Transparent Abrasive Cleaning Product Especially Manual Dishwashing Liquid

US007393820B2 (12) Ulllted States Patent (10) Patent No.: US 7,393,820 B2 Soldanski et al. (45) Date of Patent: Jul. 1, 2008 (54) TRANSPARENT ABRASIVE CLEANING 5,985,817 A 11/1999 Weibel et al. PRODUCT, ESPECIALLY MANUAL 6,159,925 A * 12/2000 Blandiaux ................. .. 510/437 DISHWASHING LIQUID (75) Inventors: Heinz-Dieter Soldanski, Essen (DE); FOREIGN PATENT DOCUMENTS Giesen, Duesseldorf DE 3439872 A1 7/1985 (73) Assignee: Heiikel Kommanditgesellschaft auf DE 19918267 A1 10/2000 Ak“°“= D“SSe1d°1'f(DE) EP 0522506 A2 1/1993 ( * ) Notice: Subject to any disclaimer, the term of this EP 0292910 B1 12/1994 patent is extended or adjusted under 35 W0 W0 97/00609 A1 1/1997 U S C 15403) by 0 days W0 W0 97/43392 A1 11/1997 ' ' ' ' W0 WO 00/36078 A1 6/2000 (21) Applp NO‘: 11/636,168 W0 W0 01/19946 A1 3/2001 W0 W0 01/77278 A1 10/2001 (22) Filed: Dec_ 8’ 2006 W0 WO 02/38720 A1 5/2002 (65) Prior Publication Data OTHER PUBLICATIONS US 2007/0167345 A1 Jul. 19, 2007 H.W. Stache (ed), “Anionic Surfactants: organic chemistry”, Related U_S_ Application Data ISIurfa;tai11(t Ser1:s),1v()5lA.‘36(,1I9S9l21)\I 0-8247-E1394-3, Marcel Dekker, Inc. eW or , pp. - , no mon given. (63) COI1tiI111ati0I1 Of application N0. 11/105,749, filed 011 Wallhauser, “Praxis der Sterilisation, Desinfektion-Konservierung: Apr. 14, 2005, now abandoned. Keimidentifizierung-Betriebshygiene”, 5d‘ Edition, Stuttgart: New York: Thieme (1995), no month given ; not translated. (51) Int. Cl. * .t db . CIID 1/88 (2006.01) C13 Y exammer CHD 3/14 (200601) Primary Examiner—Brian P Mruk CHD 9/20 (200901) (74) Attorney, Agent, or Firm—John E. Drach (52) U.S. Cl. ...................... .. 510/483; 510/236; 510/238; 510/239; 510/240; 510/397; 510/421; 510/426; (57) ABSTRACT 510/432; 510/474; 510/492; 510/505 (58) Field of Classification Search ............... .. 510/236, A Substantially transparent, liquid Cleaning product for hard 510/238, 239, 240, 397, 421, 426, 432, 474, f . . 1 15W b . h f f 510/483 492 505 sur aces, comprising at east .0 y Weig to a sur actant S 1. t. fil f 1 t h h. t’ ’ and one or more abrasive materials selected from the group ee app lca Ion e or Comp e e Seam 15 Dry’ consisting of polymers having a diameter of from 0.6 to 4 (55) References Cited mm, natural materials having a diameter of from 0.05 to 4 U.S. PATENT DOCUMENTS 5,958,856 A * 9/1999 Yianakopoulos et al. 510/236 mm, and mixtures thereof. 23 Claims, No Drawings US 7,393,820 B2 1 TRANSPARENT ABRASIVE CLEANING PRODUCT, ESPECIALLY MANUAL DISHWASHING LIQUID CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. patent applica- tion Ser. No. 11/105,749, filedApr. 14, 2005 now abandoned. This application claims priority under 35 U.S.C. § 365(c) and 35 U.S.C. § 120 of Intemational Application PCT/EP2003/ 011052, filed on Oct. 7, 2003. This application also claims priority under 35 U.S.C. § 119 ofDE 102 48 313.2, filed Oct. 16, 2002, which is incorporated herein by reference in its entirety. BACKGROUND OF THE INVENTION. The invention relates to liquid abrasive-containing clean- ing products for hard surfaces which are substantially trans- parent and contain more than 15% by weight of surfactant. Conventional abrasive-containing liquid cleaning products for hard surfaces are typically milky, opaque, thick solutions. They are also well known to the German consumer as “scour- ing milk,” a name which likewise reflects the whitish, opaque appearance of these products. In contrast, manual dishwashing liquids typically have a transparent appearance. The clear products in conjunction with the usually used luminous dyes apparently have a par- ticularly positive effect on the consumer, since they are asso- ciated with a particularly high cleaning performance. It is also desired that manual dishwashing liquids, in particular, form a sufficient foam, since the consumer also associates this with a good cleaning performance. Finally, a certain surfactant con- tent is also required to ensure a good cleaning performance. The intemational patent application WO 02/ 38720 describes clear surfactant-containing cleaning gels compris- ing macroscopic abrasive particles. Such particles may be inorganic sub stances, or else polymer granules or hard waxes. The surfactant content is between 0.1 and 15%. The gels are used to clean hard surfaces. Products having surfactant con- tents above 15% by weight are not disclosed. The patent EP 292 910 describes a stable liquid aqueous scouring cleaning product for hard surfaces. In this product, the abrasive particles are intended not to scratch the surface to be cleaned. Various plastics are proposed as abrasives, and the particles can have a size of from 10 to 150 pm. The cleaners described, which are referred to many times as “creamy”, are clearly “scouring milk”; in contrast, transparent products are not envisaged. In addition, the products are alkaline with a pH between 10 and 12. WO 00/36078 provides transparent or translucent liquid products for textiles in which encapsulated active, ingredients are suspended with the aid of polymeric thickeners. These active ingredients are enzymes, bleaches, perfumes, etc. which are to be incorporated stably in the liquid product. In contrast, abrasives are not envisaged as ingredients. The German application DE-A 19918267 finally describes manual dishwashing liquids in which microcapsules com- prising various active ingredients are suspended. An abrasive action of these suspended particles is not envisaged here either, but rather the shell of the microcapsules opens on use and releases the active ingredient present. Manual dishwashing liquids and other cleaning products for hard surfaces which exhibit good cleaning performance and comprise an abrasive to remove strongly adhering soils without scratching the surface to be cleaned in the course of 10 15 20 25 30 35 40 45 50 55 60 65 2 use, but at the same time having an appearance attractive to the consumer, have not been described to date. It is therefore an object of the present invention to provide a cleaning product for hard surfaces which comprises an abrasive, has good cleaning performance and is additionally visually attractive. DESCRIPTION OF THE INVENTION The invention therefore provides an abrasive-containing liquid cleaning product for hard surfaces which is substan- tially transparent and has a surfactant content of more than 15% by weight. In the context of this invention, a “substantially transpar- ent” product has a transmittance of light of any wavelengths in the visible range, i.e. between 400 and 800 nm, of at least 50%, measured in a cuvette with a layer thickness of 1 cm in the absence of dyes and abrasive particles. The light trans- mission is preferably above 70%, more preferably above 80%, in particular above 90%. The visual impression is pref- erably that of individual opaque particles suspended stably in a clear cleaning product. Just like the cleaning products sur- rounding them, these particles may assume any colors, and cleaning product and abrasive may be dyed in the same or different colors. The surfactant content of more than 15% by weight refers to the total amount of anionic, nonionic and amphoteric sur- factants, based on the cleaning product. The present invention likewise provides for the use of the inventive product as a manual dishwashing liquid. In this case, the product fulfills a dual function, since it can firstly, in particular in concentrated form, serve to preliminar- ily clean highly soiled tableware, soiled in some cases with bumt-on greasy soil or other impurities, the abrasives present contributing to more rapid release of the soiling substances. Secondly, it is also suitable in a customary manner for clean- ing normally soiled tableware by introduction into a dilute aqueous cleaning liquor. The surfactant content of more than 15% by weight provides the product with good cleaning performance. In addition to tableware, the products are capable of equally efiiciently cleaning other hard surfaces, for example of glass, ceramic, plastic, enamel or metal, in the household and industry. For example, kitchen and in particular cooker surfaces, ovens and other hard surfaces with sometimes per- sistent and/or grease-containing soilings can be cleaned with inventive products, as can bathroom surfaces, plastic furni- ture in the house and garden or windows and other glass surfaces, to name just a few possibilities. Accordingly, the present invention further provides for the use of the inventive product as a manual cleaning product for hard surfaces. In the context of the present invention, fatty acids, fatty alcohols and derivatives thereof represent, unless stated oth- erwise, respectively, branched or unbranched carboxylic acids, alcohols and derivatives thereof having preferably from 6 to 22 carbon atoms. Owing to their vegetable basis, the former are preferably based on renewable raw materials for ecological reasons, but without restricting the inventive teaching to them. In particular, the oxo alcohols or derivatives thereof obtainable by the ROELEN oxo process, for example, can also be used correspondingly. Whenever alkaline earth metals are specified as counteri- ons for monovalent anions hereinbelow, this means that the alkaline earth metal is of course present only in half the amount, which is sufficient to balance the charge, of the amon. US 7,393,820 B2 3 INCI means that the following or preceding designation is a name according to the International Dictionary of Cosmetic Ingredients 0fThe Cosmetic, Toiletry, and Fragrance Asso- ciation (CT FA). CAS means that the number which follows is a designation of the Chemical Abstracts Service. Abrasives In the context of this invention, the abrasives used may be substances which can be suspended as solids in the cleaning product and have a cleaning-promoting action in the inventive use of the product. This use lies in the scouring action of the particles, by means of which relatively strongly adhering soilings can also be detached and transferred into the cleaning liquor. However, it is necessary at the same time that the surface to be cleaned is not scratched, roughened or attacked in another way by the action of the abrasive. It is preferred that the particles do not have any sharp edges or tips. In particular, it is preferred when spherical or ellipsoidal, in some cases also drop-shaped, particles are used. The three-dimensional shape of these particles contributes not only to the surface- gentle property but also to the positive visual appearance of the inventive product. In order to ensure an abrasive action over a prolonged period, it is also preferred that the abrasive particles are water- insoluble. When a mixture of different abrasives is used, preference is given to at least a portion thereof being water- insoluble, but a further portion may also be water-soluble. The inventive products preferably comprise abrasives selected from the group consisting of polymers, hard waxes, natural materials, ceramic particles, inorganic substances and mixtures thereof. In a preferred embodiment, the abrasives used are polymer particles. In this context, the polymer is preferably selected from the group consisting of polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyester, polycar- bonate, polyvinyl chloride, polyvinyl acetate, polymethyl methacrylate and copolymers and mixtures thereof; particu- lar preference is given to using polystyrene spheres which may or may not contain pentane, as obtainable commercially, for example, as “expandable polystyrene (EPS)” under vari- ous brand names from Nova Chemicals; likewise obtainable from Nova Chemicals are pentane-free polystyrene particles having a rubber core, obtainable, for example, under the name “Polystyrene 843M”, which are likewise used with prefer- ence in inventive products. A further preferred embodiment comprises abrasives which are obtained from natural materials. In the context of the invention, these include, for example, comminuted shells of hazelnuts, almonds, brazil nuts, walnuts, coconuts and further nuts, and also shells of the stones of various types of fruit, for example apricots, peaches, plums, etc., but also optionally comminuted kernels of grapes and various soft fruits such as strawberries, raspberries, blackberries, etc. Under some circumstances, comminuted roots or pieces of bark may also serve as abrasives. In the course of production of such abrasives obtained from natural materials, it is of particular importance that the formation of sharp-edged par- ticles which under some circumstances attack the surface is prevented. In addition to the abrasives mentioned, it is also possible to use hard waxes, ceramic particles, glass beads and inorganic substances as scouring particles in the context of the inven- tion. The usable inorganic compounds include, for example, alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates, alkali metal borates, alkali metal phosphates, silicon dioxide, crystalline or amorphous alkali metal sili- 10 15 20 25 30 35 40 45 50 55 60 65 4 cates and sheet silicates, finely crystalline sodium aluminum silicates, aluminum oxides and calcium carbonate. In the context of the present invention, the abrasives used may be particles having a diameter of from 0.05 to 4 mm. They preferably have a diameter of from 0.3 to l .5 mm. When the shape of the particles deviates from the spherical form, the particle diameter is averaged over the three spatial directions. The content in the product of abrasives is preferably from 0.05 to 10% by weight, more preferably from 0.3 to 2% by weight. Thickeners In the context of the present invention, thickeners are poly- carboxylates, preferably homo- and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and polysaccharides, in particular heteropolysaccharides, and other customary poly- meric thickeners. In addition, it is also possible in the context of this invention to use sheet silicates and further inorganic substances known as thickeners to those skilled in the art; mixtures of different thickeners may also be used. It merely has to be ensured that, when the thickener is used, the sub- stantially transparent visual appearance is retained. However, preference is given to polymers, in particular polycarboxy- lates and/or polysaccharides, as thickeners in inventive clean- ing products. Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum Arabic, agar, algi- nates, carrageenans and salts thereof, guar, guaran, traga- canth, gellan, ramsan, dextran or xanthan and derivatives thereof, for example propoxylated guar, and mixtures thereof. Other polysaccharide thickeners such as starches or cellulose derivatives may be used alternatively, but preferably addition- ally, to a polysaccharide gum, for example starches from a wide variety of origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl-, ethyl-, hydroxyethyl-, hydroxypropyl-, hydroxypro- pylmethyl- or hydroxyethylmethylcellulose or cellulose acetate. A preferred polymer is the microbial anionic het- eropolysaccharide xanthan gum which is produced with a molecular weight of 2-l5>