Europäisches Patentamt *EP000935646B1* (19) European Patent Office Office européen des brevets (11) EP 0 935 646 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.7: C11D 3/00, C11D 1/835, of the grant of the patent: C11D 1/94, C11D 3/30 02.05.2003 Bulletin 2003/18 (86) International application number: (21) Application number: 97912764.4 PCT/US97/18774 (22) Date of filing: 15.10.1997 (87) International publication number: WO 98/017763 (30.04.1998 Gazette 1998/17) (54) LOW RESIDUE AQUEOUS HARD SURFACE CLEANING AND DESINFECTING COMPOSITIONS WÄSSRIGE REINIGUNGS- UND DESINFEKTIONSMITTEL MIT NIEDRIGEM RÜCKSTAND FÜR HARTE OBERFLÄCHEN COMPOSITIONS AQUEUSES DE NETTOYAGE ET DE DESINFECTION A FAIBLE RESIDU POUR SURFACES DURES (84) Designated Contracting States: (74) Representative: Dickson, Elizabeth Anne BE DE ES FR GB IT NL Reckitt Benckiser plc, Group Patents Department, (30) Priority: 24.10.1996 GB 9622176 Dansom Lane Hull HU8 7DS (GB) (43) Date of publication of application: 18.08.1999 Bulletin 1999/33 (56) References cited: EP-A- 0 129 980 EP-A- 0 621 335 (73) Proprietor: Reckitt Benckiser Inc. EP-A- 0 691 397 WO-A-94/22996 Wayne, New Jersey 07474 (US) WO-A-95/14757 (72) Inventor: HARRISON, Kenneth, A. Goshen, NY 10924 (US) Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 0 935 646 B1 Printed by Jouve, 75001 PARIS (FR) EP 0 935 646 B1 Description [0001] Cleaning compositions are commercially important products and enjoy a wide field of utility in assisting in the removal of dirt and grime from surfaces, especially those characterized as useful with "hard surfaces". Hard surfaces 5 are those which are frequently encountered in lavatories such as lavatory fixtures such as toilets, shower stalls, bath- tubs, bidets, sinks, etc., as well as countertops, walls, floors, etc. [0002] While the art is replete with various formulations which provide some cleaning benefit and perhaps some disinfecting benefit to surfaces, few such formulations are sufficiently formulated so to be effective sanitizing and clean- ing compositions and to appropriately satisfy the registration requirements of the United States Environmental Protec- 10 tion Administration as a "hospital strength" disinfectant. [0003] WO 95/14757 discloses aqueous hard surface cleaners comprising a germicidal quaternary ammonium sur- factant, a detergent surfactant and an organic solvent such as an alkylene glycol ether. [0004] WO 94/22996 discloses multi-surface cleaning compositions comprising an amine oxide surfactant quaternary amine surfactant and a slightly water-soluble polar compound such as an ethylene glycol ether. 15 [0005] The invention provides a aqueous liquid disinfectant cleaner which is particularly useful for cleaning and dis- infecting hard surfaces. The inventive compositions provide improved aqueous ready to use cleaning compositions which exhibit a low tendency to leave surface residues. In preferred embodiments, the inventive compositions do not undesirably degrade when subjected to an elevated temperature over an extended period of time. Preferred embodi- ments of the inventive compositions provide an aqueous cleaning and disinfecting composition which may be catego- 20 rized as a hospital strength disinfecting composition in accordance with current United States Environmental Protection Administration requirements. [0006] The invention further provides a process for the simultaneous cleaning and sanitization of hard surfaces, which process comprises the step of: providing an aqueous cleaning composition as outlined above, and applying an effective amount of the same to a surface, especially a hard surface requiring such cleaning and sanitizing treatment. 25 [0007] According to the present invention there is provided a low residue aqueous cleaning composition which pro- vides disinfecting and cleaning characteristics to treated surfaces, particularly hard surfaces, which comprises: A) a quaternary ammonium surfactant compound having germicidal properties; B) a solvent system which is solely propylene glycol n-butyl ether; 30 C) a surfactant compound selected from amine oxide compounds; D) an alkanolamine; and E) water. The compositions may include one or more further optional additive constituents, sometimes referred to as adjuvants, 35 in minor, but effective amounts. By way of non-limiting example, such optional additives include: coloring agents such as dyes and pigments, fragrances, other pH adjusting agents, pH buffer compositions, chelating agents, rheology modification agents as well as one or more further surfactant compounds, in particular nonionic surfactant compounds. Desirably, in order to reduce the likelihood of undesired buildup upon treated surfaces, especially hard surfaces, the amounts of these additive constituents are present in only minor amounts, i.e., less than 5% wt. based on the total 40 weight of the aqueous cleaning composition being provided herein. The compositions are characterized in providing a disinfecting effect, desirably sufficient to be rated a "broad spectrum disinfectant" yet more desirably sufficient to be rated a "hospital strength disinfectant" under USA guidelines. [0008] A) The compositions according to the invention include one or more quaternary ammonium surfactant com- pounds having germicidal properties. Exemplary useful quaternary ammonium compounds and salts thereof include 45 quaternary ammonium germicides which may be characterized by the general structural formula: 50 55 where at least one of R1,R2,R3and R4 is a alkyl, aryl or alkylaryl substituent of from 6 to 26 carbon atoms, which may include at least one or more amide, ether or ester linkages, and desirably the entire cation portion of the molecule has a molecular weight of at least 165. The alkyl substituents may be, for example, long-chain alkyl, long-chain alkoxyaryl, long-chain alkylaryl, halogen-substituted long-chain alkylaryl, long-chain alkylphenoxyalkyl, arylalkyl. The remaining 2 EP 0 935 646 B1 substituents on the nitrogen atoms other than the abovementioned alkyl substituents are hydrocarbons usually con- taining no more than 12 carbon atoms which may include one or more amide, ether or ester linkages. The substituents R1,R2,R3and R4 may be straight-chained or may be branched, but are preferably straight-chained, and may include one or more amide, ether or ester linkages. The counterion X may be any salt-forming anion which permits water 5 solubility of the quaternary ammonium complex. Exemplary counterions include halides, for example chloride, bromide or iodide, or methosulfate. [0009] Exemplary quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide, and the like. Other suitable types of quaternary 10 ammonium salts include those in which the molecule contains either amide, ether or ester linkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, N-(laurylcocoaminoformylmethyl)-pyridinium chloride, and the like. Other very effective types of quaternary ammonium compounds which are useful as germicides include those in which the hydrophobic radical is characterized by a substituted aromatic nucleus as in the case of lauryloxyphenylt- rimethyl ammonium chloride, cetylaminophenyltrimethyl ammonium methosulfate, dodecylphenyltrimethyl ammonium 15 methosulfate, dodecylbenzyltrimethyl ammonium chloride, chlorinated dodecylbenzyltrimethyl ammonium chloride, and the like. [0010] Preferred quaternary ammonium compounds which act as germicides and which are be found useful in the practice of the present invention include those which have the structural formula: 20 25 wherein R2 and R3 are the same or different C8-C12alkyl, or R2 is C12-16alkyl, C8- 18alkylethoxy, C8-18alkylphenolethoxy and R3 is benzyl, and X is a halide, for example chloride, bromide or iodide, or methosulfate. 30 The alkyl groups recited in R2 and R3 may be straight-chained or branched, but are preferably substantially linear. [0011] Particularly useful quaternary germicides include compositions which include a single quaternary compound, as well as mixtures of two or more different quaternary compounds. Particularly useful quaternary germicides include for example: alkyl dimethyl benzyl ammonium chlorides, dialkyl(C8-C10)dimethyl ammonium chlorides including didecyl dimethyl ammonium chloride and dioctyl dimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chlorides (ben- 35 zalkonium chloride), composition based on blends of alkyldimethylbenzyl ammonium chloride and/or alkyldimethyl- ethylbenzyl ammonium chloride, myristyldimethylbenzyl ammonium chlorides, methyldodecylbenzyl ammonium chlo- rides, methyldodecylxylene-bis-trimethyl ammonium chlorides, benzethonium chlorides, alkyl dimethyl benzyl ammo- nium chlorides, dialkyl methyl benzyl ammonium chlorides, alkyldimethylethyl ammonium bromide and LONZABAC®- 12.100 described as being based on an alkyl tertiary amine. Polymeric quaternary ammonium salts based on these 40 monomeric structures are also considered