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Wo 2008/137798 A2 (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date PCT 13 November 2008 (13.11.2008) WO 2008/137798 A2 (51) International Patent Classification: (74) Agent: SORENSEN, Andrew, D.; Ecolab Inc., 655 Lone CIlD 3/12 (2006.01) CIlD 1/00 (2006.01) Oak Drive, Eagan, MN 55121 (US). (21) International Application Number: (81) Designated States (unless otherwise indicated, for every PCT/US2008/062572 kind of national protection available): AE, AG, AL, AM, AO, AT,AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, CA, (22) International Filing Date: 2 May 2008 (02.05.2008) CH, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, (25) Language: English Filing IL, IN, IS, JP, KE, KG, KM, KN, KP, KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, (26) Publication Language: English MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PG, PH, (30) Priority Data: PL, PT, RO, RS, RU, SC, SD, SE, SG, SK, SL, SM, SV, 60/927,575 4 May 2007 (04.05.2007) US SY, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW (71) Applicant (for all designated States except US): ECOLAB INC. [US/US]; Ecolab Center, St. Paul, MN 55102 (US). (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (72) Inventors; and GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, (75) Inventors/Applicants (for US only): SMITH, Kim, R. ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), [US/US]; 8774 Rainier Alcove, Woodbury, MN 55125 European (AT,BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, (US). OLSON, Keith, E. [US/US]; 13966 Edenwood FR, GB, GR, HR, HU, IE, IS, IT, LT,LU, LV,MC, MT, NL, Court, Apple Valley, MN 55124 (US). MILLS, Kristen, NO, PL, PT, RO, SE, SI, SK, TR), OAPI (BF, BJ, CF, CG, A. [US/US] ; 1119 Landmark Trail S., Hopkins, MN 55343 CI, CM, GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG). (US). MONSRUD, Lee, J. [US/US]; 7475 Cleadis Way, Inver Grove Heights, MN 55076 (US). RISCHMILLER, Published: Michael [US/US]; 3697 Cannon Lake Tr., Faribault, MN — without international search report and to be republished 55021 (US). upon receipt of that report (54) Title: CLEANING COMPOSITIONS WITH WATER INSOLUBLE CONVERSION AGENTS AND METHODS OF MAK ING AND USING THEM (57) Abstract: The present invention relates to cleaning compositions comprising conversion agents and methods of using them. The conversion agents of the present invention comprise water insoluble compounds such as metal oxides, metal hydroxides, and combinations thereof. The compositions can be substantially free of a builder, e.g., a chelating agent, sequestrant, and/or threshold agent, while still achieving effective soil removal. CLEANING COMPOSITIONS WITH WATER INSOLUBLE CONVERSION AGENTS AND METHODS OF MAKING AND USING THEM This application is being filed on 02 May 2008, as a PCT International Patent application in the name of ECOLAB INC., a U.S. national corporation, applicant for the designation of all countries except the U.S., and Kim R. SMITH, a citizen of the U.S., Keith E. OLSON, a citizen of the U.S., Kristen A. MILLS, a citizen of the U.S., Lee J. MONSRUD, a citizen of the U.S., and Michael RISCHMILLER, a citizen of the U.S., applicants for the designation of the U.S. only, and claims priority to U.S. Provisional Patent Application Serial No. 60/927,575 filed on 04 May 2007. FIELD OF THE INVENTION The present invention relates to cleaning compositions comprising conversion agents, and methods of using them. In particular, solid cleaning compositions comprising conversion agents comprising water insoluble compounds are provided. The cleaning compositions can be substantially free of a builder, e.g., chelating agent, sequestrant, and/or threshold agent. Methods employing the cleaning compositions are also provided. BACKGROUND The level of hardness in water can have a deleterious effect in many systems. For example, when hard water alone, or in conjunction with cleaning compositions, contacts a surface, it can cause precipitation of hard water scale on the contacted surface. In general, hard water refers to water having a total level of calcium and magnesium ions in excess of about 100 ppm expressed in units of ppm calcium carbonate. Often, the molar ratio of calcium to magnesium in hard water is about 2:1 or about 3:1. Although most locations have hard water, water hardness tends to vary from one location to another. Hard water is also known to reduce the efficacy of detergents. One method for counteracting this includes adding chelating agents or sequestrants into detersive compositions that are intended to be mixed with hard water in an amount sufficient to handle the hardness. However, in many instances the water hardness exceeds the chelating capacity of the composition. As a result, free calcium ions may be available to attack active components of the composition, to cause precipitation, or to cause other deleterious effects, such as poor cleaning effectiveness or lime scale build up. SUMMARY In some aspects, the present invention provides a solid cleaning composition comprising about 1 to about 50 wt% of a conversion agent comprising a water insoluble compound; and about 10 to about 95 wt% of an alkalinity source. The conversion agent causes calcium hardness ions in a water source to substantially precipitate in a non- calcite crystalline form. In some embodiments, the conversion agent is selected from the group consisting of metal oxides, metal hydroxides, and combinations thereof. In other embodiments, the conversion agent is selected from the group consisting of magnesium oxide, aluminum oxide, titanium oxide, and combinations thereof. In still yet other embodiments, the conversion agent is selected from the group consisting of magnesium hydroxide, aluminum hydroxide, titanium hydroxide and combinations thereof. In some embodiments, the non-calcite crystalline form is aragonite. In other embodiments, the conversion agent further comprises aragonite. In still yet other embodiments, the conversion agent further comprises about 1 to about 50 wt% of aragonite. In some embodiments, the alkalinity source is selected from the group consisting of an alkali metal carbonate, an alkali metal hydroxide, and combinations thereof. In some embodiments, the alkali metal carbonate is selected from the group consisting of sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium sesquicarbonate, potassium sesquicarbonate, lithium sesquicarbonate, and combinations thereof. In still yet other embodiments, the alkali metal hydroxide is selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide, and combinations thereof. In some embodiments, the composition further comprises about 1 to about 7 wt% of a builder. In other embodiments, the composition is substantially free of a builder. In other embodiments, the composition further comprises about 1 to about 50 wt% of a salt. In some embodiments, the salt is selected from the group consisting of monovalent alkali compounds having halide or sulfate as the anion. In some embodiments, the composition further comprises about 1 to about 50 wt% water. In some embodiments, the composition further comprises a surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, or combinations thereof hi other embodiments, the surfactant is a nonionic low foaming surfactant. In some embodiments, the composition comprises: about 5 to about 30 wt% of the conversion agent; and about 20 to about 75% of the alkalinity source, hi other embodiments, the composition comprises about 10 to about 20 wt% of the conversion agent; and about 25 to about 65 wt% of the alkalinity source. In some aspects, the present invention provides a solid cleaning composition comprising: about 3 to about 30 wt% of a conversion agent comprising a water insoluble compound; and about 5 to about 90 wt% of an ingredient selected from the group consisting of a salt, a detergent filler, a surfactant, a processing aid, water and combinations thereof, wherein the conversion agent causes calcium hardness ions in a water source to substantially precipitate in a non-calcite crystalline form. In some embodiments, the composition comprises less than 1 wt% phosphate. In other embodiments, the composition comprises less than 1 wt% phosphorus. In some aspects, the present invention provides a method of cleaning an article. The method comprises: (a) providing a solid cleaning composition comprising: (i) about 1 to about 50 wt% of a conversion agent comprising a water insoluble compound; and (ii) about 10 to about 95 wt% of an alkalinity source, wherein the conversion agent causes calcium hardness ions in a water source to substantially precipitate in a non- calcite crystalline form; (b) dissolving at least a portion of the solid cleaning composition to create a use solution; and (c) contacting the article with the use solution, such that the article is cleaned. In some embodiments, the article is selected from the group consisting of a medical device, a laundry article, an article of ware, a hard surface, and combinations thereof. In other embodiments, the method is used in a presoak application hi still yet other embodiments, the method is used in a rinse application. hi some aspects,
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