Nos. 3,723,323 and 3,723,358 to Morgan et al. each describe aqueous fabri~
25 treating shampoo compositions containing anionic or nonionic surfactants as cleansing agents and neutralized polymers of acrylic or methacrylic acid with styrene or other unsaturated monomers such as alkyl acrylates and methacrylates. The polymer is said to impart anti-soiling properties to fabrics 30 cleaned with the compositions. The composition is scrubbed into the fabric, allowed to dry, and then vacuumed away with the soil because the composition gets brittle and flakes away from the fabric fibres along with the soil upon drying. U.S.
Patent No. 4,013,595 to Podella et al. teaches non-flammable 35 a~eo~C aerosol rug cleaners using hydrocarbon propellants.
They pOC~O~c reduced flammability due to the presence of at least 0.3% lauryl alcohol in combination with 0.3-10% of an metal lauryl sulfate salt as at least one of the surfactants. The Podella et al. compositions also contain W094/07980 2 1 2 1 2 fi 7 PCT/US93/09088 polymers of the type taught in the Morgan et al. Patents above.
U.S. Pat. No. 4,304,610 to Weisensel teaches a carpet cleAning method for use with extraction machinery to clean 5 carpets that contain high foaming anionic surfactants. The a~eQ~lC liquid or dry powder composition contains a cationic surfactant that reacts with and suppresses foaming of the anionic surfactant in the carpet, a nonionic surfactant as a primary cleAn1ng agent, builders, fillers and chelating lO agents, and optionally, optical brighteners, dyes and perfumes.
U.S. Pat. No. 3,734,686 to Douglas teaches a carpet cl~a~in~ shampoo composition for carpets and pile fabrics which is said to en~n~ç the abrasion resistance and 15 antistatic ~lu~Lies of the treated carpet or pile fabric.
This benefit comes from the p~ nce of an aqueous emulsion of o~en-free polyethylene of particle size 0.02 to 0.5 mic~G..~ and average molecular weight of 7,000-40,000 where at least 30% of the particles are covered with an emulsifier 20 composition. The composition is said to pOC~~-s increA~~~
foaming action and less force i~ needed to apply the shampoo ~ to the carpet.
; U.S. Pat. No. S,073,442 to Rnowlton et al. teaches a method of enhancing the soil resistance and stain resist,ance 25 of polyamide and wool fabrics by treating them with a solution containing (1) the con~nRAtion product of formaldehyde with bis(hydroxyphenyl)sulfone, phenylsulfonic acid, dihydroxy(diphenyl)sulfone or benzenesulfonic acid; (2) a fluorochemical and (3) an acrylic polymer or copolymer.
30 The compositions may q~so contain modified wax compositions such as paraffinic wax emulsions, microcrystalline wax emulsions or metalized wax emulsion~. Acrylic polymers can be added to the compositions to reduce the discoloring effect of the phenolic resin on the fabric as well as to give the 35 fabric a softer hand. The fluorochemical is said to improve ; the water and oil repellency of the treated fabric and also improves antisoiling properties. Knowlton et al. generally teach that silicones, fluorocarbons, waxes, acrylic polymers and combinations thereof have been used in repellent and wo 94/o7g80 2 1 2 1 2 6 7 4 PCT/U$g3/09088 antisoil finishes, but offer little or no protection against warm to hot liquid spills. This composition is primarily used as a treatment that is separate from normal cleaning operations.
S U.S Pat. No. 4,784,799 to Petroff teaches synergistic surfactant compositions that are a combination of alkylbenzenesulfonate anionic surfactants and at least one organic zwitterionic functional silicone surfactant such as a silicone sulfobetaine surfactant. The latter is a 10 trimethylsiloxy-endblocked polydior~AnQsiloxane com~ of ~ sulfobetaine(methyl)siloxy units and, optionally, '~ dimethylsiloxy units. These compositions can be used in A~ing detergents, liquid and powdered detergents and cleaners. Other examples of silicone polymers containing 15 betaine-functional groups can be found in U.S. Pat. Nos.
4,609,750 and 4.654,161 to Kollmeier et al. These silicone polymers are said to be useful for cosmetic preparations, especially hair care products such as hair conditioners.
U.S Pat. No. 4,269,739 to Grejsner teaches an agent for ~;' 20 treating and cleAning records and similar objects that contains, in ~ir-olved or emulsified form, from 0.001-1.2% of a natural or synthetic wax or wax-like sub~tance, from 0.001-2.5% of a fluid silicone oil with lubricating activity, 0.001-2.5% of a surface-active polysiloxane copolymer,,0.001-25 1.2% of a fluorinated organic surfactant and 0.001-2.5% of a nonionic surfactant. It is used to clean and form an anti~tatic and lubricating coating on records and plastic articles such as photographic articles, optical lenses and television screens. All stated components are required and 30 act synergistically. Nothing is taught concerning the use of such compositions in conjunction with cleaning fabrics.
U.S Pat. No. 4,780,100 to Moll teaches a foaming aqueous aerosol fabric cle~nin~ composition which has foaming surfactants, solvents, propellants, builders and water. The ~; 35 foam is said to enter the fabric pile and brings dirt up to the surface as a second foam is formed when the solvent evaporates. The only requirement for surfactants is that they form a foam and can include organosilicones. Amphoteric surfactants such as betaines can be used. Nothing is taught WOg4/07~0 2 1 2 1 2 ~ 7 PCT/US93/0~88 . _ 5 _ concerning the addition of polymer additives or waxes to these cleaning compositions.
U.S Pat. No. 4, 678, 595 to Malik et al. teaches a carpet shampoo or upholstery cleaning composition containing a 5 glycoside surfactant, a normally solid, water soluble or water ~i.srersible polymer component and w~ater. The composition is applied to a carpet, allowed to dry to form a non-tacky, friable film or polymeric residue and is then vacuumed away to remove the soil-containing residue. The 10 polymers used can be butyl acrylate/styrene (optional)/methyl methacrylate/methacrylic, acrylic, and/or itaconic acid copolymers. Optionally, antistatic aqents, foam builders and stabilizers such as amine oxides and amphoteric cycloimidines or imidazolines, optical brighteners, perfumes and the like - 15 can also be included.
U.S Pat. No. 3,335,086 to Morris teaches soil anti-ed~rosition additives to prevent the rederosition of soilonto fabrics, clothes and the like while w~hing, shampooing, al~nd~ring and dry cleAni ng such articles. The additives are 20 composed of a synergistic combination of carboxymethyl cellulose and a hydrolyzed polymer having a substantially linear hy~ Gcarbon chain and both hydroxyl a~nd carboxyl ~-o~_ along the chain. These are then added to liquid or powdered detergent compositions to improve the anti-25 redeposition properties of the detergents.
U.S Pat. No. 4,561,992 to Troger et al. teaches anaerosol cleaning agent for textile surfaces which contain~
plasticized urea-formaldehyde resin foam particles (O.005-0.120 mm), propellant, antisettling agent, suspending agent, 30 liquid and sodium aluminum silicate particles. A silicone defoamer may be included to promote the removal of soap residue. No moisture-re~A i ni ng cationic antistatic agents are said to be needed. The product is applied to textile upholstery, allowed to dry and vacuumed away from the fabric.
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35 The cle~ning agent is the sodium aluminum silicate particles.
The following further represent the state of the art.
Additional aqueous liquid carpet and fabric cleaners are taught in U.S. Pat. Nos. 3,630,919 to Sheaffer et al.;

3,639,290 to Fearnley et al.; 3,736,259 to Buck et al.; and 3,919,101 to Anstett et al. i surfactant-free carpet cleaning and soil repellent composition is taught in U.S.
Pat. No. 4,035,148 to Metzger et al. Dry powder carpet cleaners are taught in U.S. Pat. Nos. 4,659,494 to Soldanski 5 et al. and 4,566,980 to Smith. Treatment compositions for textiles h~e~ upon fluorochemical compounds are taught in U.S. Pat. Nos. 3,987,227 to Schultz and 4,043,923 to Loudas.
Acrylic polymers for use in carpet shampoo compositions are taught in U.S. Pat. Nos. 4,203,859 to Kirn et al.
10 Antisoiling and anti-redeposition polymer latices for use in conjunction with the aqueous w~C~ing of textile articles are taught in U.S. Pat. No. 4,925,588 to Berrod et al. Wax-, con~;ning compositions for use in conjunction with detergents for textiles are taught in U.S. Pat. Nos.
15 4,447,349 to Tai; 4,451,387 to Tai; and 4,599,189 to Wuhrmannet al.

Summary Disclosure of the Invention one object of the present invention is to provide an 20 aqueous shampoo composition for fabrics of the type used for carpets, rugs and upholstery and pile fabrics that are ~; cle~n~ in place. These compositions are~particularly useful for fabrics made from synthetic fibres. These compositions are especially useful for fabrics which have already been 25 pre-treated with soil-resisting products. These compositions have good cleaning properties and also leave the cleaned fabric with greatly improved resi~tance to soiling as well a~
with a conditioned feel. The combination of carpet cleaning polymer, wax and silicone betaine described below produces a 30 compo~ition with properties that are much better than is seen with the use of any one of these components alone. The co~positions are ~prayed onto the fabric to be cleaned using an aerosol or a non-aerosol trigger sprayer, worked into the fabric, allowed to dry and then vacuumed away to remove soil 35 and leave the fabric conditioned and treated with a soil repellent fini~. Fabrics which have been pre-treated with a soil-repellir.g treatment that are cleaned with the compositions of the present invention ha~e a reduced tendency for the cleaned fabric to resoil relative to other wo 94/07g80 2 1 2 1 2 6 7 PCT/US93/~9088 conventional shampoo fabric cleaning compositions. Since dirt particles may be hard and have sharp edges, the presence of dirt can damage the fibre by abrasive action. Thus, a product which reduces the amount of dirt associated with the 5 carpet fabric may prolong the life of a carpet by reducing wear due to the abrasive action of dirt within the fibres.
These and other objects and advantages of the present inv~llLion are provided by an improved carpet shampoo composition which leaves a powdery product which can be 10 vacuumed away when dry comprising an effective amount, preferably from about 0.5-20%, more preferably from about 0.5-10%, and most preferably 0.5-4%, by weight of the total composition, of at least one surfactant selected from the ~ou~ consisting of anionic, nonionic, amphoteric and 15 zwitterionic surfactants, preferably from anionic, amphoteric and zwitterionic surfactants, which are suitable for shampooing a carpet and being substantially vacuumed away when dry which surfactant is dispersed in water at a pH of from about 7 to 10.5, preferably from about 8.5-9.5, wherein 20 the im~o~ement comprises a) from about 0.5 to about 20% by weight of the total composition, more preferably from about 0.5-10%, and most preferably from about 0.5-4%, of a fabric cleaning polymer which is normally solid at 25 C. and is water soluble o~
2s water dispersible upon neutralization with an alkaline com~oul.d such as a polymer of methacrylic acid/styrene/n-butyl acrylate;
b) from about 0.1 to about 10%, preferably from 0.5-2%, by weight of the total composition of wax, preferably as 30 particles derived from an aqueous emulsion, selected from the ylOU~ consisting of a synthetic wax, a natural wax or a wax-like synthetic organic substance having a melting point of at least 50~C., preferably a pressure-emulsified oxidized : polyethylene wax; and c) from about 0.05% to about 5%, preferably from 0.25-0.5%, by weight of the total composition of a compatible ~;~ silicone betaine polymer.

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W094/07980 2 1 2 1 2 6 7 8 PCT/US93/0~88 Best Mode for carrying out the Invention The aqueous shampoo compositions of the present invention require the presence of at least one surfactant and water in addition to the three ingredients that provide the 5 improved properties poss~ssed by the compositions of the ent invention. Deionized water or low mineral content, soft water is preferred. The percentages given herein are hA~-~ upon non-volatile solids (actives) content ("NVM") unless otherwise specified.
The surfactants useful are an effective cle~njng amount, typically from 0.5% to 20% by weight of the total shampoo composition, of any anionic, nonionic, amphoteric or '-~ zwitterionic surfactant that is useful in carpet shampoo compositions and being substantially vacuumed away when dry - 15 when combined with a carpet cleAning polymer of the type described below. Examples of such surfactants are given in U.S. Pat. Nos. 3,723,323 and 3,723,358 to Morgan et al. noted above. The anionic, amphoteric and zwitterionic surfactants are more preferred. Preferably from about 0.5-10% by weight 20 of the total composition, and more preferably from about 0.5-2% of the composition is composed of such surfactants. Use of more than the minimum amount of surfactant needed to remove the soil in a fabric is undesirable since surfactant residues left in the fabric, particularly those which a~e 25 nonionic, tend to attract soil and dirt to the cleaned fabric and thus reduce the antisoiling effect of the compositions of the present invention.
Examples of suitable synthetic organic anionic - surfactants are alkyl glyceryl ether sulfonates; alkyl 30 sulfonates; alkyl monoglyceride sulfates or sulfonates; alkyl polyethoxy ether sulfonates; alkyl aryl sulfonates; acyl sarcosinates; acyl esters of isethionates; alkyl esters of sulphosuccinic acid; and alkyl phenol polyethoxy sulfonates.
In these compounds, the alkyl and the acyl groups, ~~~p~ctively, contain 10 to 20 carbon atoms. They are used -~ in the form of water soluble salts, for example, sodium, potassium or ammonium salts. Specific examples of the ~ anionic organic surfactants are sodium lauryl sulfate, sodium ,~
:' W O 94/07980 2 1 2 1 2 ~ 7 P(~r/US93/09088 _ g _ dodecyl sulfonate, sodium alkylolamide sulphosuccinate and sodium N-lauroyl sarcosinate.
Examples of nonionic synthetic surfactants are polyethylene oxide condensates of alkyl phenols wherein the 5 alkyl ~u~ contains from 6 to 12 carbon atoms and the ethylene oxide is present in a molar ratio of ethylene oxide to alkyl phenol in the range of 10:1 to 25:1; condensation ~oducts of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine wherein 10 the molecular weight of the condensation product ranges from S,000 to 11,000; the condensation product of from about 5 to 30 moles of ethylene oxide with one mole of a branched or straight-ch~in aliphatic alcohol containing from about 8 to 18 carbon atoms; trialkyl amine oxides and trialkyl phosphine 15 oxides wherein one alkyl group ranges from 10 to 18 carbon atoms and two alkyl groups range from one to three carbon atoms.
Examples of amphoteric and zwitterionic surfactants are organic alkyl betaines, alkyl sulfobetaines, alkyl amino-20 carboxylic acids and the like containing at least one longrh~ alkyl ~ ou~ of from about 8 to 22 carbon atoms.
organic alkyl betaines include cocamidoprop~l betaine, cocamidoethyl betaine, isostearamidopropyl betaine, oleamidopropyl betaine, lauramidopropyl betaine, coco- , 25 betaine, and the like. Coco-sultaine is an example of a zwitterionic surfactant. Cocamidopropyl betaine is presently preferred.
As is known from the Morgan et al. Patents noted above, the fabric cleaning polymer component of the present invention is from about 0.5% to about 20% by weight of the total composition, more preferably from about 0.5% to 10%, - and most preferably from about 0.5-2%, of an addition polymer comprising a major proportion of at least one unsaturated monomer whose homopolymer has a glass transition temperature (Tg) of 65~C. such as methyl methacrylate (Tg typically 105~C.), ethyl methacrylate (Tg typically 65~C.), cyclohexyl methacrylate (Tg typically 66~C.), isobornyl methacrylate (Tg typically 110-170~C.), and styrene (Tg typically 100~C.) plus additional monoethylenically unsaturated monomers of various wo 94/07g80 2 1 2 1 2 6 7 PCT/US93/09088 Tg values to modify the hardness and viscosity of the resulting polymer. Examples of such monomers, including the aforementioned, are the lower alkyl acrylates containing from 4 to 14 carbon atoms such as ethyl acrylate, n-propyl 5 acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, octyl acrylate and decyl acrylate, acrylonitrile, methacrylonitrile, alpha-methyl styrene, alkyl methacrylates con~in~ng from 5 to 15 carbons such as octyl methacrylate, and l-alkenes having from 2 to 30 carbon atoms and the like.
lO Such monomers are used to modify the overall Tg of the polymer obtained which ~hould typically have a Tg of at least 25~C. so that it is a solid at room temperature, and more preferably, an overall Tg of at least 65~C.
To provide water dispersability or solubility to the 15 polymer, a minor amount of the polymer, generally from about 2~ to 40% of the total polymer, is composed of a polymerizable monoethylenically unsaturated monomer cont~ining free carboxyl ~ou~ such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and maleic 20 anhydride with methacrylic acid presently being more preferred. The weight average molecular weight of the polymer can range from about 2,000 to 500,000 although a weight average molecular weight of about 20,000 to about 400,000 is more preferred with the carboxylic acid cont~nt 25 being adjusted relative to the molecular weight of the polymer so as to provide a water ~;sr~rsible or water soluble polymer. These types of polymers are well known in the art as can be seen from an examination of the Morgan et al. U.S.
;~ Pat. Nos. 3,723,323 and 3,723,358 noted above. Presently, 30 polymers of methacrylic acid/styrene/n-butyl acrylate, which may optionally further contain alpha-methyl styrene, added as an aqueous emulsion are preferred.
As taught in the Morgan et al. U.S. Pat. Nos. 3,723,323 and 3,723,358 noted above which are hereby incorporated by 35 reference to teach such polymers, the polymer should be ~ present as at least 10~ of the polymer-surfactant mixture and ;~ the weight ratio of polymer to surfactant should be from about 0.1 to 1 to 1:1. It will be understood that the specific weight ratio of the polymer to surfactant will W094/07980 PCT/US93/~9088 depend upon the polymers and surfactants selected as well as the desired ultimate physical characteristics of the shampoo composition.
An effective amount of the carboxyl groups present in s the polymer, preferably from about 80% to 100% of the stoichiometric amount, are neutralized to an alkaline pH to e,.der the polymer water dispersible or water soluble. Such ne~alization can be done with an alkaline neutralizing agent such as an organic base such as amino alcohols such as 10 triethanolamine, 2-amino-2-methyl-l-propanol, and 2-amino-2-methyl-1,3-propanediol and organic amines of from 2 to 22 carbon atoms such as triethylamine and laurylamine, or inorganic hA~c such as ammonium hydroxide, sodium hydroxide, - potassium hydroxide, sodium carbonate, and the like. The pH
15 of the shampoo composition is adjusted to from about 7 to 10.5 and more prefera~ly, from about 7.5 to 8.5 for non-~- aerosol trigger sprayer compositions and about 9.5 to 10.5 for aerosol spray compositions.
Another required component of the present invention is 20 from about 0.1% to about 10%, more preferably from about 0.1%
to about 5%, and most preferably from 0.5-2%, by weight of the total composition of a wax selected from the ~ou~
consisting of a synthetic wax, a natural wax or a wax-like synthetic organic substance having a melting point of at 25 least 50~C. and more preferably at least 100~C. Examples of such waxes are carnauba wax, paraffin wax, polyolefin waxes, modified polyethylene waxes such as oxidized polyolefin waxes such as oxidized polyethylene, maleinized polyethylene and acrylated polyethylene waxes, micro-crystalline waxes, 30 oxidized micro-crystalline waxes, montan wax and the like.
These waxes are well known in the art and are commercially available from various manufacturers.
A hard wax such as a pressure emulsified polyethylene wax is presently preferred. Such waxes are commercially sold 35 under the trade name AC Polyethylene AC 330 by Allied Chemicals of Morristown, New Jersey, U.S.A., which is an emulsifiable oxidized high density polyethylene containing some carboxyl groups and having a molecular weight of about 5,000, a Brookfield viscosity of s,OOo centipoisa (g.ooo WOg4/07980 2 1 21 2 ~ 7 - 12 - PCT/US93/~88 pascal.second) at 140~C., an acid number (0.5 g/xylene/0.1 N
alcoholic sodium hydroxide, phenolphthalien indicator) of 25-34 and a penetration value of 0.5 maximum (100 grams/Ss/25~C). This wax can be emulsified in water using a S base such as potassium hydroxide, a preservative and a small amount of a nonionic surfactant. Another example of a hard polyethylene wax is AC Polyethylene AC 316A from Allied Chemicals which is a high density oxidized polyethylene ~ r-~re emulsified wax having a Nettler dropping point of 10 140~C., an acid number of 15-18 (milligrams of KOH per gram), a density of 0.98 grams/cubic centimeter at 25~C., Brookfield v;~cocity of 8,500 centipoise (8.500 pascal.seconds) at 150~C. and a hald.~ at 25~C. of less than 0.5 dmm.
Some other specific examples of waxes are AC 629 lS Polyethylene Wax from Allied Chemicals that is a low - molecular weight, low density oxidized polyethylene that is ;~ softer than the AC 330 wax having a softening point of 104~C.
~ASTM E-28), a hardness of 5.5 (ASTM D-5), a Brookfield v~Qcity of 200 centipoise (0.2 pascal.second) at 140~C., 20 and an acid number of ~6 (mg KOH per gram). EPOLENE~ E10 Wax is an emulsifiable polyethylene wax having a ring and ball softening point of 106~C., penetration hardness of 3.0 (100 grams/s ~?con~c/25~C., tenths of a millimeter), acid number of 15, Brookfield viscosity (No. 3 spindle, 30 rpm) of ~,200 25 centipoise ~1.2 pascal.second) and EPOLENE~ Ell, E12, E14, E
15, and E20 Waxes are polyethylene waxes in the same family as EPOLENE~ E10 Wax. EPOLENE0 E43 Wax is an emulsifiable pol~vpylene wax having a weight average molecular weight of 9,100 (gel permeation chromatography), ring and ball 30 sof~ning point of 157~C., penetration hardness of <0.5 (100 grams/5 seconds/25~C., tenths of a millimeter), acid number of 47, Brookfield viscosity (No. 3 spindle, 30 rpm) of 0.3So centîpoise (0.35 pascal.second) at 12S~C. The EPOLENE~ waxes are from Eastman Chemical Products, Inc. of Kingsport, 35 Tenne~~e, U.S.A. An example of an ester of montan wax is Hoechst Wax KLE from Hoechst AG of Middlesex, England having a dropping point of 79-85~C., a viscosity of 22.60 mPa.s at 100~C. Ho~c~t PED 153 Wax from Hoechst AG is a fairly hard oxidized polyethylene wax having a dropping point of 120~C.
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wo g4/07980 2 1 2 1 2 6 7 PCT/US93/09088 (DGF-M-III 3 (75)). Other Hoechst waxes which may find use in the present invention are those sold under the designations PED 121, PED 136, PED 191, PED 261, PED 521 and PED 522.
Another required component of the present invention is from about 0.05% to about 5%, preferably from 0.25-0.5%, by weight of the total composition of a compatible silicone betaine polymer that is compatible with the other components nt in the shampoo compositions of the p~-ent invention.
10 Such polymers are known compositions and are described in U.S. Pat. Nos. 4,609,750 and 4,654,161 to Rollmeier et al.
~ which are hereby incorporated by reference to teach such - - polymers and are commercially available from the assignee of ~'~ the Kollmeier et al. patents, Th. Goldschmidt AG of ~ss~n, 15 Germany under the trademarks TEGOPREN~ and ABIL0. Another type of silicone betaine, a silicone sulfobetaine polymer is ; described in U.S Pat. No. 4,784,799 to Petroff noted above .~ . ~ ., - which is hereby incorporated by reference to teach such silicone sulfobetaine polymers.
~ The preferred silicone betaine polymers are of the Kollmeier et al. type having the general formula R2(Rl)2Sio((Rl)2SiO)X(R2RlSiO)ysi(Rl)2R2 .

25 wherein R1 can represent the same or different groups in the molecule and may be an alkyl radical with 1 to i8 carbon atoms, an aryl radical or a polyoxyalkylene radical with the proviso that at least 70% of the Rl radicals are methyl radicals, R2 may be the same as R1 with the proviso that at least one R2 radical is selected from one of the group consisting of (I) -(CH2)30CH2CHR3CH2R4 groups ' 35 in which R3 and R~ are different, one radical representing a ; hydroxyl ~L GUp and the other represents the "

2 1 2 1 2 67 14 _ PCT/US93/~88 -N+R5R6(CH2)nCoo- group in which R5 and R6 are the same or different and each ~e~-~nts an alkyl radical with l to 4 carbon atoms or a 5 benzyl radical, and n=l, 2 or 3, and (II) :~ -R7CoNHR8N+R5R6 (CH2 ) nC~~~ ~ rC

in which R7 is a divalent alkylene radical with 2 to 12 lO carbon atoms and R8 is a divalent alkylene radical with 2 to 6 carbon atoms, R5, R6 and n are as above, and each x has a value of from 0 to 200, and y has a value of from l to 50.
Specific examples of presently preferred polymers of 15 these ~y~e_ are TEGOPREN~ 6950 from Th. Go1~chmidt that, a~eo~ing to the manufa~.er, is a 30% NVM aqueous solution of~'a ~ilicone betaine polymer having a molecular weight of about 2,500 and being of the general formula (cH3)3sio(siAcH3o)m(si(cH3)2o)nsi(cH3)3 wherein A has the for~ula CH2)30CH2CH(OH)CH2N+(CH3)2CH2COO-' m and n are each greater than 0, the sum of m+n being such that the viscosity of the polymer at 25~C. is from about 50-90 square meters per secon~, its specific gravity at 25~C. is from about l.07 to l.O9 grams per cubic centimeter, and the ~ - 30 Ross Miles foam height of the polymer at 0.l~ solution in -~ water 8 dH, at 25~C. is 80.
Th. Goldschmidt also sells this product under the name ABIL~ B 99S0 which, according to the manufacturer, is a 30%
NVN a~eoll~ solution of a silicone betaine polymer of the 35 ~same general formula and with the same specific gravity value ~5~ as~the~TEGOPREN 6950, but reports a 1% solution of the 'polymèr in~water at 25~C. has a surface tension of 23-25 N.m~l~.; Th-~manufacturer states that this polymer has been . ,,.- , , wo g4/07~80 2 1 ~ 1 ~ 6 7 PCT/USg3/~88 given the Cosmetics, Toiletry and Fragrances Association ("CTFA") designation of Dimethicone Propyl PG-Betaine.
To improve cleaning of oily dirt, from about 0.5% to about 15%, more preferably from about 2% to 5%, by weight of 5 an organic solvent is optionally, but preferably, included within the compositions of the present invention. Examples of such solvents can be alcohols such as ethyl alcohol and isopropanol, glycol ether solvents such as propylene glycol monomethyl ether, propylene glycol n-butyl ether, dipropylene l0 glycol monomethyl ether, tripropylene glycol butyl ether, di~o~ylene glycol n-butyl ether, dipropylene glycol dimethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether as well as propylene carbonate.
In addition to the above required ingredients, minor 15 amounts, typicaIly less than 5% of the total composition, of entional additives may be included as optional e~ients such as preservatives and antimicrobial agents such as TR~,~C~~ DP-300 (substituted diphenyl ether) from ;~ Ciba-Geigy Co-~o~ation, Dyestuff & Chemicals Division, 20 Green~hQro~ North Carolina, U.S.A.; optical brighteners such as TINOPAL~ CBS-X (distyrylbiphenyl derivative) and TINOPA~0 5BM-GX (stilbene derivative) from Ciba-Geigy; dyes; perfumes;
stain-blocking agents such as ALGARD~ RD (aromatic sulphonic acid condensate for use on nylon carpets as a stain repe,llent 25 finish) and ALGARD~ NS (aqueous solution of an aromatic sulphonic acid condensate) from Allied Colloids of Yorkshire, England and ZELAN~ 338 (a 20-30% NVM aqueous solution of a carboxylated polymer salt) from E. I. Du Pont De Nemours &
Co. of Wilmington, Delaware, U.S.A.; antiredeposition agents 30 such as S~T~ HP22 (~.ixture of a nonionic surfactant and SOKALANo CP5--sodium salt of a modified polyacrylic acid--and SOKALAN0 CP9--sodium salt of a maleic anhydride/olefin copolymer) from BASF AG of Ludwigshafen, Germany; ultraviolet light absorbing comro~1n~e such as W INUL~ M-40 (2-hydroxy-4-35 methoxy benzophenone) and UVlNU~ MS-40 (2-hydroxy-4-methoxy ~- benzophenone-5-sulfonic acid) from BASF Corporation of ~ ~Parsippany, New Jersey, U.S.A.; detergent builders such as -;~ borax; chelating agents and other oil/stain repellents such ~ as fluorinated organic compounds such as ZONYL~ 7950 Carpet .
:~ ' wo 94/07g80 2 1 2 1 2 6 7 PCT/US93/09088 Protector(30% NVM in isopropanol) and TEFLON~ MF (TLF 5180) (72% NVM aqueous dispersion of polyaliphatic and polyfluoroaliphatic compounds) from E. I. Du Pont De Nemours & Co. of Wilmington, Delaware, U.S.A. These optional 5 additives may be added provided that they are compatible with the shampoo compositions and do not materially detract from the desirable properties of the shampoo compositions of the ~ ent invention.

Industrial ApplicabilitY
The aqueous fabric shampoo compositions of the present invention are low viscosity liquids which are typically less than lO centipoise (O.010 pascal.seconds) in viscosity at ' 25~C. that are suitable for delivery by spraying. They are l5 readily made simply by mixing the components together at room temperature or with slight heating to ~hAnce dispersion.
This is followed by adjusting the pH of the composition to the desired range of 7.0 to lO.5 with a suitable alkaline material. It is preferred that the wax compositions and the 20 fabric cleaning polymer be added as aqueous emulsions to speed the inco-~u ation of such materials into the composition h~in~ formed. Likewise, if a s~olvent is to be added, it can be used to dissolve more hydrophobic ients, with optional heating, such as waxes and 25 antimicrobial agents before addition to the aqueous components.
The fabric shampoo compositions of the present invention may be used as prepared by placing the composition in a suitable applicator package such as a conventional trigger or 30 pump sprayer bottle. Alternatively, the composition may be placed in a pressurizable container that is then pumped up with air to permit the contents to be dispensed under pressure in the form of a spray. The composition is then sprayed onto a carpet, rug or piece of uphalstery which is to 35 be cleA~. As is done with conventional shampoo compositions, the composition is worked into the fabric with ~; a brush or other suitable applicator, allowed to dry and then the dry composition, which further contains the soil and dirt removed from the fabric, is vacuumed away.

W094/07980 2 1 2 1 2 ~ 7 PCT/US93/09088 If an self-pressurized aerosol ~ormulation is desired, the shampoo composition can be charged into a pressurizable metal, glass or plastic container, sealed with a valve that is later fitted with an aerosol actuator button, and a 5 propellant such as from about 3% to 20% of the total composition of a conventional propellant such as dimethyl ether or one or more saturated alk~nes containing from 2 to 6 carbon atoms such as propane, isopropane, n-butane, isobutane, isopentane or n-h~Ane is added through the valve.
10 Mi~L~ of two or more propellants can be used. Optionally, the propellant may be added before the valve is sealed onto the container. In the interests of ecology, the container m~y be pressurized with nitrogen, air or some other compressible inert gas. The actuator button is pressed by 15 the user to atomize the shampoo composition into a spray which is then directed onto the fabric to be cleAned, usually in the form of a foam due to the p~ nce of the propellant.
If a foam is desired upon ~i~penQing from the container, a volatile propellant such as n-butane should be used since the 20 rapid evaporation of such ~L~llants upon leaving the actuator button ~Lo~ces foaming.
The shampoo compositions of the present invention can be used in the same manner as have other conventional shampoo compositions to clean fabrics such as carpets, upholstery and 25 pile fabrics with the further advantage that the fabric is not only cleaned, but is left conditioned with a soil repellent finish. It thus requires fewer cleAnings than fabric treated with conventional shampoo compositions of this type~
The following Examples are provided to show various ~pects of the present invention without departing from the scope and spirit of the invention. Unless otherwise indicated, all parts and percentages used are by weight.
In the following Examples, the "Soiling Capsule Test"
35 for use in measuring the anti-resoiling properties poss~
; by fabrics cleaned with various fabric cleaning shampoos was run as follows: A section of white nylon carpet which has a factory-applied dirt repellent coating is cut into a 25 inch by 7.5 inch (63.5 cm by 19.05 cm) test piece. The test piece is divided into four, five or six equal sections. The shampoo compositions to be tested are applied in an even layer to one of the sections and scrubbed into the test piece by hand using a medical vinyl glove to protect the hand. One 5 section is left untreated to act as a control or blank. The shampoo composition is allowed to dry at room temperature for 24 hours. The fabric is then vacuumed to remove the dried shampoo compo~it}on and soil. After drying and vacuuming, the fibres of the test piece are "fluffed up" by running the 10 fingers of one hand through the fibres to separate them from ~djacçnt fi~res.
The test piece is then placed in a drum that forms the soiling c~p~ e so that it lines the drum and the fibres of ~; the test piece point inward towards the center of the drum.
l5 Twenty grams of powdered "soil" (previously filtered through a mesh having l millimeter opçningS) is A~A to the interior of the drum as well as a tetrahedrally arranged rubber-footed tetrapod that simulates walking on the test piece during the operation of the soiling capsule. The soiling capsule drum is then rotated at about 40 revolutions per minute for five minutes.
After five minutes the rotation of the soiling capsule drum is stopped and the test piece is removed. It is shA~en free of loose soil and evaluated visually for the amount of 25 soil retained by each section. If it appears nece~sAry to remove loose dirt, the test piece may be vacuumed after removal from the soil capsule before evaluation. The condition of each section is then visually rAnk~ on a lO
point scale where lO is considered to be "totally clean" and 30 0 is "very dirty."
.
Examples 1-3 The following shampoo compositions illustrate carpet and fabric cl~Ani ng compositions in self-pressurized form that 35 can be used for day to day maintenance. ~hese compositions are intended to be used as a convenience product and for a light cleAning as well as an air freshening effect. The ~-~ composition is simply sprayed onto the fabric, allowed to dry and vacuumed away without scrubbing the composition into the .~

wog4/07980 ,2 1 2 1 2 S 7 PCT/US93/09088 fabric. These compositions further contain a sanitizer (T~.C~N~ DP-300) to reduce the level of bacteria in a fabric such as is found in a carpet to, for example, reduce odors.

S ~Y~mpl e: 1 2 3 Deionized Water 83.536 83.236 84.236 ~: Sodium Benzoate, flakes 1.500 1.500 1.500 Borax lO mol 0.500 0.500 0.500 TINOPAL~ CBS-X 0.002 0.002 0.002 10 TINOPAL~ 5BM-GX 0.002 0.002 0.002 SDA-3A Ethyl Alcohol (95%) 7.500 7.500 7.500 T~ DP-300 0.100 0.100 0.100 Sodium Lauryl Sulfate (28%)1.500 1.500 1.500 ~: . Sodium Lauryl Sarcosinate (30%) 0.410 0.410 0.410 - 15 REWOCOROSO B 30l01 0.500 0.500 0.500 Ruq C1eAn; ng Polymer A2 1.000 1.000 1.000 : AC 330 Wax Emulsion (28%)3 1.500 1.500 1.500 TEGOPREN0 6950 (30%) 0.250 0.250 0.250 ZONYL~ 7950 (30%) 0.500 0.500 0.500 20 p~r~no RD O.200 -- --ZELAN0 338 0.500 1.000 --~ragrance 0.500 0.500 0.500 Total Intermediate: 100% 100% 100%
To pH (used 50% aqu. KOH) 10.5 10.5 10;5 Final Composition: ~
Above Intermediate 85.000 85.000 85.000 n-Butane ~48 p.s.i.g. or 15.000 15.000 15.000 ~; 331 Pascal vapor pressure) 30 Total Composition: 100~ 100~ 100%

The percentages after the names are the actives content.
1. Alkenyl succinic acid, disodium salt from Rewo Chemisches Werke GmbH of Steinau, Germany.
35 2. Aqueous emulsion-polymerized polymer of methacrylic ~ acid/styrene/n-butyl acrylate in a 35/55/10 weight ratio - ~ having 25% NVM.

3. Aqueous emulsion of 28% AC Polyethylene AC 330, 7% of a nonylphenolethoxylate (lO ethoxy groups average) nonionic surfactant, 0.2~ of 37% formaldehyde, 1.4% of 50% aqueous potassium hydroxide solution, and 63.4%
S water having 35% NVM (2 grams/40 minutes/145~C.) and a pH of 8~5-9.5.

h~-e compositions are made by mixing the i,.~,e~ients together well with stirring in the order listed to form an 10 intermediate composition and adjusted to pH 10.5 with 50%
aqueous potassium hydroxide solution ~"50% aqu. KOH"). This ~; ~ intermediate is then added to a conventional pressurizable a~ l container that is then sealed with a conventional aerosol valve. The container is filled through the valve 15 with the indicated amount of n-butane and a conventional aero~ol actuator button or an actuator/overcap is placed on th'è stem of the valve. The composition can then be ~i~p~
onto a carpet or upholstery, worked into the fabric with a brush, allowed to dry and vacuumed away to leave a clean, 20 con~;tioned fabric with improved resistance to resoiling.
,~ -, ~ ~
es 4-7 t-The following shampoo compositions illustrate carpet and fabric cleA~in~ compo$itions in self-pressurized form which 25 can be used as deep cleaning aerosol compositions~

-,, ';~"~

W094/07980 - 21 2 1 2 1 2 6 7 PCT/US93/0~88 ~YAmple: 4 Deionized water 84 . 296 83 . 996 84 . 996 78 . 781 Borax 10 mol 0.500 o.500 0.500 0.500 Sodium Benzoate, flakes1.500 1.500 1.500 1.500 5 TINOPAL~ CBS-X 0.002 0.002 0.002 0.002 TINOPAL~ 5BM-GX 0.002 0.002 0.002 o.002 DOWANOLo DPNl 2.000 2.000 2.000 2.500 DOWANOLo pM2 2.000 2.000 2.000 2.500 JONCRYL~ 903 (44%) 1.000 1.000 1.000 4 . 330 10 AC 330 Wax Emulsion (28%) 1.500 1.500 1.500 1.570Sodium Lauryl Sulfate (28%)5.500 5.500 5.500 7.310 REWOCOROS~ B 3010 ~ - 0.500 TEGOPRENo 6950 (30%) 0.250 0~250 0.250 0.255 ~;~ ZONYL~ 7950 (30%) 0.500 0.500 0.500 --15 ALGUARD~ RD 0.200 -- -- --ZELAN0 338 0.500 1.000 -- --~ple (continued): 4 5 6 7 ance 0.250 0.250 0.250 0.250 Total Intermediate: 100% 100% 100~ 100%
- 20 To pH (used 50~ aqu~ KOH) 10.5 10.5 10.5 10.5 Final Composition: ~
Above Intermediate 92.500 92.500 ~2.500 92.500 n-Butane 7.500 7.500 7.500 7;500 25 Total Composition: 100% 100% 100% 100%
.
1. Dipropylene glycol monomethyl ether from Dow Chemical Company of Midland, Michigan, U.S.A.
2. Propylene glycol monomethyl ether from Dow Chemical.
30 3. Styrene/alpha-methyl styrene/acrylic acid polymer emulsion having 44% NVM (2 grams/40 minutes/145~C.), an acid value of the polymer of 65, a Brookfield viscosity of 200 mPa.s at 25~C., Tg of 110~C., a weight average molecular weight of greater than 200,000 and a pH of 8.
using ammonium hydroxide from Specialty Chemicals Mijdrecht B.V. - Polymers of Mijdrecht, the Netherlands, an associate company of S. C. Johnson & Son, Inc. of Racine, Wisconsin, U.S.A. .
~ ~ 4. Vapor pressure of 48 p.s.i.g. (331 Pascal).

WO94/07s80 PCT/US93/09088 These compositions are made by mixing the ingredients together well with stirring in the order listed to form an intermediate composition and adjusted to pH 10.5. This 5 intermediate is then added to a conventional pressurizable aerosol container that is then sealed with a conventional aerosol valve. The container is filled through the valve with the indicated amount of n-butane and a conventional aerosol actuator button or actuator/overcap is placed on the 10 stem of the valve. The composition can then be disr~n~e~
onto a carpet or upholstery, worked into the fabric with a brush, allowed to dry and vacuumed away to leave a clean, conditioned fabric with improved resistance to resoiling.
Exam~les 8-lO
- 15 The following shampoo compositions illustrate carpet and fabric clea~in~ compositions useful for trigger sprayer ~;~ application as spot and stain removers.

Example: 8 9 10 20 Deionized Water 84.650 84.350 85.350 Citric Acid, Anhydrous 0.400 0.400 0.400 ~ Sodium Carbonate 0.500 ~0.500 0.500 -~ Rug Cleaning Polymer A 3.000 3.000 3.000 Surfactant Blend A (35%)13 000 3.000 3;000 25 TEGOPREN~ 6950 (30%) 0.250 0.250 0.250 AC 330 Wax Emulsion (28%)31.500 1.500- 1.500 Fragrance 0.500 0.500 0.500 ZONYL~ 7950 (30%) 0.500 0.500 0.500 - ALGUARD~ RD 0.200 30 ZELAN0 338 0.500 1.000 --DOWANOL0 PM 3.000 3.000 3.000 Isopropanol, Anhydrous 2.000 2.000 2.000 Total: 100% 100% 100%
To pH (used 10% aqu. NaOH)8.0 8.0 8.0 ~; The percentages after the names are the actives content.
1. A 35% NVM blend of 13% sodium lauryl sulfate, 16% sodium alkyIolamide sulphosuccinate, 65% water and the balance surfactants and salts.

WOg4/0~0 2 1 2 1 2 6 7 PCT/US93/09088 These compositions are made by mixing the ingredients together well with stirring in the order listed to form the fabric cl~ning shampoo composition and adjusted to pH 8.0 5 with 10% aqueous sodium hydroxide solution ~"10% aqu. NaOH").
The composition is placed in a conventional trigger sprayer con~A i n~r . Although an entire area of fabric may be cleaned with this composition, it can also be used as a stain remover for small areas. The composition is sprayed onto a stain on 10 a carpet or upholstery and allowed to remain on the stain for 2 minutes. The area sprayed is then rubbed with a damp cloth or a mop ànd allowed to dry. If desired, the cleaned area may be vacuumed. A clean, conditioned area of fabric with im~oved resistance to resoiling results.

ples 11-12 The following shampoo compositions illustrate carpet and fabric cl~ning compositions in self-pressurized form that can be used as deep cl~ning aerosol compositions.

WO94/07s80 PCT/US93/09088 2~21267 - 24 -Example: 11 12 Deionized Water 75.493 78.812 Borax 10 mol 0.500 0.500 5 Sodium Benzoate, flakes 1.500 1.500 Rug Cleaning Polymer A 7.735 --JONCRYL~ 9o (44%) -- 4.299 REWOCOROS~ B 3010 0.500 0.500 Sodium Lauryl Sulfate (28%)5.487 7.310 10 TEGO-RF~TN~ L 71 1.706 --DOWANOL~ DPM 2.500 2.500 DOWANOLo PM 2.500 2.500 TINOPAL0 CBS-X 0.002 0.002 ~:~ . TINOPAL~ 5BM-GX 0.002 o.002 15 AC 330 Wax Emulsion (28%) 1.570 1.570 TEGOPREN~ 6950 (30%) 0.255 0.255 :~ Fragrance 0.250 0.250 ~:~ Total Intermediate: 100~ 100%
To pH (used 10% aqu. NaOH) 9.5 9.5 ~: 20 ~; Final Composition:
Above Intermediate 92.500 92.500 : n-Butane 7.500 7.500 Total Composition: 100~ 100%
1. A 30% NVM solution of cocamidopropyl betaine from Th.
Goldschmidt AG.

These compositions were made in the same manner as in 30 the previous examples by combining the ingredients in order and then placing the compositions in aerosol containers as described in Examples 4-7. These compositions are designed for use as heavy duty cleaners that are sprayed on the fabric to be cleaned and scrubbed into the fabric with a sponge mop 35 for best cleAnin~. The composition is allowed to dry and vacuumed away from the fabric.

~:, W094/07980 25 2121~67 PCT/US93/09088 Example 13 In this Example, the performance of Examples 11 and 12 were tested by the Soiling Capsule Test and in actual ~Y~o~ure to foot traffic versus commercially available carpet 5 shampoo compositions.
In the Soilinq Capsule Test results described in Table I
below, each block of results represents one soiling capsule carpet strip. The order of compositions listed from top to bottom in a block of four, five or six compositions 10 ~ ~~ents the order in which the compositions were placed on the strip from left to right. The scoring was done visually on a scale of 0 to lO where O was very dirty in appearance and 10 was totally clean in appearance:
- ..
Table I

Co~po5ition Score Composition Score WOOLITE- Deep Cleanl 5 GLORY0 Rug Cleaner2 4 Example 11 8 Example 11 6.5 20 BLANK 5 RESOLVE0 Aerosol3 1.5 WOOLITE~ }l Stainl 6 BLANK 5 WOOLITE~ Self Cl~n~n~l 7 PPZ4 4 RESOLVE~ Trigger Sprayer3 4 Example 12 5 25 Example 11 8 PPZ4 2 ~co~.vE~ Aerosol3 4 Example 11 ~ 5 BLANK 8 GLORY0 Rug Cleaner4 3 1001 TROURT~OOTER5 7 BLANK 6 PROFONDEUR6 1.5 ' ~ ' ~: .

WO 94/07980 PCI'/US93/09088 Table I (continued) PROFONDEUR6 3 RESOLVEI9 Aerosol3 PPZ4 (Sample #1) 2.5 Example 11 6 5 PPZ4 (Sample #2) 2 BLANK 4 ~T.~NK S GLORY~ Rug Cleaner2 5 Example 11 6 PPZ4 4 Example 12 6 R~.~ NK 6 Example 11 4 ppz4 2 15 1. A ~duct of Reckitt & Colman Ho~-eehold Products of Wayne, New Jer~ey, U.S.A.
2. A ~LG~UCt of S. C. Jo~n~on & Son, Inc. of Racine, Wi~conein, U.S.A.
3. A ~lvd~ct of Lehn & Fink Products of Montvale, New Jersey, U.S.A.
4. A ~G~UCt of H~n~el Solitaire of Levallois, France.
5. A product of PC r~Gducts (1001) Ltd of~Xersal Vale, Manchester, England.
6. A product of ~a Johnson Francaise S.A. of Cergy, France.
Table I shows that Examples 11 and 12 were at least as good and, in most c~ses, better in Soil Capsule Testing results for soil repellency after cle~ning than the five other commercial products tested with these compositions.
To test for soil repellency under actual conditions of use in areas having heavy foot traffic, two 200 centimeter by 100 centimeter panels of white nylon carpeting were cut and marked into six sections. The following products were applied to the sections and then allowed to dry thoroughly.
35 Each panel wa~ then tApeA down in the corridor of a ~-e-rch building for a total of four weeks to permit eYroeure to the foot traffic in that corridor. Each panel was reversed in direction after two week's time to ensure even soiling of all :~
.

wo g4/07g80 2 1 2 1 2 6 7 PCT/US93/~88 sections. The results obtained after four weeks of heavy foot traffic are reported in Table II.

Table II
Composition Score Composition Score WOOLITEo Deep Clean 3 WOOLITE~ Aerosoll 3 BLANK 6.5 BLANK 5 PROFONDEUR 4 PROFONDEUR 3.5 10 Example 11 6 Example 11 6 WOOLITEo Self Cleaning 5 HURRAO Alfombras2 4 RESOLVE0 Aerosol 3.5 HURRA~ ~cp~cial Tap.3 2.5 1. A ~L ~uct of Reckitt & Colman, St-Florent-Sur-Cher, France 2. A ~ uct of Kanfort America S.A. of Martinez Campos, Madrid, ~rA in. ~
3. HURRA~ F~recial Tapicerias from Kanfort America S.A. ~-In this testing, Example 11 was the best in the ~econA --panel and was slightly more soiled than the blank in the first panel although it still did at least ~slightly better than the other compositions tested.

Example 14 In this Example, the cleaning ability of self-pressurized aerosol foam Examples 11 and 12 were evaluated ~inct commercially available self-pres~urized aerosol foam carpet shampoo compositions of the types identified in 30 Example 13.
To carry out this evaluation, a ~ample of white hessian-backed nylon carpet was soiled with 200 grams of an oil-based soil mixture composed of dirt taken from outside a research building, soil from the ground found near an auto garage, and 35 oily synth~tic soil. The components were thoroughly mixed and the stones were removed from the soil mixture. That soil mixL~Le was sprinkled uniformly over the surface of the carpet to be tested and was impreRceA into it by walking and scuffing over the carpet sample for 5-10 minutes. The carpet ~ ~.

WO94~07g80~ ~ PCT/US93/09088 L~ fl~6'7 28-was shaken free of loose particulate matter and then left for one day to settle before applying the shampoo compositions to be tested.
Each container of aerosol carpet shampoo composition was 5 weighed initially and after each application of the composition to the soiled carpet sample to ensure that equal amounts of shampoo composition were applied to each test area. Each shampoo composition was, according to the use i.._L~ctions provided, $ha~en well and then sprayed as a foam 10 onto a marked section of the soiled carpet sample from a distance of 50-60 centimeters from the carpet sample. The foam was then worked into the pile of the carpet using a damp .~. After visually A~C~ing the ease of application, the carpet sample was then allowed to dry. The dry 15 composition was then removed by vacuuming. -Each cl~a~ section of the carpet sample was then A~~e~ed visually for cleA~ing performance and conditioning using a scale of 1 to 5 where 1 represented very poor cl~Anin~ or very poor conditioning and 5 represented very 20 good clD~ing or effective conditioning.
Examples 11 and 12 were found to all have a greater foam volume and greater foam stability than the ~Henkel PPZ
composition and were on par, if not marginally superior, to the PROFONDEUR composition. Example 11 produced the 25 creamiest foam which proved to be slightly more difficult to rub into the pile on the carpet.
The compositions tested and their order of ranking from best to worst for cle~ning efficiency on the carpet sample using the oil-based soil mixture were as follows:
Example 11 (best) Example 12 PROFONDEUR
Henkel PPZ (worst) The con~itioning effect of each cleaning shampoo composition was also evaluated with the ranking being as follows:

' - 29 -Example ll~Example 12 (best-tie) Henkel PPZ
PROFONDEUR (worst) The same evaluation procedure was carried out using a "water-base~" soil mixture which was simply 200 grams of soil from the ~ou~d near an auto garage without adding any oily soil as was done above. This water-based soil mixture was applied to the same ty~e of nylon carpet sample as described 10 above. The shampoo compositions were applied in the same manner as described above. In this test, two different samples of ~enkel PPZ (PPZl and PPZ2) were used to compare the performance of each although both samples were pur~h at the same time from the same store.
Ue~el PPZ1 (best) r l-le 11 Example 12 Hç~el PPZ2 20 PROFONDEUR (worst) -The difference in performance of the H~enkel PPZl and PPZ2 on the water-hase~ soil mixture could not be explained.
The individual numerical ratings of several tests using, 25 water-b~s~ soil mixtures were combined to obtain an overall performance rating. PPZl was the highest in these tests with an overall numerical score of 30 which was closely ~ollowed by Example 11 with a score of 28. Example 12 was next with an overall score of 24 followed by PPZ2 with a score of 19 30 points. PROFONDEUR was last with an overall score of 9.
Examples 11 and 12 and PPZ1 were also more effective in conditioning the carpet sample than PPZ~ and PROFONDEUR.

Exam~les 15-23 In these Examples, the effect of substituting various ~y~e- of waxes in the shampoo compositions of the present invention was explored using the Soiling Capsule Test.
A base composition was prepared having the following formulation: 76.351~ deionized water; 0.500% borax 10 mol;
':

~ ~ 1 2 6 ~ 30 _ PCT/US93/~88 1.500~ sodium benzoate; 0.500% REWOCOROS~ B 3010; 4.330%
JONCRYL~ 90 (45%); 7.310% sodium lauryl sulfate; 2.500%

DOWANOL~ DPM; 2.500% DOWANOL~ PM; 0.002~ TINOPAL0 CBS-X;
0.002% TINOPALo 5BM-GX; 0.255 TEGOPREN0 6950 and 0.250%
5 fragrance. This composition prepared by mixing the components together in the order listed followed by adjusting the pH of the composition to 9. 5 with 50% aqueous potassium hydroxide solution to form "BASE A".
Examples 15 through 23 were made by mixing 96.000 parts 10 by weight of BASE A with the following amounts of wax emulsions and deionized water:
Example 15: 1.705 parts of AC 330 Wax Emulsion (28%) and 2.295 parts of deionized water.
Example 16: 2.822 parts of an aqueous emulsion of 15 ~oech~t Wax KLE (19.47%) and 1.178 parts of deionized water.
Example 17: 2.822 parts of an aqueous emulsion of 17%
Carnauba Wax, Light North Country, T-3 and 3% of a nonionic fatty alcohol polyglycol ether surfactant (MULSIFAN0 RT 359 from ~ immer & Schwartz of Lahnstein, Germany (total NVM of 20 19.47%) and 1.178 parts of deionized water.
Example 18: 2.753 parts of a mixture of 3.4% Carnauba Wax, Light North Country, T-3 (82.5-85~C. melting point), 13.6% paraffin wax (minimum melting point 55-57~C.) and 3% of MULSIFAN~ RT 359 (total NVM of 19.96~) and 1.247 parts of 25 deionized water.
Example 19: 1.657 parts of an aqueous emulsion of 22.9% AC 629 Wax and 8.3% LUTENSOL~ ON70 surfactant from BASF
AG (synthetic fatty alcohol with average of 7 ethoxy groups) (total NVM of 33.2~) and 2.343 parts of deionized water.
Example 20: 1.651 parts of an aqueous emulsion of 25.5%
Hoechst PED 153 Wax and 6.4% LUTENSOL~ ON70 (total NVM of 33.3%) and 2.349 parts of deionized water.
Example 21: 1.363 parts of an aqueous emulsion of 29.1 EPOLENE~ E43 and 8.7% NEODOL~ 25-9 surfactant from Shell 35 Chemical Company of Houston, Texas, U.S.A. (C12-C15 linear primary alcohol ethoxylate) (total NVM of 40.31~) and 2.637 parts of deionized water.

wo 94/07g80 2 1 2 1 2 6 7 PCT/US93/09088 - 3l -Example 22: 1. 633 parts of an aqueous emulsion of 13.4%
EPOLENE0 E10, 13.4% EPOLENE~ E20, and 6.7~ LUTENSOL0 ON70 (total NVM of 33.65%) and 2. 367 parts of deionized water.
Example 23: A control sample which just added 4.000 5 parts of deionized water to the 96.000 parts of BASE A.
The Soil CAP~11 e Test performed used two panels of carpet contAinin~ six test areas on each. The results for each panel are ~e~o~Led below in Table III in the same fashion as was done in Example 13:
~0 '::
Table III

çç~Dosition Score Composition Score Example 16 6 Example 20 6 15 Example lS 7 Example 15 7 Example 17 5 Example 21 5.5 ~; ExL~ple 18 4.5 Example 22 5 BLANX 3.5 BLANK 3 Example 19 6.5 Example 23 6.5 Thus the compositions containing various types of waxes were all improved over the untreated BLANK panel (10 is best in antiresoiling ability) with Example 18 containing soft paraffin wax in addition to carnauba wax being the lowest 25 performer in this group. The compositions were all comparable to control Example 23 containing a polymer anti-resoiling polymer with Example 15 being the best performer in this Test.

Examples 24-37 In this series of Examples, shampoo eompositions were evaluated using the Soiling Capsule Test where the compositions contained less than all three of the required components of the present invention ~fabric cleaning polymer, 35 wax and silicone betaine polymer) as well as combinations of all three required components~ Examples 24-33 are comparative examples.
An antistatic agent for textiles used in some commercially available carpet shampoo compositions that is - -.~

WO94/07g80 PCT/US93/~88 sold by Rewo Chemische Werke GmbH of Steinau, Germany under the name REWOQUAT0 CPEM was included in some of the formulations. REWOQUAT0 CPEM is N-methyl-N-(pentaethoxy)-N-coco ammonium methosulfate at 100% NVM.
Examples 24-29 had the following formulations:
All of the Intermediates for Examples 24-29 contained 0.50% borax 10 mol; 1.50% sodium benzoate; 0.50% REWOCO~OS~ B
3010; 2.00% DOWANOL~ DPM; 1.00% SDA-3A Ethyl Alcohol (95%);
and 0.25% fragrance. In addition to these components, the 10 Intermediate oompositions further cont~ine~ the following components listed as percentages present:

lntermediate for Example: 24 25 26 Deionized Water 78.11 76.75 73.48 15 Rug Cl~nin~ Polymer A 8.22 8.04 9.51 Surfactant Blend A (35%) 6.95 -- 8.04 ...
Sodium Lsuryl Sulfate (28%) -- 8.51 --S,~lNAQUATo CPEM (100%~ 0.97 0.95 --AC 330 Wax Emulsion (28%) -- -- 3.22 20 TEGOPREN~ 6950 (30%) -- -- --Intermediate for Example: 27 28 29 Deionized Water 73.57 82.46 81.37 Rug CleA~ing Polymer A 9.28 6.11 6;01 25 Surfactant Blend A (35~) -- 5.16 --Sodium Lauryl Sulfate (28%)8.26 -- ~ 6.36 ~ IN ~QUAT~ CPEM (100%) -- -- --AC 330 Wax Emulsion (28%) 3.14 -- --.TEGOPREN~ 6950 (30%) -- 0.52 0.51 The Intermediates were prepared simply by mixing the components together in the following order with good stirring: water, borax, sodium benzoate, Rug Cleaning Polymer A, REWOCOROS~ B 3010, Surfactant Blend A, sodium lauryl sulfate, DOWANQL~ DPM, alcohol, STEINAQUATo CPEM, AC
330 Wax Emulsion, TEGOPREN0 6950 and fragrance followed by adjusting the pH of each Intermediate to 9.5 with 10% aqu. :
NaOH. The final compositions for Examples 24-29 were ..
composed of 92.5% of the Intermediate for each Example and .

wo g4,0,980 2 1 2 1 2 6 7 PCT/US93/~88 7.5% of n-Butane. These compositions were packaged in aerosol containers as described in Examples 1-3.
The Intermediates for Examples 30-37 were blends of the Intermediates of Examples 24-29:
The Intermediate for Example 30 was a 1:1 blend of the Intermediates for Examples 24 and 26.
The Intermediate for Example 31 was a ~:1 blend of the Intermediates for Examples 24 and 28.
The Intermediate for Example 32 was a 1:1 blend of the 10 Intermediates for Examples 25 and 27.
The Intermediate for Example 33 was a 1:1 blend of the Intermediates for Examples 25 and 29.
The Intermediate for Example 34 was a 1:1 blend of the Intermediates for Examples 26 and 28.
The Intermediate for Example 35 was a 1:1 blend of the Intermediates for Examples 27 and 29.
The Intermediate for Example 36 was a 1:1:1 blend of the Intermediates for Examples 24, 26 and 28. ~' The Intermediate for Example 37 was a 1:1:1 blend of the 20 Intermediates for Examples 25, 27 and 29.
The final compositions for Examples 30-37 were composed of 92.5% of the Intermediate for each Example and 7.5% of n-~;~ Butane. ~hese compositions were packaged in aerosol containers as described in Examples 4-7.
To conduct the Soiling Capsule Test, a nylon fabric test panel was divided into 5 marked sec~îons. In addition to Examples 24-37, c~mmercially available fabric shampoo compositions were also included in this test: PROFONDEUR, Henkel PPZ, GLORY~ Rug Cleaner, and Henkel PPZ of Example 13, 30 WOOL~TE~ Tapis Moquette from Reckitt & Colman, SAPUR from Thompson GmbH of Dusseldorf, Germany, TUBA from Erdal GmbH of Hallein, Germany, and EXPRESS POUDRE from La Johnson Francaise S.A. Each composition to be tested was sprayed into a marked section for a standard length of time so that 35 the section was evenly covered with the foam shampoo composition. The foam shampoo composition was scrubbed into the section by hand and left to dry at room temperature for ; ~ about 26 hours. One section on each panel was not cleaned ;~-.

~ 2 1 ~ 6~ 34 PCT/USg3/09088 (BLANK) to act as a control. The dry panel was then subjected to the Soiling Capsule Test.
The results of the Soil Capsule Test are reported in Table IV by ranking the cleanest sample as 1, the next 5 cleanest as 2, and so forth up to 5 as the dirtiest of the five sections. As in Example 13, the order of listing of the compositions in Table IV relates to their position on the carpet panel.

Table IV

Composition: Rankin~: ComDosition:Ranking:
PROFONDEUR 5 Example 29 3 ~ Example 24 2 SAPUR 4 15 R~ T.l~l~K

Example 27 3 Example 30 2 SAPUR 4 Example 34 3 BLANX* 2 BLANK
Example 31* 3 Example 33 2 Example 32* 1 PROFONDEUR 5 25 Example 36 2 PROFONDEUR 5 PROFONDEUR 5 Example 37 ~ 2 Example 35 3 SAPUR 4 SAPUR 4 Example 24 3 ~e~ PPZ 2 TUBA 2 Example 24 4 Example 24 3 35 WOOLITE~ Tappis 3 GLORY~ Rug Cleaner 4 Moquette . . .

W094/07980 _ 35 2 1 2 1 2 6 7 PCT/US93/09088 Table IV (continued) RT.A~K 2 Example 30 4 S SAPUR 3 Example 31 5 Example 24 4 Example 32 2 EXPRESS POUDRE 1 Example 33 3 BLANK
10 Example 34 5 Example 35 3 Example 36 4 -~
Example 37 2 15 * - All three starred compositions were very close.
-;
For Examples 24, 27 and 29, the results for one material of the three required by the present invention were poor.
For Examples 30-35, the results were better. Examples 36-37 20 were generally the best of the compositions tested. The co~mmercial products tested generally were not as good as the other shampoo compositions tested.

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Claims

That which I claim is:

1. An improved fabric cleaning shampoo composition which leaves a powdery product which can be vacuumed away when dry comprising an effective amount of at least one surfactant selected from the group consisting of anionic, nonionic, amphoteric and zwitterionic surfactants which are suitable for shampooing a fabric and being substantially vacuumed away when dry which surfactant is dispersed in water at a pH of from about 7 to about 10.5, wherein the improvement comprises a) from about 0.5 to about 20% by weight of the total composition of a fabric cleaning polymer which is normally solid at 25°C. and is water soluble or water dispersible upon neutralization with an alkaline compound;

b) from about 0.1 to about 10% by weight of the total composition of a wax selected from the group consisting of a synthetic wax, a natural wax or a wax-like synthetic organic substance having a melting point of at least 50°C.; and c) from about 0.05% to about 5% by weight of the total composition of a compatible silicone betaine polymer.

2. The fabric cleaning shampoo composition of Claim 1 wherein the surfactant is present in an amount of from about 0.5% to about 20% by weight of the total composition.

3. The fabric cleaning shampoo composition of Claim 2 wherein the surfactant is present in an amount of from about 0.5% to about 4%, the fabric cleaning polymer is present in an amount of from about 0.5% to about 4%, the wax is present in an amount of from about 0.5% to about 2%, and the silicone betaine polymer is present in an amount of from about 0.25%
to about 0.5%.

4. The fabric cleaning shampoo composition of Claim 1 wherein the surfactant is selected from the group consisting of anionic surfactants, amphoteric surfactants and zwitterionic surfactants and is present in an amount of from about 0.5% to about 4%.

5. The fabric cleaning shampoo composition of Claim 1 wherein the fabric cleaning polymer is selected from the group consisting of at least one polymer of (a) a minor amount of an unsaturated carboxylic-acid functional monomer selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, maleic acid, and itaconic acid and (b) a major amount of at least one unsaturated organic monomer selected from the group consisting of alkyl acrylates containing from 4 to 14 carbons, alkyl methacrylates containing from 5 to 15 carbons, styrene, alpha-methyl styrene, acrylonitrile, methacrylonitrile, and 1-alkenes having from 2 to 30 carbon atoms.

S. The fabric cleaning shampoo composition of Claim 1 wherein the wax is in the form of an aqueous emulsion of particles and is selected from the group consisting of pressure-emulsified, oxidized polyethylene and oxidized polypropylene having a melting point of at least 100°C.

7. The fabric cleaning shampoo composition of Claim 1 wherein the silicone betaine polymer is of the general formula R2 (R1)2SiO((R1)2SiO)x(R2R1SiO)ySi(R1)2R2 wherein each R1 is an alkyl radical with 1 to 18 carbon atoms, an aryl radical or a polyoxyalkylene radical wherein at least 70% of the R1 radicals are methyl radicals, R2 may be the same as R1 wherein at least one R2 radical is selected from one of the group consisting of (I) -(CH2)3OCH2CHR3CH2R4 groups in which R3 and R4 are different, one radical representing a hydroxyl group and the other represents the nonionic, amphoteric and zwitterionic surfactants which are suitable for shampooing a fabric and being substantially vacuumed away when dry which surfactant is dispersed in water at a pH of from about 7 to about 10.5, wherein the improvement comprises a) from about 0.5 to about 10% by weight of the total composition of a fabric cleaning polymer which is normally solid at 25°C. and is water soluble or water dispersible upon neutralization with an alkaline compound which is selected from the group consisting of at least one polymer of (a) from about 2% to 40% by weight of the total polymer of an unsaturated calboxylic-acid functional monomer selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, maleic acid, and itaconic acid and (b) from about 60% to 98% by weight of the total polymer of at least one unsaturated organic monomer selected from the group consisting of alkyl acrylates containing from 4 to 14 carbons, alkyl methacrylates containing from 5 to 15 carbons, styrene, alpha-methyl styrene, acrylonitrile, methacrylonitrile, and 1-alkenes having from 2 to 30 carbon atoms;

b) from about 0.1 to about 10% by weight of the total composition of a wax selected from the group consisting of a hard wax-like synthetic organic substance selected from the group consisting of oxidized polyethylene and oxidized polypropylene having a melting point of at least 100°C.; and c) from about 0.05% to about 5% by weight of the total composition of a compatible silicone betaine polymer wherein the silicone betaine polymer is of the general formula R2 (R1)2SiO((R1)2SiO)x(R2R1SiO)ySi(R1)2R2 wherein each R1 is an alkyl radical with 1 to 18 carbon atoms, an aryl radical or a polyoxyalkylene radical wherein at least 70% of the R1 radicals are methyl radicals, R2 may be the same as R1 wherein at least one R2 radical is selected from one of the group consisting of (I) -(CH2)3OCH2CHR3CH2R4 groups in which R3 and R4 are different, one radical representing a hydroxyl group and the other represents the -N+R5R6(CH2)nCOO- group in which each R5 and R6 represents an alkyl radical with 1 to 4 carbon atoms or a benzyl radical, and n=1, 2 or 3, and (II) -R7CONHR8N+R5R6(CH2)nCOO- groups in which R7 is a divalent alkylene radical with 2 to 12 carbon atoms, R8 is a divalent alkylene radical with 2 to 6 carbon atoms, each x has a value of from 0 to 200, and y has a value of from 1 to 50.

11. The fabric cleaning shampoo composition of Claim 10 wherein the surfactant is present in an amount of from about 0.5% to about 4%, the fabric cleaning polymer is present in an amount of from about 0.5% to about 4%, the wax is present in an amount of from about 0.5% to about 2%, and the silicone betaine polymer is present in an amount of from about 0.25%
to about 0.5%.

12. The fabric cleaning shampoo composition of Claim 11 wherein the surfactant is selected from the group consisting of anionic surfactants, amphoteric surfactants and zwitterionic surfactants.

13. The fabric cleaning shampoo composition of Claim 12 wherein the wax is in the form of an aqueous emulsion of particles and is a pressure-emulsified oxidized polyethylene having a melting point of at least 100°C.

14. The fabric cleaning shampoo composition of Claim 13 wherein the fabric cleaning polymer is a polymer of methacrylic acid, styrene and n-butyl acrylate, and optionally, alpha-methyl styrene.

15. The fabric cleaning shampoo composition of Claim 15 wherein the silicone betaine polymer is of the general formula (CH3)3SiO(SiACH3O)m(Si(CH3)2O)nSi(CH3)3 wherein A has the formula -(CH2)3OCH2CH(OH)CH2N+(CH3)2CH2COO-, m and n are each greater than 0, the sum of m+n being such that the viscosity of the polymer at 25°C. is from about 50-90 square meters per second, its specific gravity at 25°C. is from about 1.07 to 1.09 grams per cubic centimeter, and the Ross Miles foam height of the polymer at 0.1% solution in water 8 dH, at 25°C. is 80.