EP2164944B1 - Stabilized concentrated cleaning solutions and methods of preparing the same - Google Patents

Stabilized concentrated cleaning solutions and methods of preparing the same Download PDF

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Publication number
EP2164944B1
EP2164944B1 EP07796891A EP07796891A EP2164944B1 EP 2164944 B1 EP2164944 B1 EP 2164944B1 EP 07796891 A EP07796891 A EP 07796891A EP 07796891 A EP07796891 A EP 07796891A EP 2164944 B1 EP2164944 B1 EP 2164944B1
Authority
EP
European Patent Office
Prior art keywords
concentrated cleaning
chelating agent
cleaning solution
stabilized
cleaning solutions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP07796891A
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German (de)
English (en)
French (fr)
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EP2164944A1 (en
Inventor
Siegfried Bragulla
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecolab Inc
Original Assignee
Ecolab Inc
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Publication of EP2164944A1 publication Critical patent/EP2164944A1/en
Application granted granted Critical
Publication of EP2164944B1 publication Critical patent/EP2164944B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/06—Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/28—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids

Definitions

  • the invention is directed to stabilized concentrated cleaning solutions, and to a method of preparing them.
  • the production of such residue is caused or at least facilitated by commercially acceptable levels of impurities present in the raw materials used in the manufacture of the concentrated commercial cleaning solutions.
  • these raw materials are available at various costs and associated levels of purity, i.e., a raw material solution with fewer impurities may be obtained for greater cost.
  • the cost for a substantially pure raw material may so erode the profit margin of a product that the product would not be commercially viable to produce.
  • environmental regulations may limit or prohibit the use of manufacturing processes that would produce substantially pure raw materials. In this instance then, even if a manufacturer would be willing to pay more for a raw material with fewer impurities, such a raw material may simply not be commercially available.
  • concentrated cleaning solutions In order to enhance the convenience and customer satisfaction associated with concentrated cleaning solutions, the solutions would desirably be produced so that long-term storage thereof 3a is possible without visible deterioration and/or other change in product quality. Desirably, concentrated cleaning solutions could also be rendered more shelf stable in a manner that is more cost and/or time efficient than previously described. Additionally, such concentrated solutions could desirably be stabilized so that the introduction of impurities via a diluent would not result in the production of commercially unacceptable amounts of visible precipitates.
  • EP 0 519 603 A1 describes a phosphate-free, gel-like automatic dishwasher detergent compositions comprising a low molecular weight polyacrylate, a polymeric thickener, a chlorine bleach compound in an amount to provide 0.2 to 4 % availabel chlorine and water.
  • the composition may further contain builder salts, alkali metal silicate, alkali metal hydroxide, organic detergent, foam depressant, and a long-chain fatty acid.
  • US 4,228,048 describes a foam cleaner for food plants comprising modified polyacrylic acid salt, sodium tripolyphosphate, sodium hydroxide, sodium silicate, sodium hypochlorite, sodium alkane sulfonate, and optionally sodium polyacrylate.
  • GB 1 527 706 describes an improved detergent composition and its use in a dishwashing machine.
  • EP 0 824 145 A1 describes a bleaching composition.
  • the bleaching composition comprises hypochlorite, an alkaline source, and polyacrylate polymers.
  • US 5,972,866 describes a thickened, non-corrosive cleaner which comprises hypochlorite bleach used to reduce staining on the surface, an alkalinity source, a thickening agent, and water.
  • the present invention provides stabilized concentrated cleaning solutions and methods of stabilizing concentrated cleaning solutions according to claims 1 to 19.
  • stabilized concentrated cleaning solutions may be provided that are shelf stable, i.e., that do not form commercially unacceptable levels of precipitates or experience a reduction in efficacy, when stored at or about room temperature for periods of up to at least 10 weeks and even up to 1 year or more.
  • concentrated cleaning solutions produced according to the method of the present invention are stabilized so that the introduction of levels of impurities that may be commonly seen in water supplies do not result in the production of commercially unacceptable amounts of visible precipitates.
  • the method is not overly time consuming and is inexpensive, relative to methods employing multiple and/or more expensive chemicals, and as such, the stabilized solutions can be produced readily.
  • stabilized concentrated cleaning solutions comprise from 5 wt% to about 35 wt% of a source of hydroxide ions, from about 20 wt% to about 70 wt% of a source of hypochlorite ions, and from about 0.002 wt% to about 0.5 wt% chelating agent.
  • the stabilized cleaning solutions may comprise from about 15 wt% to about 30 wt% of a hydroxide ion source, from about 20 wt% to about 70 wt% of a hypochlorite ion source and from about 0.0002 wt% to about 0.50 wt% chelating agent.
  • the chelating agent may be EDTA, MGDA, NTA, IDS, polyacrylate or combinations of these. In certain embodiments, EDTA, MGDA or NTA are preferred.
  • a method of stabilizing a concentrated cleaning solution comprising a source of hypochlorite ions comprises providing such a solution, providing a chelating agent, and adding the chelating agent to the cleaning solution.
  • the chelating agent(s) are desirably added to the cleaning solution in amounts so that the concentration of chelating agent provided in the cleaning solution ranges from about 0.0001 wt% to about 2.00 wt%, more typically from about 0.0002 wt% to about 0.5 wt%, and preferably may be present in amounts as low as from about 0.0005 wt% to about 0.05 wt%.
  • the present invention provides stabilized concentrated cleaning solutions, and methods of preparing these solutions. It was recently discovered that concentrated cleaning solutions comprising at least one hypochlorite ion source can tend to form visible precipitates upon prolonged storage, or upon the addition of a diluent comprising impurities. It is believed that the precipitates, generally found to be iron oxide, nickel oxide, copper oxide and/or cobalt oxide, were resulting from the reaction of heavy metal impurities in the starting raw materials or diluent, as the case may be, with the oxidant in the concentrated cleaning solutions. If enough impurities are present, and react with enough of the oxidant, the efficacy of the concentrated cleaning solutions may be reduced. Even if the efficacy remains acceptable, the presence of visible precipitates may be commercially unacceptable in products intended to be used in cleaning applications.
  • Stabilized concentrated cleaning solutions according to the present invention do not form visible amounts of precipitates after storage at or about room temperature for periods of at least 10 weeks, 3 months, 6 months or even up to one year. This effect is provided via the inclusion of a small amount(s) of one or more chelating agents to the concentrated cleaning solutions. This result is surprising because as described in copending PCT application WO 2007/121785 A1 , these same chelating agents were not effective at reducing or preventing the formation of precipitates in these solutions in greater amounts.
  • the chelating agents are extremely effective at reducing or even eliminating the amount of visible precipitates that may form in the cleaning solutions upon prolonged storage. Further, these results are achieved by and large with the use of only one readily commercially available, relatively safe chelating agent in very small amounts, representing a cost and time savings over other known methods of stabilizing these types of cleaning solutions, as well as providing significant advantages in storage and handling safety.
  • chelating agents are polydentate ligands that reversibly bind to a metal ion typically via two or more hydrogen or ionic bonds.
  • preferred chelating agents for use in the stabilized concentrated cleaning solutions and methods of preparing them include ethylene diamine tetraacetic acid (EDTA), methylglycinediacetic acid (MGDA), nitrilotriacetic acid (NTA), iminodisuccinate (IDS), polyacrylate, or combinations of these.
  • very low concentrations of the chelating agents are very effective at providing the concentrated cleaning solutions with the desired stability, i.e., the reduction or even elimination of visible precipitates upon prolonged storage, or upon the addition of a diluent comprising copper, iron, nickel or cobalt impurities. More particularly, amounts of from about 0.0001 wt% to about 2.00 wt%, more typically from about 0.0002 wt% to about 0.5 wt%, and even in amounts as low as from about 0.0005 wt% to about 0.05 wt% have been found capable of providing the concentrated cleaning solutions with the desired stability.
  • the chelating agent is, e.g., EDTA provided as a 38 wt% solution, amounts ranging from about 0.4 ppm to about 7600 ppm, or from about 0.76 ppm to about 1900 ppm or even from about 1.9 ppm to about 190 ppm, or may be used.
  • Cost/efficiency considerations may dictate that the no more chelating agent than that required to achieve the desired effect should be used, and indeed, at higher concentrations the chelating agent(s) may not be effective at reducing or eliminating the visible precipitates that may occur upon storage for prolonged periods of time. For these reasons, amounts of the chelating agent greater than 2.5 wt% based upon the total weight of the stabilized concentrated cleaning solution, should be avoided.
  • Concentrated cleaning solutions that benefit from application of the present method include those comprising an amount of hypochlorite ions.
  • Sources of hypochlorite ions include, but are not limited to, chlorine, hypochlorite salts, chloramine T, dichloramine T, trichloroisocyanuric acid and any of these, or combinations thereof are suitable for use in the present stabilized concentrated cleaning solutions.
  • the stabilized concentrated cleaning solutions comprise one or more hypochlorite salts as the source of hypochlorite ions, and calcium hypochlorite, potassium hypochlorite and/or sodium hypochlorite are particularly preferred.
  • the source of hypochlorite ions in typical concentrated cleaning solutions ranges from about 5 to about 80 wt%, or from about 20 wt % to about 70 wt%, and more particularly from about 40 wt% to about 60 wt%, and these concentration ranges are suitable for use in the stabilized concentrated cleaning solutions of the present invention.
  • hypochlorite ions that are, in turn, formed via the dissociation of hypochlorite salts or hypochlorous acid in water.
  • Hypochlorous acid in turn, can be formed when chlorine reacts with water in amounts that depend upon the pH of the solution: Cl 2 + H 2 O HOCl + HCl
  • the equilibrium of this reaction, and thus the amount of hypochlorous acid produced, depends on the pH of the solution. In alkaline solution, more hypochlorous acid is produced thereby increasing the bactericidal effect that can be seen.
  • the stabilized concentrated cleaning solutions of the present invention are also desirably alkaline, and include a sufficient amount of a hydroxide ion source to render them so.
  • hydroxide ions are provided in cleaning solutions via the inclusion of one or more caustic, or base, solutions.
  • caustic, or base, solutions Such solutions are well known in the art, and any of these may be used, with preference given to sodium hydroxide and potassium hydroxide for their ready availability and ease of use.
  • the source of hydroxide ions is typically included in conventional concentrated cleaning solutions in amounts of from about 1 wt% to about 40 wt%, preferably from about 5 wt% to about 35 wt%, or more typically from about 15 wt% to about 30 wt% of one or more hydroxide ion sources, and these ranges again provide a cleaning solution that would desirably be stabilized against the formation of visible precipitates and thus could benefit from application of the method of the present invention.
  • particular stabilized concentrated cleaning solutions according to the present invention may comprise from about 15 wt% to about 30 wt% hydroxide ion source, such as sodium hydroxide or potassium hydroxide, from about 40 wt% to about 60 wt% hypochlorite ion source, such as sodium hypochlorite, and from about 0.0005 wt% to about 0.05 wt%chelating agent, such as EDTA.
  • hydroxide ion source such as sodium hydroxide or potassium hydroxide
  • hypochlorite ion source such as sodium hypochlorite
  • EDTA wt%chelating agent
  • stabilized concentrated cleaning solutions may comprise any of the other components typically included in conventional concentrated cleaning solutions.
  • many such solutions include one or more sequestrants, surfactants, corrosion inhibitors, builders, solubilizers, solvents, other additives, or combinations of these.
  • Sequestrants are typically included in cleaning solutions to reduce or prevent water hardness scaling.
  • suitable sequestrants include, polyphosphates, organic phosponates, citrates, lactic acid, combinations of these and the like.
  • One or more surfactants may also be included in the stabilized concentrated cleaning solutions to enhance the cleaning performance thereof.
  • any type of surfactant i.e., anionic, cationic, non-ionic or amphoteric, may be added to the present concentrated cleaning solutions without detrimentally impacting the stability thereof, anionic and/or non-ionic surfactants are particularly appropriate for inclusion therein since the stabilized concentrated cleaning solutions may typically be alkaline.
  • anionic surfactants include, but are not limited to, alkyl arene sulfonates, such as alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkylsulfonates, alpha olefin sulfonates or alkyl sulfates.
  • alkyl arene sulfonates such as alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkylsulfonates, alpha olefin sulfonates or alkyl sulfates.
  • a particularly preferred anionic surfactant that may be included in the present stabilized solutions is sodium lauryl sulfate.
  • Examplary non-ionic surfactants include ethoxylated and/or propoxylated fatty alcohols or fatty amines, alkyl polyglucosides and aminoxides, or combinations thereof.
  • Aminoxides are preferred, and examples of these include coconut alkyl dimethylamine oxide and lauryl dimethylamine oxide.
  • Cationic surfactants may also be included in the present cleaning solutions.
  • Cationic surfactants believed to be capable of providing some cleaning activity when in alkaline solution are exemplified by the quaternary ammonium salts.
  • Preferred quaternary ammonium salts may be saturated or unsaturated and are those derived from trialkanol amines esterified with fatty acids and then quaternized with appropriate alkylation agents.
  • Amounts of surfactant from about 1 wt% to 30 wt%, preferably from about 2 wt% to about 20 wt% and most preferably from about 4 wt% to about 15 wt% based upon the total weight of the stabilized concentrated solution may be employed.
  • Solubilizers typically act to facilitate the dispersion of organic components, including any of the non-critical components such as surfactants, in aqueous solution, and one or more may also optionally be included in the stabilized cleaning solutions.
  • solubilizers include sodium, potassium, ammonium and alkanol ammonium salts of sulfonates of xylene, toluene, ethylbenzoate, isopropylbenzene, naphthalene or alkyl naphthalene, phosphate esters of alkoxylated alkyl phenols, phosphate esters of alkoxylated alcohols and sodium, potassium and ammonium salts of alkyl sarcosinates, and mixtures of these.
  • the one or more solubilizer(s) may be present in amounts of from about 1 to about 35 wt%, or from about 5 to about 25 wt% and more preferably from about 9 to about 20 wt%.
  • the stabilized concentrated cleaning solution may also optionally contain one or more of other components commonly used in cleaning solutions including, but not limited to, builders, solvents, and other additives. Amounts of up to about 20%, or up to about 15 wt%, or even up to about 10% are suitable for each of these.
  • Examplary builders that may be included in the stabilized concentrated cleaning solutions are sodium carbonate, sodium sesquicarbonate, sodium sulfate, sodium hydrogencarbonate, phosphates like pentasodium triphosphate, or its salt, citric acid or its salt, or combinations of these.
  • Table 1 shows the storage stability of several exemplary stabilized concentrated cleaning solutions prepared in accordance with the present invention, as well as several comparative solutions. Each solution was prepared by simply mixing the components in the order and amounts indicated. Further, all amounts indicated are weight percents, based on the total weight of the solution.
  • the solutions were stored at or about room temperature (25Ā°C) and visual evaluations taken at 10 weeks, 3 months, 6 months and 1 year.
  • 0.05% EDTA effectively prevents the formation of visible levels of precipitates in all of the tested solutions.
  • Table 2 shows the storage stability of several exemplary stabilized concentrated cleaning solutions prepared in accordance with the present invention, as well as a comparative solution. Each solution was prepared by simply mixing the components in the order and amounts indicated. Further, all amounts indicated are weight percents, based on the total weight of the solution.
  • the solutions were stored at or about room temperature (25Ā°C) and visual evaluations taken at 10 weeks, 3 months, 6 months and 1 year.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP07796891A 2007-07-17 2007-07-17 Stabilized concentrated cleaning solutions and methods of preparing the same Active EP2164944B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2007/016147 WO2009011676A1 (en) 2007-07-17 2007-07-17 Stabilized concentrated cleaning solutions and methods of preparing the same

Publications (2)

Publication Number Publication Date
EP2164944A1 EP2164944A1 (en) 2010-03-24
EP2164944B1 true EP2164944B1 (en) 2013-03-06

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Country Status (8)

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EP (1) EP2164944B1 (es)
JP (1) JP5443351B2 (es)
CN (1) CN101679921B (es)
AU (1) AU2007356500B2 (es)
BR (1) BRPI0721689A2 (es)
CA (1) CA2686590C (es)
MX (1) MX2009013256A (es)
WO (1) WO2009011676A1 (es)

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Publication number Priority date Publication date Assignee Title
JP5603057B2 (ja) * 2009-12-08 2014-10-08 ć‚Øć‚¹ćƒ†ćƒ¼ę Ŗ式会ē¤¾ ę“—ęæÆę§½ē”Øę“—ęµ„å‰¤ēµ„ęˆē‰©
CN103820800A (zh) * 2014-02-20 2014-05-28 č‹å·žé¾™č…¾äø‡é‡ŒåŒ–å·„ē§‘ęŠ€ęœ‰é™å…¬åø äø€ē§ä½Žęø©č„±č„‚ęø…ę“—å‰‚
WO2016192787A1 (en) * 2015-06-03 2016-12-08 Ecolab Inc. Highly alkaline cleaning chlorinated composition with chlorine stabilisation
JP2017115010A (ja) * 2015-12-24 2017-06-29 ę°“ļ½‰ļ½Žļ½‡ę Ŗ式会ē¤¾ ę“—ęµ„å‰¤ēµ„ęˆē‰©ć€ćć®č£½é€ ę–¹ę³•ć€åŠć³ć“ć‚Œć‚’ē”Øć„ćŸę“—ęµ„ę–¹ę³•
CN105950315B (zh) * 2016-01-28 2018-07-03 ęØę—„å‡ 农äŗ§å“ęø…ę“—å‰‚åŠē”Ø其ęø…ę“—å†œäŗ§å“ēš„ę–¹ę³•

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Also Published As

Publication number Publication date
CA2686590A1 (en) 2009-01-22
EP2164944A1 (en) 2010-03-24
AU2007356500A1 (en) 2009-01-22
BRPI0721689A2 (pt) 2013-03-26
CA2686590C (en) 2014-04-01
CN101679921A (zh) 2010-03-24
JP5443351B2 (ja) 2014-03-19
CN101679921B (zh) 2013-05-01
WO2009011676A1 (en) 2009-01-22
MX2009013256A (es) 2010-01-25
JP2010533765A (ja) 2010-10-28
AU2007356500B2 (en) 2013-01-17

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