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US 2016O2301.23A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2016/0230123 A1 Smith et al. (43) Pub. Date: Aug. 11, 2016 (54) CALCIUM SEQUESTERING COMPOSITION (60) Provisional application No. 61/477,774, filed on Apr. 21, 2011. (71) Applicant: RIVERTOP RENEWABLES, INC., Missoula, MT (US) Publication Classification (72) Inventors: Tyler N. Smith, Missoula, MT (US); (51) Int. C. Richard Shirley, Missoula, MT (US) CID3/20 (2006.01) (52) U.S. C. (21) Appl. No.: 15/133,699 CPC .................................... CI ID3/2086 (2013.01) (57) ABSTRACT (22) Filed: Apr. 20, 2016 This invention relates to compositions which are capable of sequestering calcium ions and are derived in part from renew able carbohydrate feedstocks. The calcium sequestering Related U.S. Application Data compositions are mixtures containing one or more hydroxy (63) Continuation of application No. 13/452,560, filed on carboxylic acid salts, one or more oxoacid anion salts, and Apr. 20, 2012, now Pat. No. 9,347,024. one or more citric acid salts. US 2016/02301.23 A1 Aug. 11, 2016 CALCIUM SEQUESTERING COMPOSITION 0004. Many chemical compounds that have traditionally been used as metal sequestering agents are phosphorus based. CROSS-REFERENCE TO RELATED Through environmental regulations, the use of phosphorus APPLICATION compounds in applications where the material is discharged into Surface water continues to be restricted. These regula 0001. This claims priority to U.S. Provisional Patent tions have created a need for environmentally acceptable Application No. 61/477,774, filed on Apr. 21, 2011, the con materials for use as metal sequestering agents for a variety of tents of which are herein fully incorporated by reference. applications. FIELD OF THE INVENTION 0005 One application in which metal sequestering agents are useful is in detergent formulations. Detergents are clean 0002 This invention relates to compositions which are ing mixtures composed primarily of Surfactants, builders, capable of sequestering calcium ions and are derived in part bleaching-agents, enzymes, and fillers. Two of the major from renewable carbohydrate feedstocks. The calcium components are surfactants and builders. The Surfactants are sequestering compositions include one or more hydroxycar responsible for emulsification of oil and grease while builders boxylic acid salts including hydroxymonocarboxylic acids are added to extend or improve the cleaning properties of the and hydroxydicarboxylic acids, one or more Suitable oxoacid Surfactant. The builder can be a single Substance or a mixture anion salts, and one or more citric acid salts. of Substances and commonly serve multiple functions. An important builder function is the sequestration of metal cat BACKGROUND OF THE INVENTION ions, typically calcium and magnesium cations in hard water. 0003 Hydroxycarboxylic acids and hydroxycarboxylic The builders act as water softening agents by sequestering acid salts have been described as chelating agents capable of calcium and magnesium cations and thus prevent the forma sequestering metal ions in solution (Mehltretter, 1953; tion of water insoluble salts between the cations and anion Abbadi, 1999). Hydroxycarboxylic acid salts as sequestering components in the wash solution, such as Surfactants and agents for metal ions such as calcium and magnesium, in carbonate. In the case of laundry detergents, builders also general perform poorly compared to common sequestering help prevent the cations from binding to cotton, a major cause agents such as sodium tripolyphosphate (STPP), ethylenedi of soil retention on cotton fabrics. Other functions of builders aminetetraacetate (EDTA), or nitrilotriacetate (NTA). In spite include increasing alkalinity of detergent solutions, defloc of low sequestering capacity, hydroxycarboxylic acid salts culating Surfactant micelles, and inhibiting corrosion. are of interest because they are typically biodegradable, non 0006. The first builders used in commercial detergents toxic, and derived from renewable resources such as carbo were phosphate salts and phosphate salt derivatives. Sodium hydrates. Therefore, the use of hydroxycarboxylic acid salts tripolyphosphate (STPP) was, at one time, the most common as replacement sequestering agents for STPP and EDTA is builder in both consumer and industrial detergents. Phosphate advantageous, especially in applications where the com builders were also touted as corrosion inhibitors for the metal pounds may be discharged into the environment. The perfor Surfaces of Washing machines and dishwashers. Phosphates mance of hydroxycarboxylic acid salts as sequestering agents have been gradually phased out of detergents over the past 40 for hard water ions can be boosted by the addition of suitable years primarily due to environmental concerns regarding dis oxoacid anion compounds Such as borate and aluminate. The charge of phosphate rich waste water into Surface waters boost in performance arises from the formation of diester giving rise to eutrophication and ultimately hypoxia (Lowe, complexes between the two adjacent hydroxyl groups of the 1978). High performance replacements for phosphates in hydroxycarboxylic acid salt and the borate or aluminate as detergents are still sought after. described by van Duinetal (Carb. Res. 1987, 162, 65-78 and 0007 Conventional detergents used in the vehicle care, J. Chem. Soc. Dalton Trans. 1987, 8, 2051-2057). The work food and beverage (e.g., the dairy, cheese, Sugar, meat, food, of van Duin et al. shows that diester complex formation and brewery and other beverage industries), warewashing and occurs with compounds containing two vicinal hydroxyl laundry industries include alkaline detergents. Alkaline deter groups, preferably in the threo configuration. The stability of gents, particularly those intended for institutional and com the complexes is pH dependent with improved stability com mercial use, generally contain phosphates, nitrilotriacetic ing at higher pHs. Complexes between salts of hydroxycar acid (NTA) and ethylenediaminetetraacetic acid (EDTA). boxylic acids and either sodium borate or Sodium aluminate Phosphates, NTA and EDTA are components commonly used have been described as calcium sequestering agents for use in in detergents to aid in soil removal and to sequester metalions detergent applications (Hessen, U.S. Pat, No. 4,000.083; Such as calcium, magnesium and iron. Tumerman, U.S. Pat. No. 3,798,168; and Miralles et al., U.S. 0008. In particular, NTA, EDTA or polyphosphates such Pat. No. 8,153,573). Therefore it is well known that com as Sodium tripolyphosphate and their salts are used in deter plexes between salts of polyhydroxycarboxylic acids and gents because of their ability to solubilize preexisting inor Suitable oxoacid anion salts such as sodium aluminate and ganic salts and/or soils. When calcium, magnesium and iron Sodium borate are useful as divalent metal ion sequestering salts precipitate, the crystals may attach to the Surface being agents for use in applications such as detergents. Surprisingly, cleaned and cause undesirable effects. For example, calcium we have found that the calcium sequestering performance of carbonate precipitation on the Surface of ware can negatively the complexes between salts of polyhydroxycarboxylic acids impact the aesthetic appearance of the ware, giving an and Suitable oxoacid anion salts can be improved by the unclean look. In the laundering area, if calcium carbonate addition of certain sequestering agents such as citrate salts. precipitates and attaches onto the Surface of fabric, the crys This is unexpected considering that performance of citrate is tals may leave the fabric feeling hard and rough to the touch. not improved by the addition of sodium aluminate or sodium In the food and beverage industry, the calcium carbonate borate as shown by van Duin et al. (Carb. Res. 1987, 162, residue can affect the acidity levels of foods. The ability of 65-78). NTA, EDTA and polyphosphates to remove metal ions facili US 2016/02301.23 A1 Aug. 11, 2016 tates the detergency of the Solution by preventing hardness tartronate salt, and at least one glycolate salt. In one embodi precipitation, assisting in Soil removal and/or preventing soil ment, the mixture of hydroxycarboxylic acids may include redeposition into the wash solution or wash water. about 30% to about 75% of the at least one glucarate salt, 0009 While effective, phosphates and NTA are subject to about 0% to about 20% of the at least one gluconate salt, about government regulations due to environmental and health con 0% to about 10% of the at least one 5-keto-gluconate salt, cerns. Although EDTA is not currently regulated, it is about 0% to about 10% of the at least one tartrate salt, about believed that government regulations may be implemented 0% to about 10% of the at least one tartronate salt, and about due to environmental persistence. There is therefore a need in 0% to about 10% of the at least one glycolate salt. The mixture the art for an alternative, and preferably environment friendly, comprises about 40% to about 60% of the at least one glucar cleaning composition that can replace the properties of phos ate salt, about 5% to about 15% of the at least one gluconate phorous-containing compounds such as phosphates, phos salt, about 3% to about 9% of the at least one 5-keto-gluconate phonates, phosphites, and acrylic phosphinate polymers, as salt, about 5% to about 10% of the at least one tartrate salt, well as non aminocarboxylates such

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