USOO6432892B2 (12) United States Patent (10) Patent No.: US 6,432,892 B2 Meine et al. (45) Date of Patent: Aug. 13, 2002

(54) CLEANING OF FRUIT, VEGETABLES, (56) References Cited AND MEATS COMPRISING ALKYL-POLYGLYCOSIDE FOREIGN PATENT DOCUMENTS WO WO98/07331 3/1995 (75) Inventors: Georg Meine, Mettmann; Brigitte WO WO95/12326 5/1995 Giesen; Kerstin Ziganke, both of WO WO97/O1288 1/1997 Duesseldorf, all of (DE) WO WO97/O1289 1/1997 WO WO97/01290 1/1997 (73) Assignee: Henkel Kommanditgesellschaft auf WO WO97/152O2 5/1997 Aktien, Duesseldorf (DE) WO WO98/18352 5/1998 (*) Notice: Subject to any disclaimer, the term of this OTHER PUBLICATIONS patent is extended or adjusted under 35 K. H. Wallhaeusser, Praxis der Sterilisation, Desinfektion U.S.C. 154(b) by 0 days. Konservierung. Keimidentifizierung-BetriebShygiene, (1995, 5' Ed) (table of contents only). (21) Appl. No.: 09/822,301 Primary Examiner Necholus Ogden (22) Filed: Mar. 28, 2001 (74) Attorney, Agent, or Firm-Stephen D. Harper; Glenn (30) Foreign Application Priority Data E. J. Murphy Mar. 28, 2000 (DE) ...... 100 15 126 (57) ABSTRACT A low-foaming clear composition for cleaning fruit, (51) Int. Cl." ...... C11D 17/00 vegetables, or meat that can be diluted by the user before use and/or directly sprayed on and that shows high cleaning (52) U.S. Cl...... 510/111; 510/422; 510/470; performance, particularly in dissolving wax, and also high 426/478 wetting power. The compositions contain Co alkyl polyg lycosides. (58) Field of Search ...... 510/111, 470, 510/422; 426/478 22 Claims, No Drawings US 6,432,892 B2 1 2 CLEANING OF FRUIT, VEGETABLES, cosides are disclosed as optional nonionic Surfactants. AND MEATS COMPRISING Unfortunately, the compositions in question tend to cloud ALKYL-POLYGLYCOSIDE undesirably in both concentrated and dilute form, particu larly where they are used with hard water. CROSS-REFERENCE TO RELATED The problem addressed by the present invention was to APPLICATIONS overcome some or all of the difficulties mentioned above and This application claims priority under 35 U.S.C. S 119 of to provide a clear composition for cleaning fruit and Veg DE 100 15 126.4, filed Mar. 28, 2000 in the German patent etables which would develop high cleaning performance, office, the entire disclosure of which is hereby incorporated particularly in removing waxes, and wetting power and which would remain clear even in the presence of hardneSS by reference. elements introduced into the cleaning process both via water FIELD OF THE INVENTION and via the dirt on the fruit/vegetables to be cleaned. This problem is Surprisingly solved by the use of Co This invention relates generally to the cleaning of fruit alkyl polyglycosides. and vegetables. 15 DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION Accordingly, the present invention relates to the use of It is generally known and recognized among consumers one or more Co alkyl polyglycosides for cleaning fruit that fruit and vegetables should be thoroughly washed and/or vegetables. before eating to remove dirt and other unwanted residues which can undesirably adhere to their Surfaces. In addition, Accordingly, in a Second embodiment, the present inven Some consumers like to remove the artificial “wax-like” tion relates to a water-based composition Suitable for clean coating which is applied to Some fruit in order to delay the ing fruit and/or vegetables containing one or more Coalkyl loSS of moisture for an extended life and to improve appear polyglycosides. ance. A majority of consumers are aware of the need for 25 The composition according to the invention is also Suit thorough cleaning but generally use only tap water for this able for cleaning meat. Accordingly, in a third embodiment, purpose. Only a Small percentage of consumers use a the present invention relates to the use of a composition domestic cleaner-normally a manual dishwashing according to the invention for cleaning fruit, vegetables detergent-to achieve more thorough cleaning. However, and/or meat. dishwashing detergents are only Suitable to a limited extent In the context of the teaching according to the invention, for this application because they are generally characterized fruit is understood in particular to be the fruit-edible by Vigorous foaming and a Stable foam which makes them raw-of perennial trees and bushes growing wild or in difficult to remove from the fruit and vegetables washed with plantations. them. The formulation of really effective compositions for Vegetables in the context of the teaching according to the cleaning fruit and vegetables, particularly those which can 35 invention are understood in particular to be any annual be safely used by individual consumers, also represents a plants or parts thereof which are used raw or processed for particular problem insofar as many known cleaning ingre human nutrition. dients do not appear Suitable for use in direct contact with Meats in the context of the teaching according to the foods from which they might not be able to be completely 40 invention are understood in particular to be any parts of removed again. animals, for example ungulates, Such as cattle or pigs, and In addition, it would be particularly desirable to provide of fowl, fish and other saltwater and freshwater animals. effective, toxicologically Safe compositions for cleaning Substances which also serve as ingredients of cosmetic fruit and vegetables in the form of Substantially low-foaming preparations may be referred to in the following by their liquid Solutions which are clear or at least only very slightly 45 names under the INCI nomenclature (INCI=Intemational cloudy. Liquid Solutions are convenient for the user because Nomenclature of Cosmetic Ingredients). Chemical com they can be directly applied to “dirty' fruit and vegetables pounds bear an INCI name in English while vegetable and then rinsed off with tap water. The clarity of the liquid ingredients are all referred to by their Latin names according Signifies cleanliness to the user and is thus particularly to Linné, so-called trivial names such as “water”, “honey” or desirable. The low foaming is another important attribute 50 “sea salt” also being shown in Latin. The INCI names can be which guarantees quick and easy removal of the Solution by found in the International Cosmetic Ingredient Dictionary rinsing. In addition, it would be of advantage if Such and Handbook-7th Edition (1997) which is published by compositions could be formulated as concentrates which can the Cosmetic, Toiletry and Fragrance Association (CTFA), be diluted by the consumer before use and/or sprayed 1101 17th Street, NW, Suite 300, Washington, D.C. 20036, directly onto the fruit and vegetables. 55 USA and which contains more than 9,000 INCI names and In addition, many toxicologically Safe cleaning ingredi references to more than 37,000 commercial names and ents do not meet the above-mentioned need for clear, low technical names, including the associated distributors from foaming, dilutable liquid products. Thus, many Surfactants more than 31 countries. The International Cosmetic Ingre form cloudy or even opaque Suspensions in water. Moreover, dient Dictionary and HandbOOk assigns the ingredients to many Surfactants are actually formulated to be high 60 one or more chemical classes, for example Polymeric foaming. Also, concentrated Surfactants form phases that are Ethers, and one or more functions, for example relatively difficult to handle. Surfactants-Cleansing Agents, which in turn are explained Water-based compositions for cleaning fruit and Veg in detail and to which reference may also be made in the etables which contain oleic acid or oleate are known from following. International patent applications WO95/12326 A1, WO 65 The initials CAS mean that the following sequence of 97/01288 A1, WO 97/O1289 A1, WO 97/01290 A1, WO digits is a reference number of the Chemical Abstracts 97/15202 A1 and WO 98/18352 A1. Cos alkyl polyglu Service. US 6,432,892 B2 3 4 Unless otherwise stated, the embodiments of the inven Alkyl polyglycosides are obtainable, for example, under tion described in the following always relate to all three the names of APG(R), Plantaren(E), Plantacare(E) and Gluco Subjects of the invention, i.e. uses, compositions and ponE) from Cognis Deutschland GmbH and from Cognis procedures, even when they are explicitly disclosed for only Corporation (USA). one Subject, for example a composition or a use. The content of one or more Co alkyl polyglycosides is In Selecting the ingredients to be used, the expert routinely normally 0.01 to 50% by weight, preferably 0.1 to 20% by takes into account the requirements arising from the par weight, more preferably 0.5 to 10% by weight, most pref ticular application envisaged for the composition. erably 1 to 5% by weight and, in one most particularly Alkyl Polyglycosides preferred embodiment, 1.5 to 2% by weight, for example The short-chain Co alkyl polyglycosides (APG-I) essen 1.6, 1.7, 1.8 or 1.9% by weight. tial to the invention preferably correspond to general for Other Surfactants mula I: Besides the short-chain Co alkyl polyglycosides essen tial to the invention, the composition according to the in which 15 invention may contain one or more Surfactants from the R" is a linear or branched, Saturated or unsaturated alkyl group of nonionic, anionic, amphoteric and cationic Surfac group containing 4 to 9, preferably 5 to 9, more tantS. preferably 6 to 9, most preferably 7 to 9 and, in one The total surfactant content is normally 0.01 to 50% by most particularly preferred embodiment, 8 to 9 carbon weight, preferably 0.1 to 30% by weight, more preferably atOmS, 0.5 to 20% by weight, most preferably 1 to 10% by weight G is a glycosidic Sugar unit, more particularly a glucose and, in one most particularly preferred embodiment, 2 to 5% unit, by weight, for example 3 or 4% by weight. The very high X1 is a number of 1 to 10, preferably 1.1 to 3, more levels of up to 50% by weight can be reached in concen preferably 1.2 to 2, most preferably 1.3 to 1.8 and, in trated or highly concentrated embodiments and normally one most particularly preferred embodiment, 1.4 to 1.6, 25 call for corresponding dilution before use. AO is a C- alkyleneoxy group, preferably an ethyl The content by weight of short-chain Co alkyl polygly eneoxy and/or propyleneoxy group and more preferably an coside (APG-I) essential to the invention, based on the total ethyleneoxy group and a1 Stands for the average degree of Surfactants, preferably based on the total nonionic Surfac alkoxylation of 0 to 20, preferably 0 to 10, more preferably tants and more preferably based on the total alkyl 0 to 5 and most preferably 0. polyglycosides, is normally 10 to 100%, preferably 20 to The group (AO) may also contain different alkyleneoxy 90%, more preferably 30 to 80%, most preferably 40 to 70% units, for example ethyleneoxy and propyleneoxy units, in and, in one most particularly preferred embodiment, 50 to which case a1 Stands for the average total degree of 65%. In one particular embodiment of the invention, the alkoxylation, i.e. the degree ethoxylation and the degree of content by weight of APG-I, based on the total surfactants, propoxylation added together. The alkyl group R is pref 35 preferably based on the total nonionic Surfactants and more erably Saturated and more particularly Saturated and linear. preferably based on the total alkyl polyglycosides, is at least Unless indicated in detail or otherwise indicated in the and more particularly above 50%. following, the alkyl groups R' of the APG-I are linear Other Nonionic Surfactants Saturated groups with the indicated number of carbon atoms. Suitable nonionic Surfactants are, for example, other alkyl Alkyl polyglycosides (APGs) are nonionic Surfactants 40 polyglycosides, C-2 alkyl alcohol polyglycol ethers and and represent known Substances which may be obtained by nitrogen-containing Surfactants or even SulfoSuccinic acid the relevant methods of preparative organic chemistry. The C-2 alkyl esters and mixtures thereof. Other nonionic index x1 indicates the degree of oligomerization (DP Surfactants in the context of the invention are alkoxylates, degree), i.e. the distribution of mono- and oligoglycosides, Such as alkyl phenol polyglycol ethers, polyglycol ethers, and is a number of 1 to 10. Whereas x1 in a given compound 45 end-capped polyglycol ethers, mixed ethers and hydroxy must always be an integer and, above all, may assume a mixed ethers and also fatty acid polyglycol esters and fatty value of 1 to 6, the value X1 for a certain alkyl oligoglyco acid polyglycol ethers. Suitable polyglycol ethers Side is an analytically determined calculated quantity which (polyalkylene glycols, polyglycols) are, above all, polyeth is generally a broken number. Alkyl glycosides having an ylene glycols (polymeric ethylene oxide) and polypropylene average degree of oligomerization X1 of 1.1 to 3.0 are 50 preferably used. Alkyl-glycosides having a degree of oli glycols (polymeric propylene oxide) and block polymers gomerization of less than 1.7 and, more particularly, and block copolymers thereof. between 1.2 and 1.6 are preferred from the applicational The composition according to the invention contains one or more other nonionic Surfactants, more particularly other point of View. The glycosidic Sugar used is preferably Xylose alkyl polyglycosides, in a quantity-based on the but especially glucose. 55 composition-of typically 0 to 30% by weight, preferably The alkyl group R may be derived from primary alcohols 0.01 to 20% by weight, more preferably 0.1 to 10% by containing 4 to 9 carbon atoms. Typical examples are weight, most preferably 0.5 to 4% by weight and, in one caproic alcohol, caprylic alcohol and nonyl alcohol and most particularly preferred embodiment, 1 to 1.5% by mixtures thereof or the technical mixtures containing them weight, for example 1.1, 1.2, 1.3 or 1.4% by weight. which are obtained as linear alcohols, for example in the 60 hydrogenation of technical fatty acid methyl esters, or as Other alkyl polyglycosides branched alcohols, for example in the hydrogenation of In one preferred embodiment, the composition according aldehydes from Roelen's oxosynthesis. to the invention contains one or more long-chain Co. alkyl Particularly preferred APG-I are not alkoxylated (a1 =0), polyglycosides (APG-II) in addition to the short-chain Co for example C and/or Co alkyl polyglucoside with a DP of 65 alkyl polyglycosides essential to the invention (APG-I). In 1.4, 1.5 or 1.6, more particularly Cs alkyl polyglucoside with one particular embodiment of the invention, the composition a DP of 1.5 (Cs alkyl-1,5-glucoside). contains only alkyl polyglycosides as Surfactants. US 6,432,892 B2 S 6 The long-chain alkyl polyglycosides (APG-II) preferably and with a DP degree of 1.6 as APG(R) 225, Plantacare(E) 800 correspond to general formula II: or Glucopon(R) 225 from Cognis Deutschland GmbH (DE) or from Cognis Corporation (US). A mixture with a DP degree of 1.5 is particularly preferred. Alkyl Alcohol Polyglycol Ethers in which C-2 alkyl alcohol polypropylene glycol/polyethylene R is a linear or branched, Saturated or unsaturated alkyl glycol ethers are preferred known nonionic Surfactants. group containing 10 to 22, preferably 10 to 20, more They may be described by formula RO-(CH2CH(CH)O). preferably 10 to 18, most preferably 11 to 16 and, in (CHCHO)-H, in which R is a linear or branched, one most particularly preferred embodiment, 12 to 14 aliphatic alkyl and/or alkenyl group containing 6 to 22, carbon atoms, preferably 8 to 18 and more preferably 10 to 16 carbon G is a glycosidic Sugar unit, more particularly a glucose atoms, p is 0 or a number of 1 to 3 and e is a number of 1 unit, to 20. X2 is a number of 1 to 10, preferably 1.1 to 3, more The C- alkyl alcohol polyglycol ethers corresponding preferably 1.2 to 2, most preferably 1.3 to 1.8 and, in 15 to the above formula may be obtained by addition of one most particularly preferred embodiment, 1.4 to 1.6, propylene oxide and/or ethylene oxide onto alkyl alcohols, AO is a C- alkyleneoxy group, preferably an ethyl preferably onto oxoalcohols, the branched-chain primary eneoxy and/or propyleneoxy group and more prefer alcohols obtainable by the oxosynthesis, or onto fatty ably an ethyleneoxy group and a2 Stands for the aver alcohols, more particularly onto fatty alcohols. Typical age degree of alkoxylation of 0 to 20, preferably 0 to examples are polyglycol ethers corresponding to the above 10, more preferably 0 to 5 and most preferably 0. formula, in which R is an alkyl group containing 8 to 18 Apart from the different number of carbon atoms in the carbon atoms, p=0 to 2 and e is a number of 2 to 7. Preferred alkyl group, the foregoing observations on the APG-I apply representatives are, for example Co. fatty alcohol--1PO+ equally to the APG-II. 6EO ether (p=1, e=6), C fatty alcohol-5.5 EO (p=0, The alkyl group R may be derived from primary alcohols 25 e=5.5), C is fatty alcohol--7EO ether (p=0, e=7) and containing 10 to 22 carbon atoms. Typical examples are isodecanol +6EO (R=isomer mixture of Co oxoalcohol capric alcohol, undecyl alcohol, lauryl alcohol, myristyl radicals, p=0, e=6) and mixtures thereof. In particular alcohol, cetyl alcohol, palmitoleyl alcohol, Stearyl alcohol, mixtures, at least one representative corresponding to the isoStearyl alcohol, oleyl alcohol, elaidyl alcohol, petroSeli above formula with a linear alkyl chain R is combined with nyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl at least one representative corresponding to the above for alcohol and erucyl alcohol and mixtures thereof or the mula with a branched alkyl chain R, for example C fatty technical mixtures containing them which are obtained as alcohol--5.5EO and isodecanol--6EO. In this case, the linear linear alcohols, for example in the hydrogenation of tech alkyl chain preferably contains more carbon atoms than the nical fatty acid methyl esters, or as branched alcohols, for branched alkyl chain. Cs fatty alcohol--1.2PO+8.4EO, Cso example in the hydrogenation of aldehydes from Roelen's 35 fatty alcohol--5EO, C-1 fatty alcohol--6EO C fatty oxosynthesis. The alkyl or alkenyl group R is preferably alcohol-3EO and mixtures thereof are particularly pre derived from capric alcohol, undecyl alcohol, lauryl alcohol, ferred. Nonionic Surfactants and alkyl alcohol polyglycol myristyl alcohol and cetyl alcohol and mixtures thereof, ethers in particular produce an increase in the Volume of the more particularly from capric alcohol and/or undecyl alco lower phase. hol. 40 End-capped C- alkyl alcohol polyglycol ethers, i.e. Particularly preferred APG-II are also not alkoxylated compounds in which the free OH group in the above formula (a2=0), for example Co and/or C alkyl polyglucoside with is etherified, may also be used. The end-capped C- alkyl a DP of 1.4, 1.5 or 1.6, more particularly Co alkyl poly alcohol polyglycol etherS may be obtained by relevant glucoside with a DP of 1.5 (Co alkyl-1,5-glucoside). methods of preparative organic chemistry. Preferably, C. Preferred mixtures of APG-I and APG-II contain Co 45 alkyl alcohol polyglycol ethers are reacted with alkyl APG-I and Co., APG II, more particularly Cso APG-I and halides, more especially butyl or benzyl chloride, in the Co. APG-II and most preferably Cso APG-I and Co presence of bases. Typical examples are mixed ethers cor APG-II, for example Cas APG-I and Co APG-II, Cs responding to formula II, in which R" is a technical fatty APG-I and Co APG-II, Co APG-I and Co., APG-II, C, alcohol moiety, preferably a C cocoalkyl moiety, p=0 APG-I and Co APG-II or C, APG-I and Co APG-II (“-” 50 and e=5 to 10, which are end-capped with a butyl group. stands for “to”; “f” stands for “and”; i.e. “C” stands for Nitrogen-containing Nonionic Surfactants “Clio to C” whereas "Cs” stands for “C. and Cs” and does Suitable nitrogen-containing nonionic Surfactants are, for not include “C.”). example, amine oxides, fatty acid polyhydroxyamides, for A Suitable mixture of APG-I and APG-II contains-based example glucamides, and ethoxylates of alkyl amines, vici on the weight of the mixture-about 21% C, APG-I, 45% 55 nal diols and/or carboxylic acid amides containing alkyl C APG-II and 33% C, APG-II and in all about 1% C, groups with 10 to 22 carbon atoms and preferably 12 to 18 APG-I and C, APG-II. Such a mixture with a DP degree of carbon atoms. The degree of ethoxylation of these com 1.4 is obtainable as APGCE 300 or Plantaren(E) 300 and pounds is generally between 1 and 20 and preferably with a DP degree of 1.6–as APG(R) 300 or Plantaren(R) 300 between 3 and 10. Ethanolamide derivatives of alkanoic from Cognis Deutschland GmbH (DE) or from Cognis 60 acids containing 8 to 22 carbon atoms and preferably 12 to Corporation (US). 16 carbon atoms are preferred. Particularly suitable com A preferred mixture of APG-I and APG-II contains pounds include lauric acid, myristic acid and palmitic acid based on the weight of the mixture-about 0 to 2% C, monoethanolamides. APG-I, 55 to 63% C, APG-I, 33 to 43% C, APG-II and 0 Amine Oxides to 7% C, APG-II. Such a mixture with a DP degree of 1.4 65 Amine oxides Suitable for the purposes of the invention is obtainable as APG(R) 200 or Plantacare(R) 700, with a DP include alkylamine oxides, more particularly alkyl dimethyl degree of 1.5 as APG(R), Plantacare(R 220 or Glucopon(R) 215 amine oxides, alkylamidoamine oxides and alkoxyalkyl US 6,432,892 B2 7 8 amine oxides. Preferred amine oxides correspond to the The group of polyhydroxyfatty acid amides also includes formula RRRN"-O- in which R' is a saturated or compounds corresponding to formula (IV): unsaturated C-22 alkyl group, preferably a Cs-1s alkyl group, more preferably a Saturated Co- alkyl group, for (IV) example a Saturated C. alkyl group which, in the alkyla midoamine oxides, is attached to the nitrogen atom N via a R1-O-R2 carbonylamidoalkylene group -CO-NH-(CH) - and, R-CO-N-Z in the alkoxyalkyl amine oxides, via an oxa-alkylene group -O-(CH) - where Z is a number of 1 to 10, preferably 2 to 5 and more preferably 3, and R and R independently in which R is a linear or branched alkyl or alkenyl group of one another represent an optionally hydroxySubstituted containing 7 to 12 carbon atoms, R is a linear, branched or Calkyl group Such as, for example, a hydroxyethyl group, cyclic alkyl group or an aryl group containing 2 to 8 carbon more particularly a methyl group. atoms and R is a linear, branched or cyclic alkyl group or Examples of Suitable amine oxides are the following an aryl group or an oxyalkyl group containing 1 to 8 carbon compounds identified by their INCI names: Almondami atoms, C alkyl or phenyl groups being preferred, and Z dopropylamine Oxide, BabasSuamidopropylamine Oxide, 15 is a linear polyhydroxyalkyl group, of which the alkyl chain Behenamine Oxide, Cocamidopropyl Amine Oxide, Coca is Substituted by at least two hydroxyl groups, or midopropylamine Oxide, Cocamine Oxide, Coco alkoxylated, preferably ethoxylated or propoxylated, deriva Morpholine Oxide, Decylamine Oxide, Decyltetradecy tives of that group. lamine Oxide, Diaminopyrimidine Oxide, Dihydroxyethyl Z is preferably obtained by reductive amination of a Cso Alkoxypropylamine Oxide, Dihydroxyethyl Co reduced Sugar, for example glucose, fructose, maltose, Alkoxypropylamine Oxide, Dihydroxyethyl Cas Alkox lactose, galactose, mannose or Xylose. The N-alkoxy- or ypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, N-aryloxy-Substituted compounds may then be converted Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stear into the required polyhydroxyfatty acid amides by reaction amine Oxide, Dihydroxyethyl Tallowamine Oxide, Hydro with fatty acid methyl esters in the presence of an alkoxide genated Palm Kernel Amine Oxide, Hydrogenated Tallowa 25 as catalyst, for example in accordance with the teaching of mine Oxide, Hydroxyethyl Hydroxypropyl Cas International patent application WO-A-95/07331. Alkoxypropylamine Oxide, IsoStearamidopropylamine Anionic Surfactants Oxide, ISOStearamidopropyl Morpholine Oxide, Laurami Suitable anionic Surfactants are normally at least one dopropylamine Oxide, Lauramine Oxide, Methyl Morpho linear or branched, Saturated or unsaturated alkyl or acyl line Oxide, Milkamidopropyl Amine Oxide, Minkamidopro group containing 6 to 22 carbon atoms or a derivative pylamine Oxide, Myristamidopropylamine Oxide, thereof and at least one anionic head group Such as, for Myristamine Oxide, Myristyl/Cetyl Amine Oxide, Oleami example, aliphatic Sulfates Such as fatty alcohol Sulfates, dopropylamine Oxide, Oleamine Oxide, Olivamidopropy fatty alcohol ether Sulfates, dialkyl ether Sulfates and lamine Oxide, Palmitamidopropylamine Oxide, Palmita monoglyceride Sulfates, aliphatic Sulfonates Such as alkane mine Oxide, PEG-3 Lauramine Oxide, Potassium 35 Sulfonates, olefin Sulfonates, ether Sulfonates, n-alkylether Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Sulfonates, ester Sulfonates and lignin Sulfonates, alkylben Trisphosphonomethylamine Oxide, Sesamidopropylamine Zene Sulfonates, fatty acid cyanamides, SulfoSuccinic acid Oxide, Soyamidopropylamine Oxide, Stearamidopropy esters, fatty acid isethionates, acylaminoalkane Sulfonates lamine Oxide, Stearamine Oxide, Tallowamidopropylamine (fatty acid taurides), fatty acid sarcosinates, ether carboxylic Oxide, Tallowamine Oxide, Undecylenamido-propylamine 40 acids and alkyl (ether) phosphates. Particularly Suitable Oxide und Wheat Germamidopropylamine Oxide. A pre anionic Surfactants are Cs is alkyl Sulfates, Cs-1s alkyl ether ferred amine oxide is, for example, Cocamine Oxide Sulfates, i.e. the Sulfation products of the above-described (N-cocoalkyl-N,N-dimethylamine oxide), Dihydroxyethyl alkyl alcohol polyglycol ethers, and/or Css alkyl Tallowamine Oxide (N-tallowalkyl-N,N-dihydroxyethyl benzene Sulfonates, more particularly dodecyl 45 benzeneSulfonate, but also Css alkaneSulfonates, Css amine oxide) and/or Cocamidopropylamine Oxide C-olefin Sulfonates, Sulfonated Cs-1s fatty acids, Cs-22 car (cocoamidopropyl amine oxide), more particularly Cocami boxylic acid amide ether Sulfates, SulfoSuccinic acid mono dopropylamine Oxide. C-2-alkyl esters, Css alkyl polyglycol ether carboxylates, Polyhydroxyfatty Acid Amides Css N-acyl taurides, Css N-Sarcosinates and Css alkyl Other suitable surfactants are polyhydroxyfatty acid 50 isethionates and mixtures thereof. amides corresponding to formula (III): The anionic Surfactants are normally used in the form of their alkali metal and alkaline earth metal Salts, more par (III) ticularly Sodium, potassium and magnesium Salts, ammo R1 nium and mono-, di-, tri- and tetra-alkyl ammonium Salts 55 and-in the case of the Sulfonates-in the form of their R-CO-N-Z corresponding acid, for example dodecyl benzeneSulfonic acid. Where Sulfonic acid is used, it is normally neutralized in which RCO is an aliphatic acyl group containing 6 to 22 in Situ to the above-mentioned Salts with one or more carbon atoms, R is hydrogen, an alkyl or hydroxyalkyl corresponding bases, for example alkali metal and alkaline group containing 1 to 4 carbon atoms and Z is a linear or 60 earth metal hydroxides, more particularly Sodium, potas branched polyhydroxyalkyl group containing 3 to 10 carbon sium and magnesium hydroxide, ammonia or mono-, di-, tri atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty or tetra-alkylamine. acid amides are known Substances which may normally be Soaps obtained by reductive amination of a reducing Sugar with The compositions according to the invention may also ammonia, an alkylamine or an alkanolamine and Subsequent 65 contain one or more Soaps, i.e. Salts of Saturated or unsat acylation with a fatty acid, a fatty acid alkyl ester or a fatty urated C. carboxylic acids, and/or the corresponding acid chloride. acids, for their foam-Suppressing properties. Preferred Salts US 6,432,892 B2 9 10 are the alkali metal Salts, more particularly the Sodium Preferred amphoteric surfactants are the alkyl betaines and/or potassium Salts and most preferably the potassium corresponding to formula A1, the alkylamidobetaines cor Salts. Preferred C2 carboxylic acids are Saturated and/or responding to formula A2, the Sulfobetaines corresponding unsaturated, particularly monounsaturated, fatty acids con to formula A3 and the amidoSulfobetaines corresponding to taining 6 to 22, preferably 8 to 22, more preferably 10 to 20 formula A4. and most preferably 12 to 18 carbon atoms, for example oleic acid, Stearic acid, tallow acid, lauric acid and/or erucic R-N(CH)-CHCOO (A1) acid (Z-13-docoSenoic acid). However, Soaps regularly give rise to Solubility problems and unwanted clouding resulting R-CO-NH-(CH2)-N'(CH)-CHCOO (A2) therefrom, particularly if the water used is relatively hard. If one or more anionic Surfactants, including the Soaps, R-N(CH)-CHCH(OH)CHSO, (A3) are used, their content in the composition according to the invention, based on the composition, is normally 0.01 to 30% by weight, preferably 0.1 to 20% by weight, more in which R is as defined for formula A. preferably 0.1 to 20% by weight, most preferably 0.5 to 10% Particularly preferred amphoteric Surfactants are the car by weight and, in one most particularly preferred 15 bobetaines and more particularly the carbobetaines corre embodiment, 1 to 5% by weight, for example 2% by weight. sponding to formulae A1 and A2, the alkylamidobetaines In one preferred embodiment, however, the composition corresponding to formula A2 being most particularly pre contains hardly any anionic Surfactants including Soaps in ferred. accordance with the quantity data shown above and, in one Examples of Suitable betaines and Sulfobetaines are the particularly preferred embodiment, is entirely free from following compounds identified by their INCI names: Soaps and even from anionic Surfactants. Almondamidopropyl Betaine, Apricotamidopropyl Betaine, Amphotetic Surfactants Avocadamidopropyl Betaine, BabasSuamidopropyl Betaine, Behenamidopropyl Betaine, Behenyl Betaine, Betaine, Suitable amphoteric Surfactants (Zwifterionic Surfactants) Canolamidopropyl Betaine, Capryl/Capramidopropyl are, for example, betaines, alkylamidoalkyl amines, alkyl 25 Substituted amino acids, acylated amino acids and Betaine, Carnitine, Cetyl Betaine, Cocamidoethyl Betaine, biosurfactants, of which the betaines are preferred for the Coca mido propyl Be taine, Coca mid o propyl purposes of the invention. HydroxySultaine, Coco-Betaine, Coco-HydroxySultaine, If one or more amphoteric Surfactants are used, their Coco/Oleamidopropyl Betaine, Coco-Sultaine, Decyl content in the composition according to the invention, based Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl on the composition, is normally 0.01 to 30% by weight, Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihy preferably 0.1 to 20% by weight, more preferably 0.5 to 10% droxyethyl Tallow Glycinate, Dimethicone Propyl by weight and most preferably 1 to 5% by weight PG-Betaine, Erucamidopropyl Hydroxysultaine, Hydroge Betaines nated Tallow Betaine, IsoStearamidopropyl Betaine, Laura midopropyl Be taine, Lauryl Be taine, Lauryl Suitable betaines are the alkyl be taines, the 35 alkylamidobetaines, the imidazolinium betaines, the Sulfo Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl betaines (INCI Sultaines) and the phosphobetaines and Betaine, Minkamidopropyl Betaine, Myristamidopropyl preferably correspond to the formula (R')(R)(R)N" Betaine, Myristyl Betaine, Oleamidopropyl Betaine, Olea CHCOO, where R is a Cses and preferably Co. alkyl midopropyl Hydroxysultaine, Oleyl Betaine, Olivamidopro group optionally interrupted by hetero atoms or hetero atom pyl Betaine, Palmamidopropyl Betaine, Palmitamidopropyl groups and R and R may the same or different and 40 Betaine, Palmitoyl Carnitine, Palm Kernelamidopropyl represent C-1 alkyl groups, more particularly Co-s alky Betaine, Polytetrafluoroethylene Acetoxypropyl Betaine, ldimethyl carboxymethyl betaines and C, alkylami Ricinoleamidopropyl Betaine, Sesamidopropyl Betaine, dopropyl dimethyl carboxymethyl betaines, or to formula A: Soyamidopropyl Betaine, Stearamidopropyl Betaine, Stearyl Betaine, Tallowamidopropyl Betaine, Tallowami 45 dopropyl Hydroxysultaine, Tallow Betaine, Tallow Dihy CH.), Y- (A) droxyethyl Betaine, Undecylenamidopropyl Betaine und in which Wheat Germamidopropyl Betaine. Ein preferred amphoteric R" is a Saturated or unsaturated C- alkyl group, pref Surfactant is Coca mid op ropyl Be taine erably a Css alkyl group and more preferably a (Cocoamidopropylbetaine). A particularly preferred ampho Saturated Co- alkyl group, for example a Saturated 50 teric Surfactant is Capryl/Capramidopropyl Betaine (CAB) C12-14 alkyl group, which is commercially obtainable, for example, as Tego X is NH, NR with the C alkyl group R, O or S, tens(E) B 810 from Th. Goldschmidt AG. n is a number of 1 to 10, preferably 2 to 5 and more Alkylamido Alkylamines preferably 3, The alkylamido alkylamines (INCI Alkylamido X is 0 or 1, preferably 1, 55 Alkylamines) are amphoteric Surfactants corresponding to R" and R' independently of one another represent an formula B: optionally hydroxySubstituted C alkyl group Such as, for example, a hydroxyethyl group, but especially a methyl group, 60 m is a number of 1 to 4, more particularly 1, 2 or 3, in which y is 0 or 1 and R is a Saturated or unsaturated C-22 alkyl group, Y is COO, SO, OPO(OR)O or P(O)(OR)O, where RY preferably a Css alkyl group and more preferably a is a hydrogen atom H or a C alkyl group. Saturated Co- alkyl group, for example a Saturated The alkyl betaines and alkylamidobetaines, betaines cor 65 C12-14 alkyl group, responding to formula A with a carboxylate group R' is a hydrogen atom H or a C- alkyl group, prefer (Y=COO), are also known as carbobetaines. ably H, US 6,432,892 B2 11 12 i is a number of 1 to 10, preferably 2 to 5, more preferably Alkyl-Substituted amino acids 2 or 3, According to the invention, preferred alkyl-Substituted R' is a hydrogen atom H or CHCOOM (for M, see amino acids (INCI Alkyl-Substituted Amino Acids) are below), monoalkyl-Substituted amino acids corresponding to for j is a number of 1 to 4, preferably 1 or 2, more preferably mula C: 1, R-NH-CH(R)-(CH),-COOM' (C) k is a number of 0 to 4, preferably 0 or 1, I is 0 or 1, k being 1 where I is 1, in which Z is CO, SO, OPO(OR") or P(O)(OR") where R is a R is a Saturated or unsaturated C- alkyl group, C. alkyl group or M (see below) and preferably a C- alkyl group and more preferably a M is a hydrogen atom, an alkali metal, an alkaline earth Saturated Co- alkyl group, for example a Saturated metal or a protonated alkanolamine, for example pro C2-alkyl group, R is a hydrogen atom H or a C tonated mono-, di- or triethanolamine. alkyl group, preferably H, Preferred representatives correspond to formulae B1 to 15 u is a number of 1 to 4, preferably 0 or 1, more preferably B4: 1, and M" is a hydrogen atom, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example pro tonated mono-, di- or triethanolamine, alkyl-Substituted imino acids corresponding to formula D: R'-N-(CH2)-COOM", (D)

in which 25 R" is a Saturated or unsaturated C-22 alkyl group, preferably a Css alkyl group and more preferably a in which R', R' and M are as defined for formula B. Saturated Co- alkyl group, for example a Saturated Examples of alkylamido alkylamines are the following C12-14 alkyl group, compounds identified by their INCI names: Cocoamphod v is a number of 1 to 5, preferably 2 or 3, more ipropionic Acid, Cocobetainamido Amphopropionate, DEA preferably 2, and Cocoamphodipropionate, Disodium Caproamphodiacetate, M" is a hydrogen atom, an alkali metal, an alkaline DiSodium Cap roamphodipropionate, DiSodium earth metal or a protonated alkanolamine, for Caprylo a mph O diac et a te, DiSodium example protonated mono-, di- or triethanolamine, Caprylo ampho dip ropio nate, Disodium M" in the two carboxy groups may have the same Cocoamphocarboxyethylhydroxypropylsulfonate, Diso 35 meaning or two different meanings, for example may dium Coco ampho diacetate, Disodium be hydrogen and Sodium or just Sodium, Coco ampho dip ropio nate, Disodium and mono- or dialkyl-Substituted natural amino acids ISO Ste a roampho diacetate, Disodium corresponding to formula E: ISO Stearoamphodipropionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, 40 RXi N(RI)-CH(RI)-COOM" (E) DiSodium Lauro amphodipropio nate, DiSodium Oleoamphodipropionate, Disodium PPG-2-Isodeceth-7 in which Carboxyamphodiacetate, Disodium Stearoamphodiacetate, R" is a saturated or unsaturated C- alkyl group, Disodium Tallow ampho diacetate, Disodium preferably a Css alkyl group and more preferably Wheatgermamphodiacetate, Lauroamphodipropionic Acid, 45 a Saturated Co. alkyl group, for example a Quaternium-85, Sodium Caproamphoacetate, Sodium Saturated C2-alkyl group, Capro amphohydroxypropyl Sulfonate, Sodium R" is a hydrogen atom or an optionally hydroxy- or Caproamphopropionate, Sodium Capryloamphoacetate, amine-Substituted C. alkyl group, for example a Sodium Capryloamphohydroxypropylsulfonate, Sodium methyl, ethyl, hydroxyethyl or aminopropyl grOup, Capryloamphopropionate, Sodium Cocoamphoacetate, 50 Sodium Cocoamphohydroxypropylsulfonate, Sodium R' is the residue of one of the 20 natural O-amino Cocoamphopropionate, Sodium Cornamphopropionate, acids HNCH(R')COOH and Sodium ISO Ste a roampho acetate, Sodium M" is a hydrogen atom, an alkali metal, an alkaline ISOStearoamphopropionate, Sodium Lauroamphoacetate, earth metal or a protonated alkanolamine, for Sodium Lauroamphohydroxypropylsulfonate, Sodium Lau 55 example protonated mono-, di- or triethanolamine. roampho P G - Acetate Phosphate, Sodium Particularly preferred alkyl-Substituted amino acids are Lauroamphopropionate, Sodium Myristoamphoacetate, the aminopropionates corresponding to formula C. Sodium Oleoamphoacetate, Sodium Oleoamphohydrox ypropylsulfonate , Sodium Oleoamphopropionate, Sodium R-NH-CHCHCOOM' (C) Ricinoleoamphoacetate, Sodium Stearoamphoacetate, 60 in which R and M' have the same meanings as in formula Sodium Stearoamphohydroxypropylsulfonate, Sodium C. Stearoamphopropionate, Sodium Tallamphopropionate, Examples of alkyl-Substituted amino acids are the follow Sodium Tallow ampho acetate, Sodium ing compounds identified by their INCI names: Aminopro Unde cyle no ampho acetate, Sodium pyl Laurylglutamine, Cocaminobutyric Acid, Cocaminopro Undecylenoamphopropionate, Sodium Wheat Germam 65 pionic Acid, DEA-Lauraminopropionate, Disodium phoacetate und Trisodium Lauroampho PG-Acetate Chlo Cocaminopropyl Iminodiacetate, Disodium Dicarboxyethyl ride Phosphate. Cocopropylenediamine, Disodium Lauriminodipropionate, US 6,432,892 B2 13 14 DiSodium Ste a rimino dipropio nate, DiSodium EDTA, Disodium Azacycloheptane Diphosphonate, Diso Tallowiminodipropionate, Lauraminopropionic Acid, Lau dium EDTA, Disodium Pyrophosphate, EDTA, Etidronic ryl Aminopropylglycine, Lauryl Diethylenediaminoglycine, Acid, Galactaric Acid, Gluconic Acid, Glucuronic Acid, Myristaminopropionic Acid, Sodium C. Alkoxypropyl HEDTA, Hydroxypropyl Cyclodextrin, Methyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Lauraminopropionate, Sodium Lauriminodipropionate, Aminotrimethylene Phosphonate, Pentasodium Ethylenedi Sodium Lauroyl Methylaminopropionate, TEA amine Tetramethylene Phosphonate, Pentasodium Pentetate, Lauraminopropionate und TEA-Myristamino-propionate. Pentasodium Triphosphate, Pentetic Acid, Phytic Acid, Acylated Amino Acids Potassium Citrate, Potassium EDTMP, Potassium Acylated amino acids are amino acids, more particularly Gluconate, Potassium Polyphosphate, Potassium Trispho the 20 natural C.-amino acids, which carry the acyl group sphonomethylamine Oxide, Ribonic Acid, Sodium Chitosan RCO of a saturated or unsaturated fatty acid RCOOH at Methylene Phosphonate, Sodium Citrate, Sodium Diethyl the amino nitrogen atom (R' being a saturated or unsatur enetriamine Pentamethylene Phosphonate, Sodium ated C-2 alkyl group, preferably a Css alkyl group and Dihydroxyethylglycinate, Sodium EDTMP, Sodium more preferably a Saturated Co. alkyl group, for example 15 Gluceptate, Sodium Gluconate, Sodium Glycereth-1 a Saturated C- alkyl group). The acylated amino acids Polyphosphate, Sodium Hexametaphosphate, Sodium may also be used in the form of an alkali metal Salt, an Metaphosphate, Sodium Metasilicate, Sodium Phytate, alkaline earth metal Salt or alkanolammonium Salt, for Sodium Polydimethylglycinophenolsulfonate, Sodium example mono-, di- or triethanolamine. Examples of acy Trimetaphosphate, TEA-EDTA, TEA-Polyphosphate, Tet lated amino acids are the acyl derivatives known collectively rahydroxyethyl Ethylenediamine, Tetrahydroxypropyl by the INCI name of Amino Acids, for example Sodium Ethylenediamine, Tetrapotassium Etidronate, Tetrapotas Cocoyl Glutamate, Lauroyl Glutamic Acid, Capryloyl Gly sium Pyrophosphate, Tetrasodium EDTA, Tetrasodium cine oder Myristoyl Methylalanine. Etidronate, Tetrasodium Pyrophosphate, Tripotassium Complexing Agents EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium In addition, the composition according to the invention 25 EDTA, Trisodium HEDTA, Trisodium NTA und Trisodium preferably contains one or more complexing agents in a Phosphate. quantity, based on the composition, of typically 0.01 to 20% Preferred complexing agents are the citrates, more par by weight, preferably 0.1 to 10% by weight, more preferably ticularly alkali metal citrates, especially Sodium citrate and/ 0.5 to 10% by weight, most preferably 1 to 5% by weight or potassium citrate and most particularly potassium citrate. and, in one most particularly preferred embodiment, 1.5 to In the context of the present invention, the citrates are the 4% by weight. Salts of 3x-deprotonated citric acid unless otherwise Specifi Complexing agents (INCI Chelating Agents), also known cally Stated. However, the mono- and dihydrogen citrates as Sequestering agents, are ingredients which are capable of may also be used in accordance with the invention. complexing and inactivating metal ions to prevent them The complexing Salts mentioned may also be used in the adverse affecting the Stability and appearance of the 35 form of their corresponding acids or bases which are then composition, for example clouding, and in particular to partly or completely neutralized, depending on the pH value guarantee a clear Solution, even where the composition is to be established, for example citric acid in the form of its used with hard water. On the one hand, it is important in this monohydrate citric acid-1. HO instead of citrate. regard to complex the calcium and magnesium ions of water pH Value hardneSS which are incompatible with many ingredients. On 40 The pH of the composition according to the invention the other hand, complexing of the ions of heavy metals, Such may be adjusted to a value within a wide range from Strongly as iron or copper, delays the oxidative decomposition of the acidic via neutral to Strongly alkaline and is normally in the final composition. In addition, complexing agents Support range from 1 to 14, preferably in the range from 2 to 13, the cleaning effect. more preferably in the range from 3 to 12, most preferably Suitable complexing agents are, for example, alkali metal 45 in the range from 3.5 to 11 and, in one most particularly citrates, gluconates, nitrilotriacetates, carbonates and preferred embodiment, in the range from 4 to 10.5. bicarbonates, more particularly Sodium and potassium In a preferred acidic embodiment, the pH value of the citrate, gluconate and nitrilotriacetate. They also include the composition according to the invention is in the range from Salts of glutaric acid, Succinic acid, adipic acid, tartaric acid 2 to 6, preferably in the range from 2.5 to 5.5, more and benzeneheXacarboxylic acid and aminotrimethylene 50 preferably in the range from 3 to 5, most preferably in the phosphonic acid, hydroxyethane-1,1-diphosphonic acid, range from 3.5 to 4.5 and, in one most particularly preferred 1-aminoethane-1,1-diphosphonic acid, ethylenediamine embodiment, is pH 4. tetra(methylene phosphonic acid), diethylenetriamine penta In a neutral embodiment, the pH of the composition (methylenephosphonic acid), 2-phosphonobutane-1,2,4- according to the invention is in the range from 6 to 8 and tricarboxylic acid, phosphonates and phosphates, for 55 preferably in the range from 6.5 to 7.5 and more preferably example the Sodium Salts of methanediphosphonic acid, the is 7. pentasodium triphosphate known as Sodium tripolyphoS In a particularly preferred alkaline embodiment, the pH phate or Sodium hexametaphosphate Such as, for example, a value of the composition according to the invention is in the mixture of condensed orthophosphates with an average range from 8 to 13, preferably in the range from 9 to 12, degree of condensation of about 12. 60 more preferably in the range from 9.5 to 11.5, most prefer Suitable complexing agents are the following compounds ably in the range from 10 to 11 and, in one most particularly identified by their INCI names (some of which have already preferred embodiment, is pH 10.5. been mentioned): Aminotrimethylene Phosphonic Acid, To adjust, control and/or stabilize the pH value, the Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Cit composition according to the invention preferably contains ric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic 65 one or more pH regulators (INCI pH Adjusters), more Acid, Diammonium Citrate, Diammonium EDTA, Diethyl particularly from the group of acids, bases and buffering enetriamine Pentamethylene Phosphonic Acid, Dipotassium agents and mixtures thereof, in a quantity-based on the US 6,432,892 B2 15 16 composition-of normally 0.01 to 15% by weight, prefer Solvents ably 0.1 to 10% by weight, more preferably 0.5 to 5% by The water-based composition according to the invention weight, most preferably 1 to 4% by weight and, in one most contains water as primary Solvent in a quantity, based on the particularly preferred embodiment, 1.5 to 3% by weight. composition, of normally 40 to 99.99% by weight, prefer Suitable pH regulators are, for example, the following ably 50 to 99% by weight, more preferably 60 to 95% by compounds identified by their INCI names: Acetic Acid, weight, most preferably 70 to 92% by weight and, in one Acetyl Mandelic Acid, Adipic Acid, Aluminum Triformate, 2-Aminobutanol, Aminoethyl Propanediol, Aminomethyl most particularly preferred embodiment, 80 to 90% by Propanediol, Aminomethyl Propanol, Ammonia, Ammo weight, for example 85 or 89% by weight. The very low nium Bicarbonate, Ammonium Carbamate, Ammonium water contents down to only 40% by weight- or even Carbonate, Ammonium Glycolate, Ammonium Hydroxide, 1O lower-may be reached in concentrated or highly concen Ammonium Phosphate, AScorbic Acid, AZelaic Acid, Ben trated embodiments and normally necessitate corresponding zoic Acid, Bis-Hydroxyethyl Tromethamine, Calcium dilution before use. Citrate, Calcium Dihydrogen Phosphate, Calcium Organic Solvents Hydroxide, Calcium Oxide, Citric Acid, Diethanolamine, In addition, the composition according to the invention Diethanolamine Bisulfate, Diisopropanolamine, 15 preferably contains one or more organic Solvents in a Diisopropylamine, Dimethyl MEA, Dioleoyl Edetolmonium quantity-based on the composition-of 0.01 to 30% by Me thosulfate, Dipotassium Phosphate, weight, preferably 0.1 to 20% by weight, more preferably 1 Dipropylenetriamine, Disodium Phosphate, Disodium to 15% by weight, most preferably 2 to 10% by weight and, Pyrophosphate, Disodium Tartrate, Ethanolamine, Ethano in one most particularly preferred embodiment, 3 to 7% by lamine HCl, Formic Acid, Fumaric Acid, Galacturonic Acid, weight, for example 5% by weight. Glucoheptonic Acid, Glucosamine HCl, Glucuronic Acid, Suitable organic Solvents are, for example, Saturated or Glycolic Acid, Glyoxylic Acid, Guanidine Carbonate, unsaturated, preferably Saturated, branched or unbranched Hydrochloric Acid, Imidazole, Isopropanolamine, C'hydrocarbons, preferably C-1s hydrocarbons, contain Isopropylamine, Ketoglutaric Acid, Lactic Acid, Lacto ing one or more hydroxy groups, preferably one hydroxy bionic Acid, Lithium Hydroxide, Magnesium Carbonate, 25 group, and optionally one or more ether functions C-O- Magnesium Carbonate Hydroxide, Magnesium Hydroxide, C, i.e. oxygen atoms interrupting the carbon atom chain. Magnesium Oxide, Maleic Acid, Malic Acid, Malonic Acid, Preferred Solvents are the Calcohols, more particularly Metaphosphoric Acid, Methylethan olamine, ethanol, n-propanol and/or isopropanol, preferably ethanol, Methylglucamine, Mixed Isopropanolamines, Monosodium polyols, Such as glycerol, and the C- alkylene glycols and Citrate, Morpholine, Oxalic Acid, Pentapotassium poly-C-alkylene glycol ethers-optionally etherified on Triphosphate, Pentasodium Triphosphate, Phosphoric Acid, one side with a C- alkanol-containing on average 1 to 9 Potassium Bicarbonate, Potassium Biphthalate, Potassium identical or different, preferably identical, alkylene glycol Borate, Potassium Carbonate, Potassium Citrate, Potassium groups per molecule, more particularly the poly-C- Hydroxide, Potassium Phosphate, Propionic Acid, Quinic alkylene glycol ethers etherified on one Side with a C Acid, Ribonic Acid, Sebacic Acid, Sodium Aluminate, 35 alkanol and containing on average 1 to 9 and preferably 2 to Sodium Bicarbonate, Sodium Bisulfate, Sodium Borate, 3 ethylene or propylene glycol groups, for example PPG-2 Sodium Carbonate, Sodium Citrate, Sodium Fumarate, Methyl Ether (dipropylene glycol monomethyl ether). Par Sodium Hydroxide, Sodium Oxide, Sodium ticularly preferred organic Solvents are the C alcohols Sesquicarbonate, Sodium Silicate, Sodium Succinate, ethanol, n-propanol or isopropanol, more particularly etha Sodium Trimetaphosphate, Strontium Hydroxide, Succinic 40 nol. Acid, Sulfuric Acid, Tartaric Acid, Tetrapotassium Other Suitable organic Solvents are the following com Pyrophosphate, Tetrasodium Pyrophosphate, pounds identified by their INCI names (some of which have Trie thanolamine, Triisopropanolamine, TriSodium already been mentioned): Alcohol (Ethanol), Buteth-3, Phosphate, Tromethamine, Vinegar. Butoxydiglycol, Butoxyethanol, Butoxyisopropanol, Preferred pH regulators are citric acid (as acid), hydrox 45 Butoxypropanol, n-Butyl Alcohol, t-Butyl Alcohol, Buty ides (as bases) and the citrates, carbonates and hydrogen lene Glycol, Butyloctanol, Diethylene Glycol, carbonates (as buffering agents), the hydroxides and/or Dimethoxydiglycol, Dimethyl Ether, Dipropylene Glycol, buffering agents preferably being alkali metal Salts, more Ethoxydiglycol, Ethoxyethanol, Ethyl Hexanediol, Glycol, particularly Sodium and/or potassium Salts and most par Hexanediol, 1,2,6-Hexanetriol, Hexyl Alcohol, Hexylene ticularly potassium Salts. 50 Glycol, Isobutoxypropanol, Isopentyldiol, Isopropyl Alco A number of compounds act both as complexing agents hol (iso-Propanol), 3-Methoxybutanol, Methoxydiglycol, and as pH regulators and, by Virtue of this dual functionality, Methoxyeth an ol, Methoxy is op rop an ol, are preferably used as Such because they provide for par Methoxymethylbutanol, Methoxy PEG-10, Methylal, ticularly efficient formulation of the composition according Methyl Alcohol, Methyl Hexyl Ether, Methylpropanediol, to the invention. 55 Neopentyl Glycol, PEG4, PEG-6, PEG-7, PEG-8, PEG-9, Accordingly, in one particularly preferred embodiment, PEG-6 Methyl Ether, Pentylene Glycol, PPG-7, PPG-2- the composition according to the invention contains citric Buteth-3, PPG-2. Butyl Ether, PPG-3. Butyl Ether, PPG-2 acid and alkali metal hydroxide- or corresponding Methyl Ether, PPG-3 Methyl Ether, PPG-2 Propyl Ether, citrate-together with alkali metal carbonate and/or hydro Propanediol, Propyl Alcohol (n-Propanol), Propylene gen carbonate, more particularly citric acid and potassium 60 Glycol, Propylene Glycol Butyl Ether, Propylene Glycol hydroxide together with potassium carbonate. Propyl Ether, Tetrahydrofurfuryl Alcohol, Trimethylhex In another particular embodiment of the composition anol. according to the invention, the content of carbonate ions Monomeric or homo- or heteropolymeric, more particu CO, based on the composition, is 0.01 to less than 1% by larly monomeric and homo-, di- and trimeric C alkylene weight, preferably 0.1 to 0.9% by weight, more preferably 65 glycols etherified or esterified with aliphatic or aromatic 0.3 to 0.8% by weight and most preferably 0.5 to 0.7% by alcohols, for example methanol, ethanol, n-propanol, weight, for example 0.6% by weight. n-butanol, tert.-butanol or phenol, or carboxylic acids, for US 6,432,892 B2 17 18 example acetic or carbonic acid, are marketed, for example, N'-phenyldiguanido-Ns,N)-hexane tetrahydrochloride, under the name of Dowanol(R) by Dow Chemical and under 1,6-di-(N,N'-phenyl-N,N-methyldiguanido-N,N)- the names of Arcosolv(R) and Arconate(R) by Arco Chemical, hexane dihydrochloride, 1,6-di- (N,N'-o- such as the products listed below under their INCI names chlorophenyldiguanido-Ns,N)-hexane dihydrochloride, (Intemational Dictionary of Cosmetic Ingredients published 1,6-di-(N,N'-2,6-dichlorophenyldiguanido-N,Ns)- by The Cosmetic, Toiletry and Fragrance ASSociation hexane dihydrochloride, 1,6-di-N,N'-f-(p- (CTFA)), for example butoxy diglycol (Dowanol(R) DB), methoxyphenyl)-diguanido-N,N'-hexane methoxydiglycol (Dowanol(R) DM), PPG-2 Methyl Ether dihydrochloride, 1,6-di-(NN'-C.-methyl-f- (Dowanol (R DPM), PPG-2 Methyl Ether Acetate phenyidiguanido-N,N)-hexane dihydrochloride, 1,6-di (Dowanol& DPMA), PPG-2 Butyl Ether (Dowanole) (N,N'-p-nitrophe nyidiguanido-Ns, Ns")-hexane DPnB), PPG-2 Propyl Ether (Dowanol& DPnP), Butoxy dihydrochloride, ():co'-di-(N,N'-phenyldiguanido-Ns.Ns)- ethanol (Dowanol(R) EB), Phenoxyethanol (Dowanol(R) di-n-propyl ether dihydrochloride, co: (1)-di-(N,N'-p- EPh), Methoxyisopropanol (Dowanol?FPM), PPG-1 Methyl chlorophenyldiguanido-Ns,Ns")-di-n-propyl ether Ether Acetate (Dowanol(R) PMA), Butoxyisopropanol tetrahydro chloride, 1,6-di-(N,N'-2,4- (Dowanol(R) PnB), Propylene Glycol Propyl Ether 15 dichlorophe nyl diguanido-Ns, Ns') - he X an e (Dowanol?& PnP), Phenoxyisopropanol (Dowanol(R) PPh), tetrahydro chloride, 1,6-di- (N,N'-p- PPG-3 Methyl Ether (Dowanol(R) TPM) and PPG-3 Butyl methylphenyldiguanido-Ns,Ns)-hexanedihydrochloride, Ether (Dowanol(R) TPnB) and Ethoxyisopropanol 1,6-di-(N,N'-2,4,5-trichlorophenyldiguanido-N,N)- (Arcosolv(R) PE), tert.-Butoxyisopropanol (Arcosol(R) PTB), hexane tetrahydrochloride, 1,6-di-N,N'-O-(p- PPG-2 tert-butyl ether (Arcosolv(R DPTB) and Propylen chlorophenyl)-ethyldiguanido-Ns, N3'-hexane ecarbonate (Arconate(R) PC), of which butoxy isopropanol dihydrochloride, co: (1)-di-(N,N'-p-chlorophenyidiguanido (dipropylene glycol-n-butyl ether, Dowanol(R) PnB) and par N,N)-m-xylene dihydrochloride, 1,12-di-(N, N'-p- ticularly PPG-2 Methyl Ether (dipropylene glycol methyl chloropheny idiguanido-Ns, Ns') - do de cane ether, Dowanol(R) DPM) are preferred. dihydrdochloride, 1,10-di-(N,N'-phenyldiguanido-Ns, Antimicrobial Agents 25 Ns")-decane tetrahydrochloride, 1,12-di-(N,N'- To control microorganisms, the cleaning composition phenyldiguanido-Ns.Ns)-dodecane tetrahydrochloride, 1,6- according to the invention may contain one or more anti di-(N,N'-o'-chlorophenyldiguanido-Ns,Ns")-hexane microbial agents. Depending on the antimicrobial spectrum dihydrochloride, 1,6-di-(N,N'-O-chlorophenyidiguanido and the action mechanism, antimicrobial agents are classi N,N')-hexane tetrahydrochloride, ethylene-bis-(1- fied as bacterioStatic agents and bactericides, fungistatic tolylbiguanide), ethylene-bis-(p-tolylbiguanide), ethylene agents and fungicides, etc. Important representatives of bis-(3,5-dimethylphenylbiguanide), ethylene-bis-(p- these groups are, for example, benzalkonium chlorides, tert. a myl phenylbiguanide), ethylene-bis alkylaryl Sulfonates, halophenols and phenol mercuriacetate. (nonylphenylbiguanide), ethylene-bis-(phenylbiguanide), In the present context, the expressions “antimicrobial activ ethylene-bis-(N-butylphenylbiguanide), ethylene-bis-(2,5- ity' and “antimicrobial agent' have the usual meanings as 35 die thoxyphenylbiguanide), ethylene-bis-(2,4- defined, for example, by K. H. Wallhau?er in “Praxis der dimethyl phenylbiguanide), ethylene-bis-(o- Sterilisation, De Sinfektion diphenylbiguanide), ethylene-bis-(mixed-amylnaphthyl Konservierung: Keimidentifizierung-Betriebshygiene' biguanide), N-butylethylene-bis-(phenylbiguanide), (5th Edition, Stuttgart/New York: Thieme, 1995), any of the trimethylene-bis-(o-tolylbiguanide), N-butyltrimethylene substances with antimicrobial activity described therein 40 bis-(phenylbiguanide) and the corresponding salts, Such as being uSable. Suitable antimicrobial agents are preferably acetates, gluconates, hydrochlorides, hydrobromides, Selected from the groups of alcohols, amines, aldehydes, citrates, bisulfites, fluorides, polymaleates, N-cocoalkyl antimicrobial acids and Salts thereof, carboxylic acid esters, Sarco Sinate S, phosphite S, hypophosphite S, acid amides, phenols, phenol derivatives, diphenyls, perfluorooctanoates, Silicates, Sorbates, Salicylates, diphenylalkanes, urea derivatives, oxygen and nitrogen 45 male ate S, tart rates, fumarates, ethylene diamine acetals and formals, benzamidines, isothiazolines, phthalim tetraacetates, iminodiacetates, cinnamates, thiocyanates, ide derivatives, pyridine derivatives, antimicrobial Surface arginates, pyromellitates, tetracarboxybutyrates, benzoates, active compounds, guanidines, antimicrobial amphoteric glutarates, monofluorophosphates, perfluoropropionates and compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, mixtures thereof. Halogenated Xylene and creSol derivatives, iodo-2-propylbutyl carbamate, iodine, iodophores, peroxo 50 Such as p-chloro-m-creSol or p-chloro-m-Xylene, and natural compounds, halogen compounds and mixtures of the above. antimicrobial agents of vegetable origin (for example from The antimicrobial agent may be selected from ethanol, Spices or herbs), animal and microbial origin are also n-propanol, i-propanol, butane-1,3-diol, phenoxyethanol, Suitable. Preferred antimicrobial agents are antimicrobial 1,2-propylene glycol, glycerol, undecylenic acid, benzoic Surface-active quaternary compounds, a natural antimicro acid, Salicylic acid, dihydracetic acid, o-phenylphenol, 55 bial agent of vegetable origin and/or a natural antimicrobial N-methyl morpholine acetonitrile (MMA), 2-benzyl-4- agent of animal origin and, most preferably, at least one chlorophenol, 2,2'-methylene-bis-(6-bromo4-chlorophenol), natural antimicrobial agent of vegetable origin from the 4,4'-dichloro-2'-hydroxydiphenyl ether (Dichlosan), 2,4,4'- group comprising caffeine, theobromine and theophylline trichloro-2'-hydroxydiphenyl ether (Trichlosan), and essential oils, Such as eugenol, thymol and geraniol, chlorohexidine, N-(4-chlorophenyl)-N-3,4-dichlorophenyl)- 60 and/or at least one natural antimicrobial agent of animal urea, N,N'-(1,10-decanediyldi-1-pyridinyl-4-ylidene)-bis origin from the group comprising enzymes, Such as protein (1-octanamine)-dihydrochloride, N,N'-bis-(4- from milk, lysozyme and lactoperoxidase and/or at least one chlorophenyl)-3,12-diimino-2,4,11,13-tetraazatetradecane antimicrobial Surface-active quaternary compound contain diimidoamide, glucoprotamines, antimicrobial Surface ing an ammonium, Sulfonium, phosphonium, iodonium or active quaternary compounds, guanidines, including the bi 65 arSonium group, peroxo compounds and chlorine com and polyguanidines Such as, for example, 1,6-bis-(2- pounds. Substances of microbial origin, So-called ethylhexylbiguanidohexane)-dihydrochloride, 1,6-di-(N, bacteriozines, may also be used. US 6,432,892 B2 19 20 The quaternary ammonium compounds (QUATS) suitable Perfumes as antimicrobial agents have the general formula (R')(R) The composition also contains one or more perfumes, (R)(R')NX, in which R" to R' may be the same or typically in the form of one or more perfume oils, in a different and represent C alkyl groups, C.7s aralkyl quantity of normally 0.001 to 1% by weight, preferably groups or heterocyclic groups, two or-in the case of an 0.005 to 0.5% by weight, more preferably 0.01 to 0.1% by aromatic compound, Such as pyridine-even three groups weight and most preferably 0.02 to 0.05% by weight. together with the nitrogen atom forming the heterocycle, for example a pyridinium or imidazolinium compound, and X Another advantage of the invention is that a certain represents halide ions, Sulfate ions, hydroxide ions or similar perfume intensity is achieved in the composition according anions. In the interests of optimal antimicrobial activity, at to the invention even with unusually Small amounts of least one of the Substituents preferably has a chain length of perfume oil. This is presumably attributable to the short 8 to 18 and, more preferably, 12 to 16 carbon atoms. chain alkyl polyglycoside essential to the invention. QUATS can be obtained by reaction of tertiary amines Other Ingredients with alkylating agents Such as, for example, methyl chloride, Depending on the formulation of the composition accord benzyl chloride, dimethylsulfate, dodecyl bromide and also ing to the invention, one or more auxiliaries and additives ethylene oxide. The alkylation of tertiary amines with one 15 typical of the particular application envisaged-more par long alkyl chain and two methyl groups is particularly ticularly from the group of Solubilizers, hydrotropes, Simple. The quaternization of tertiary amines containing two emulsifiers, enzymes, preservatives, corrosion inhibitors, long chains and one methyl group can also be carried out colorants and Viscosity regulators, more particularly under mild conditions using methyl chloride. Amines con thickeners-may be present as further ingredients. taining three long alkyl chains or hydroxy-Substituted alkyl Use chains lack reactivity and are preferably quaternized with In a fourth embodiment, the present invention relates to a dimethyl sulfate. process for cleaning fruit, vegetables and/or meat in which Suitable QUATS are, for example, benzalkonium chloride the fruit, vegetables and/or meat to be cleaned are first (N-alkyl-N,N-dimethylbenzyl ammonium chloride, CAS treated with a composition according to any of the preceding No. 8001-54-5), benzalkon B (m.p-dichlorobenzyl 25 dimethyl-C-alkyl ammonium chloride, CAS No. 58390 composition claims in undiluted or diluted form, after which 78-6), benzoxonium chloride (benzyldodecyl-bis-(2- the composition is removed again. hydroxyethyl)-ammonium chloride), cetrimonium bromide To carry out the treatment, the composition may either be (N-hexadecyl-N,N-trimethyl ammonium bromide, CAS No. applied undiluted, preferably by Spraying, or the produce to 57-09-0), benzetonium chloride (N,N-dimethyl-N-2-2-p- be cleaned may be introduced into a cleaning bath prepared (1,1,3,3-tetramethylbutyl)-phenoxy-ethoxy-ethyl-benzyl by diluting the composition with water. Typical cleaning ammonium chloride, CAS No. 121-54-0), dialkyl dimethyl baths contain 0.1 to 10 ml, preferably 0.5 to 5 ml and more ammonium chlorides, Such as di-n-decyldimethyl ammo preferably 1 to 3.5 ml of the composition per 100 ml of bath. nium chloride (CAS No. 7173-51-5-5), didecyidimethyl The composition is preferably removed again by rinsing ammonium bromide (CAS No. 2390-68-3), dioctyl dimethyl with running water. Alternate means of removal include ammonium chloride, 1-cetylpyridinium chloride (CAS No. 35 immersion, Spraying, or wiping with water or an aqueous 123-03-5) and thiazoline iodide (CAS No. 15764-48-1) and fluid. mixtures thereof. Particularly preferred QUATS are the benzalkonium chlorides containing Css alkyl groups, more particularly C2-alkylbenzyl dimethyl ammonium chlo EXAMPLES ride. 40 Compositions E1 to E3 according to the invention and Benzalkonium halides and/or Substituted benzalkonium comparison composition C were prepared. Their ingredi halides are commercially obtainable, for example, as Bar ents and pH values are shown in Table 1 below. quatcE) from Lonza, Marquate from Mason, Variquate from Witco/Sherex and Hyamine(R) from Lonza and as Bardac(R) TABLE 1. from Lonza. Other commercially obtainable antimicrobial 45 agents are N-(3-chloroallyl)-hexaminium chloride, Such as Composition 76 by weight E1 E2 E3 C1 Dowicide(E) and Dowicil(E) from Dow, benzethonium Cs alkyl-1,5-glucoside 18al 8|al 18tal - chloride, such as Hyamine(R) 1622 from Rohm & Haas, Co alkyl-1,5-glucoside 12(b) 2(b) 1.2bl - methylbenzethonium chloride, such as Hyamine(R) 10x from Erucic acid 2 Rohm & Haas, cetyl pyridinium chloride, Such as cepa 50 Oleic acid 2.4 colchloride from Merrell Labs. Citric acid 1 HO 1.6 2.5 1.6 O.6 KOH 1.1 1. 1.4 0.5 In one particularly preferred embodiment, the composi KCO 1.5 1.5 tion according to the invention contains benzoic acid and/or NaHCO O.7 derivatives thereof, more particularly Salicylic acid or Salts Ethanol 4.8 4.8 4.8 2 Glycerol 2 thereof, as the one or more antimicrobial agents. 55 Salicylic acid O The antimicrobial agents are used in quantities of nor Perfume oil O.05 O.OS O.05 -- mally 0.0001% by weight to 5% by weight, preferably Water to 100 to 100 to 100 to 100 0.001% by weight to 2% by weight, more preferably 0.005% pH value 10.5 4.0 10.5 11.6 by weight to 1% by weight, most preferably 0.01% by Residue % 32 25 54 22 weight to 0.5% by weight and, in one most particularly 60 lcontains at most 0.06% by weight Ce alkyl-1,5-glycoside preferred embodiment, 0.05% by weight to 0.2% by weight. contains at most 0.2% by weight C, alkyl-1,5-glycoside The particular quantity used will be Selected by the expert with the particular antimicrobial agent or mixture and the Another comparison composition C containing 3% by antimicrobial effect to be obtained in mind so that, in weight of a C- alkyl-1,4-glucoside was prepared simi particular embodiments of the invention, a content of anti 65 larly to E1. Whereas the above-mentioned compositions microbial agents outside the range mentioned may also be were obtained as clear Solutions, C was cloudy even in appropriate. undiluted form. US 6,432,892 B2 21 22 Cleaning Performance 2. A water-based composition for cleaning fruit, The compositions were tested for cleaning performance. vegetables, or meat, comprising one or more Co alkyl To this end, waxed apples (“Jona Gold”) were cleaned polyglycosides. with water and with the four compositions. The apples were 3. The composition of claim 2, comprising one or more then rinsed with pentane and quantities of 10 g of the additional Surfactants. extracts obtained were concentrated in a Stream of nitrogen. 4. The composition of claim 3, wherein the one or more The concentrated extracts were then Sillylated and quantified additional Surfactants comprise one or more nonionic Sur by HT gas chromatography. The Sum of the peak areas on the factants. gas chromatograms obtained are shown in Table 1 as the percentage residue, based on the 100% value for the apple 5. The composition of claim 4, wherein the one or more pretreated with water. additional Surfactants comprise one or more Co. alkyl All the compositions performed considerably better than polyglycosides. the tap water normally used for this purpose in the home. 6. The composition of claim 2, comprising no Soaps. Sensitivity to Water Hardness 7. The composition of claim 2, comprising no anionic Surfactants. The Sensitivity of the compositions to water hardneSS was 15 also tested. 8. The composition of claim 2, comprising one or more To this end, quantities of 1 and 3.5 ml of the particular complexing agents. composition were diluted to 100 ml with water differing in 9. The composition of claim 3, comprising one or more hardness (0, 2, 4, 8, 16, 24, 32, 40, 48 and 64 d=German complexing agents. hardness) and the resulting cleaning liquid was visually 10. The composition of claim 2, comprising one or more evaluated. pH regulators. With the comparison composition C, a clear liquid was 11. The composition of claim 9, comprising one or more only obtained with water of Od; even water of 2 d led to pH regulators. clouding which increased with increasing water hardness. 12. The composition of claim 2, comprising one or more Finally, the dilutions with water of 40 d or higher produced 25 organic Solvents. a flocculent sediment which, in the case of the 1 ml dilution 13. The composition of claim 11, comprising one or more with water of 32 d, was even noticeable in the liquid. organic Solvents. Compositions E1 and E2 produced clear liquids even 14. The composition of claim 2, comprising one or more when diluted with the water of 64 d. Composition E3 also antimicrobial agents. produced a clear liquid in the case of the 1 ml dilution with water of 16 dand, with water of 48 d, led to a translucently 15. The composition of claim 13, comprising one or more hazy liquid which resembled the liquid obtained in the case antimicrobial agents. of the same dilution of C, with water of only 2 d. The 3.5 16. The composition of claim 2, comprising one or more ml dilution of E3 with water of 16 d resulted in a slightly perfumes. opaque liquid and, only with water of 64 d, led to a milky 35 17. The composition of claim 15, comprising one or more liquid which resembled the liquid obtained in the case of the perfumes. same dilution of C with water of only 8 d. 18. The composition of claim 2, having a pH value of 1 Accordingly, the compositions according to the invention to 14. are far leSS Sensitive to water hardness. 19. The composition of claim 2, having a pH value of 2 What is claimed is: 40 to 13. 1. A method of cleaning fruit, vegetables, or meat, com 20. The composition of claim 2, having a pH value of 3 prising the Steps of applying a cleaning effective amount of to 12. one or more Co alkyl polyglycosides to a piece of fruit, 21. The composition of claim 2, having a pH value of 3.5 vegetable, or meat in need of cleaning of Soil, residue, to 11. coating, or any other undesirable Substance, and removing 45 22. The composition of claim 2, having a pH value of 4 the one or more Co alkyl polyglycosides and the of Soil, to 10.5. residue, coating, or other undesirable Substance from the fruit, vegetable, or meat by an appropriate means. UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION

PATENT NO. : 6,432,892 B2 Page 1 of 1 DATED : August 13, 2002 INVENTOR(S) : Meine et al.

It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

Title page, Item 56, References Cited, FOREIGN PATENT DOCUMENTS, delete “WO98/07331, and insert therefor-- WO95/07331 --. Column 21 Line 46, after "the", delete “of”.

Signed and Sealed this Ninth Day of September, 2003

JAMES E ROGAN Director of the United States Patent and Trademark Office