WO2013142457A1 - Composition de nettoyage comprenant un terpolymère contenant des monomères acide maléique, acétate de vinyle et acrylate d'alkyle pour un effet antitartre accru - Google Patents

Composition de nettoyage comprenant un terpolymère contenant des monomères acide maléique, acétate de vinyle et acrylate d'alkyle pour un effet antitartre accru Download PDF

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Publication number
WO2013142457A1
WO2013142457A1 PCT/US2013/032895 US2013032895W WO2013142457A1 WO 2013142457 A1 WO2013142457 A1 WO 2013142457A1 US 2013032895 W US2013032895 W US 2013032895W WO 2013142457 A1 WO2013142457 A1 WO 2013142457A1
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WIPO (PCT)
Prior art keywords
approximately
weight
cleaning composition
acid
terpolymer
Prior art date
Application number
PCT/US2013/032895
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English (en)
Inventor
Erik C. Olson
Carter Silvernail
Stephen Christensen
Lauren M. HUNKER
Brandon G. BEYER
Kerrie E. WALTERS
Original Assignee
Ecolab Usa Inc.
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Publication date
Priority claimed from US13/428,643 external-priority patent/US20130252870A1/en
Priority claimed from US13/428,632 external-priority patent/US8740993B2/en
Priority claimed from US13/428,637 external-priority patent/US20130252871A1/en
Priority claimed from US13/428,622 external-priority patent/US8623151B2/en
Application filed by Ecolab Usa Inc. filed Critical Ecolab Usa Inc.
Publication of WO2013142457A1 publication Critical patent/WO2013142457A1/fr

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions

Definitions

  • the present invention is related to a cleaning composition including at least one alkalinity source and a polymer including maleic acid, vinyl acetate and alkyl acrylate segments or monomers for enhanced scale control.
  • Alkaline cleanings particularly those intended for institutional and commercial use, in combination with the presence of hard water commonly results in heavy scale formation that is difficult to control, particularly in warewash applications at elevated temperatures.
  • Alkaline cleanings often contain polymers, phosphonates, phosphates, chelating agents such as nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA) to help control scale, remove soils, and/or sequester metal ions such as calcium, magnesium and iron.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • Chelating agents and/or threshold agents are often used in high alkaline cleanings because of their ability to solubilize metal salts and/or prevent calcium, magnesium and iron salts from precipitating.
  • the crystals may attach to the surface being cleaned and cause undesirable effects. For example, calcium carbonate precipitation on the surface of ware can negatively impact the aesthetic appearance of the ware, giving an unclean look.
  • the present invention includes a cleaning composition for removing soils and/or preventing hard water scale accumulation.
  • the cleaning composition includes at least an alkalinity source, and a polymer comprising maleic acid, vinyl acetate and alkyl acrylate monomers for enhanced scale control.
  • the present invention is a cleaning composition including an alkalinity source in an amount between approximately 10% and approximately 90% by weight and a polymer containing maleic acid, vinyl acetate and alkyl acrylate monomers in an amount greater than or equal to approximately 0.1% by weight.
  • the diluted use solution has a pH between about 7 and about 14.
  • the cleaning composition is used in a method to prevent scale formation, accumulation and/or adhesion during a wash cycle.
  • the polymer containing maleic acid, vinyl acetate and alkyl acrylate monomers are mixed with an alkalinity source and a surfactant system to form a cleaning composition.
  • the cleaning composition is then diluted at a dilution ratio of between about 1: 10 and about 1: 10,000 to form a use solution.
  • the use solution is then contacted with a substrate to be cleaned.
  • the temperature of the wash cycle is between about 70 degrees and 185 degrees Fahrenheit.
  • the present invention provides a cleaning composition with an alkalinity source and a polymer including maleic acid, vinyl acetate and alkyl acrylate monomers.
  • Such composition may be particularly useful in reducing and/or inhibiting scale formation, precipitation and/or substrate adhesion of hard water scale and may be used in a solid block form. Further, such compositions can be biodegradable and substantially free of phosphorus containing components to comply with various regulatory requirements.
  • the cleaning composition can be applied in any environment where it is desirable to remove soils, solubilize metal salts and/or prevent the precipitation of magnesium, calcium and/or iron salts.
  • the cleaning composition can be used in vehicle care applications, warewashing applications, laundering applications and food and beverage applications.
  • Such applications include, but are not limited to: machine and manual warewashing, presoaks, laundry and textile cleaning and destaining, healthcare, carpet cleaning and destaining, vehicle cleaning and care applications, surface cleaning and destaining, kitchen and bath cleaning and destaining, floor cleaning and destaining, cleaning in place operations, general purpose cleaning and destaining, and industrial or household cleaners.
  • the cleaning composition can be a detergent or can be builder which can be combined with at least one surfactant to from a detergent.
  • Methods of using the cleaning composition including the polymer containing maleic acid, vinyl acetate and alkyl acrylate monomers are also provided.
  • the cleaning composition generally includes an alkalinity source and a polymer including maleic acid, vinyl acetate and alkyl acrylate monomers or segments.
  • the cleaning composition can include an effective amount of alkalinity to enhance cleaning of the desired substrate and improve soil removal performance and prevent hard water scale accumulation on surfaces.
  • An effective amount of the alkalinity source may provide a use composition (i.e., an aqueous solution containing the composition) having a pH of between about 7 and about 13.
  • a suitable concentration range of the components in the cleaning composition include between approximately 10% and approximately 90% by weight of the alkalinity source, and greater than or equal to approximately 0.1% by weight of the polymer containing maleic acid, vinyl acetate and alkyl acrylate monomers.
  • a particularly suitable concentration range of the components in the cleaning composition include between approximately 10% and approximately 90% by weight of the alkalinity source, and between approximately 0.1% and approximately 20% by weight of the polymer containing maleic acid, vinyl acetate and alkyl acrylate monomers.
  • a more particularly suitable concentration range of the components in the cleaning composition include between approximately 20% and approximately 70% by weight of the alkalinity source, and between approximately 1% and 15% by weight of the polymer containing maleic acid, vinyl acetate and alkyl acrylate monomers.
  • An alkalinity source can be present in an effective amount to enhance cleaning of the desired substrate and can provide a use composition having a pH of at least about 7.
  • a suitable concentration range for the components of this cleaning composition include between approximately 10% and approximately 90% by weight of the alkalinity source and between approximately 0.1% and 20% by weight of the polymer containing maleic acid, vinyl acetate and alkyl acrylate monomers.
  • a particularly suitable concentration range of the components in the cleaning composition include between approximately 20% and approximately 70% by weight of the alkalinity source and between approximately 1% and 15% by weight of the polymer containing maleic acid, vinyl acetate and alkyl acrylate monomers.
  • suitable alkalinity sources of the cleaning composition include, but are not limited to alkali metal carbonates, alkali metal hydroxides and alkali metal silicates.
  • Exemplary alkali metal carbonates that can be used include, but are not limited to: sodium or potassium carbonate, bicarbonate, sesquicarbonate, and mixtures thereof.
  • Exemplary alkali metal hydroxides that can be used include, but are not limited to: sodium or potassium hydroxide.
  • the alkali metal hydroxide may be added to the composition in any form known in the art, including as solid beads, dissolved in an aqueous solution, or a combination thereof.
  • Examples of alkali metal silicates include, but are not limited to sodium or potassium silicate or polysilicate, sodium or potassium metasilicate and hydrated sodium or potassium metasilicate or a combination thereof.
  • the alkalinity source controls the pH of the resulting solution when water is added to the cleaning composition to form a use solution.
  • the pH of the use solution must be maintained in the alkaline range in order to provide sufficient detergency properties. In one embodiment, the pH of the use solution is between approximately 7 and approximately 13. If the pH of the use solution is too low, for example, below approximately 7, the use solution may not provide adequate detergency properties. If the pH of the use solution is too high, for example, above approximately 13, the use solution may be too alkaline and attack or damage the surface to be cleaned.
  • the alkalinity source may also function as a hydratable salt to form a solid cast.
  • the hydratable salt can be referred to as substantially anhydrous.
  • substantially anhydrous it is meant that the component contains less than about 2% by weight water based upon the weight of the hydratable component.
  • the amount of water can be less than about 1% by weight, and can be less than about 0.5 % by weight. There is no requirement that the hydratable component be completely anhydrous.
  • the cleaning composition also includes water of hydration to hydrate the alkalinity source/hydratable salt.
  • water includes water of hydration and free water.
  • the phrase "water of hydration" refers to water which is somehow attractively bound to a non- water molecule.
  • An exemplary form of attraction includes hydrogen bonding.
  • the water of hydration also functions to increase the viscosity of the mixture during processing and cooling to prevent separation of the components. The amount of water of hydration in the cleaning composition will depend on the alkalinity source/hydratable salt.
  • the cleaning composition further includes a polymer containing maleic acid, alkyl acrylate and vinyl acetate monomers.
  • the maleic acid, alkyl acrylate and vinyl acetate polymer may include one or more alkyl acrylate monomers.
  • Suitable alkyl acrylate monomers include, but are not limited to methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isopropyl acrylate and tert-butyl acrylate.
  • the polymer is a terpolymer containing maleic acid, alkyl acrylate and vinyl acetate monomers.
  • a suitable maleic acid, alkyl acrylate and vinyl acetate terpolymer has a molecular weight between about 500 g/mol and about 5,000 g/mol.
  • a more suitable maleic acid, alkyl acrylate and vinyl acetate terpolymer has a molecular weight between about 500 g/mol and about 3,000 g/mol.
  • the polymer may comprise between about 40% and about 99% by weight maleic acid, between about 1% and about 50% by weight vinyl acetate and between about 1% and about 50% by weight alkyl acrylate.
  • the terpolymer may comprise between about 40% and about 99% by weight maleic acid, between about 1% and about 50% by weight vinyl acetate and between about 1% and about 50% by weight ethyl acrylate.
  • the maleic acid, alkyl acrylate and vinyl acetate polymer can be biodegradable.
  • a suitable maleic acid, alkyl acrylate and vinyl acetate terpolymer can be at least about 15% biodegradable.
  • a particularly suitable maleic acid, alkyl acrylate and vinyl acetate terpolymer can be between about 15% and 60% biodegradable after 35 days using the test protocol of OECD 302B.
  • Example commercially available maleic acid, alkyl acrylate and vinyl acetate terpolymers include Belclene® 283 and Belclene® 810 both available from BWA, Tucker, GA.
  • the alkyl acrylate and vinyl acetate monomers may hydrolyze in the concentrate or in the use composition.
  • the alkyl acrylate and/or vinyl acetate segments can hydrolyze to carboxylic acids.
  • reference to an alkyl acrylate and/or vinyl acetate monomer includes all hydrolyzed forms of such monomer.
  • the vinyl acetate or alkyl acrylate may be partially or completely hydrolyzed in the concentrate and/or use composition.
  • the polymer may include at least one hydrolyzed vinyl acetate or alkyl acrylate monomer.
  • maleic acid monomers include monomers of maleic acid and salts thereof.
  • the cleaning composition can be phosphorus-free and/or nitrilotriacetic acid (NTA)- free to make the cleaning composition more environmentally beneficial.
  • NTA nitrilotriacetic acid
  • Phosphorus-free means a composition having less than approximately 0.5%, more particularly less than approximately 0.1 wt%, and even more particularly less than approximately 0.01 wt% phosphorus based on the total weight of the composition.
  • NTA-free means a composition having less than approximately 0.5 wt%, less than approximately 0.1 wt%, and particularly less than approximately 0.01 wt% NTA based on the total weight of the composition. When the composition is NTA-free, it is also compatible with chlorine, which functions as an anti-redeposition and stain- removal agent.
  • the cleaning composition can also include various additional functional
  • the alkalinity source, a surfactant, and the maleic acid, alkyl acrylate and vinyl acetate polymer make up a large amount, or even substantially all of the total weight of the cleaning composition, for example, in embodiments having few or no additional functional materials disposed therein.
  • the cleaning composition consists essentially of a surfactant, an alkalinity source that includes an alkali metal carbonate and a maleic acid, vinyl acetate and alkyl acrylate terpolymer.
  • the cleaning composition consists essentially of a surfactant, an alkalinity source that includes an alkali metal carbonate and a maleic acid, vinyl acetate and ethyl acrylate terpolymer.
  • the component concentration ranges provided above for the composition are representative of the ranges of those same components in the cleaning composition.
  • functional materials are added to provide desired properties and functionalities to the cleaning composition.
  • the term "functional materials” includes a material that when dispersed or dissolved in a use and/or concentrate solution, such as an aqueous solution, provides a beneficial property in a particular use.
  • the cleaning composition includes one or more secondary polymer(s) in addition to the alkalinity source and the terpolymer containing maleic acid, alkyl acrylate and vinyl acetate monomers.
  • Polymers comprise of the terpolymer containing maleic acid, alkyl acrylate and vinyl acetate monomers and the secondary polymer, can be present in an effective amount to enhance scale control of the desired substrate.
  • a suitable concentration range for the components of this cleaning composition include between approximately 0.1% and 20% by weight of the polymer containing maleic acid, vinyl acetate and alkyl acrylate monomers, between approximately 0.1% and 20% by weight of a secondary polymer, and between approximately 10% and 90% by weight of the alkalinity source.
  • a particularly suitable concentration range of the components in the cleaning composition include between approximately 0.1% and 15% by weight of the polymer containing maleic acid, vinyl acetate and alkyl acrylate monomers, between approximately 0.1% and 15% by weight of a secondary polymer, and between approximately 20% and 70% by weight of the alkalinity source.
  • suitable secondary polymer sources of the cleaning composition include, but are not limited to polycarboxylic acid, polyacrylic acid, polymethacrylic acid, polymaleic acid homopolymers, copolymer of acrylic acid, copolymer of methacrylic acid, copolymer of maleic acid, acrylic acid, methacrylic acid, maleic acid terpolymers, or combinations thereof.
  • surfactants include, but are not limited to polycarboxylic acid, polyacrylic acid, polymethacrylic acid, polymaleic acid homopolymers, copolymer of acrylic acid, copolymer of methacrylic acid, copolymer of maleic acid, acrylic acid, methacrylic acid, maleic acid terpolymers, or combinations thereof.
  • the cleaning composition may also include a surfactant.
  • a surfactant can be used in the cleaning composition, including, but not limited to: anionic, nonionic, cationic, and zwitterionic surfactants. Exemplary surfactants that can be used are commercially available from a number of sources. For a discussion of surfactants, see Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, volume 8, pages 900-912.
  • the cleaning composition includes a surfactant as a cleaning agent, the cleaning agent is provided in an amount effective to provide a desired level of cleaning.
  • the cleaning composition when provided as a concentrate, can include the surfactant cleaning agent in a range of about 0.05% to about 20% by weight, about 0.5% to about 15% by weight, about 1% to about 15% by weight, about 1.5% to about 10% by weight, and about 2% to about 8% by weight.
  • Additional exemplary ranges of surfactant in a concentrate include about 0.5% to about 8% by weight, and about 1% to about 5% by weight.
  • anionic surfactants useful in the cleaning composition include, but are not limited to: carboxylates such as alkylcarboxylates and polyalkoxycarboxylates, alcohol ethoxylate carboxylates, nonylphenol ethoxylate carboxylates; sulfonates such as alkylsulfonates, alkylbenzenesulfonates, alkylarylsulfonates, sulfonated fatty acid esters; sulfates such as sulfated alcohols, sulfated alcohol ethoxylates, sulfated alkylphenols, alkylsulfates, sulfosuccinates, and alkylether sulfates.
  • Exemplary anionic surfactants include, but are not limited to: sodium alkylarylsulfonate, alpha-olefinsulfonate, and fatty alcohol sulfates.
  • nonionic surfactants useful in the cleaning composition include, but are not limited to, those having a polyalkylene oxide polymer as a portion of the surfactant molecule.
  • nonionic surfactants include, but are not limited to:
  • alkyl-capped polyethylene glycol ethers of fatty alcohols polyalkylene oxide free nonionics such as alkyl polyglycosides; sorbitan and sucrose esters and their ethoxylates; alkoxylated amines such as alkoxylated ethylene diamine; alcohol alkoxylates such as alcohol ethoxylate propoxylates, alcohol propoxylates, alcohol propoxylate ethoxylate propoxylates, alcohol ethoxylate butoxylates; nonylphenol ethoxylate, polyoxyethylene glycol ether; carboxylic acid esters such as glycerol esters, polyoxyethylene esters, ethoxylated and glycol esters of fatty acids; carboxylic amides such as diethanolamine condensates, monoalkanolamine condensates, polyoxyethylene fatty acid amides; and polyureamides such as diethanolamine condensates, monoalkanolamine condensates, polyoxyethylene fatty acid amide
  • An example of a commercially available ethylene oxide/propylene oxide block polymer includes, but is not limited to, PLURONIC ® , available from BASF Corporation, Florham Park, NJ.
  • An example of a commercially available silicone surfactant includes, but is not limited to, ABIL ® B8852, available from Goldschmidt Chemical Corporation, Hopewell, VA.
  • a particularly suitable surfactant is D500, an ethylene oxide/propylene oxide polymer available from BASF Corporation, Florham Park, NJ.
  • n-tetradecyldimethylbenzylammonium chloride monohydrate and a naphthylene- substituted quaternary ammonium chloride such as dimethyl- 1- naphthylmethylammonium chloride.
  • the cationic surfactant can be used to provide sanitizing properties.
  • the surfactants selected can be those that provide an acceptable level of foaming when used inside a dishwashing or warewashing machine.
  • Cleaning compositions for use in automatic dishwashing or warewashing machines are generally considered to be low-foaming compositions.
  • Low foaming surfactants that provide the desired level of detersive activity are advantageous in an environment such as a dishwashing machine where the presence of large amounts of foaming can be problematic.
  • defoaming agents can also be utilized to reduce the generation of foam. Accordingly, surfactants that are considered low foaming surfactants can be used.
  • other surfactants can be used in conjunction with a defoaming agent to control the level of foaming.
  • the cleaning composition can include one or more building agents, also called chelating or sequestering agents (e.g., builders), including, but not limited to:
  • a chelating agent is a molecule capable of coordinating (i.e., binding) the metal ions commonly found in natural water to prevent the metal ions from interfering with the action of the other detersive ingredients of a cleaning composition.
  • Preferable levels of addition for builders that can also be chelating or sequestering agents are between about 0.1% to about 70% by weight, about 1% to about 60% by weight, or about 1.5% to about 50% by weight.
  • the concentrate can include between approximately 1% to approximately 60% by weight, between approximately 3% to approximately 50% by weight, and between approximately 6% to approximately 45% by weight of the builders. Additional ranges of the builders include between approximately 3% to approximately 20% by weight, between approximately 6% to approximately 15% by weight, between approximately 25% to approximately 50% by weight, and between approximately 35% to approximately 45% by weight.
  • condensed phosphates include, but are not limited to: sodium and potassium orthophosphate, sodium and potassium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate.
  • a condensed phosphate may also assist, to a limited extent, in solidification of the cleaning composition by fixing the free water present in the composition as water of hydration.
  • phosphonates include, but are not limited to: 2-phosphonobutane- 1,2,4- tricarboxylic acid (PBTC), 1-hydroxyethane-l, 1-diphosphonic acid,
  • a preferred phosphonate combination is ATMP and DTPMP.
  • a neutralized or alkali phosphonate, or a combination of the phosphonate with an alkali source prior to being added into the mixture such that there is little or no heat or gas generated by a neutralization reaction when the phosphonate is added is preferred. In one embodiment, however, the cleaning composition is phosphorous-free.
  • Useful aminocarboxylic acid materials containing little or no NTA include, but are not limited to: N-hydroxyethylaminodiacetic acid, ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA),
  • DTP A diethylenetriaminepentaacetic acid
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid-N,N-diacetic acid
  • EDDS ethylenediaminesuccinic acid
  • HEIDA 2- hydroxyethyliminodiacetic acid
  • IDS iminodisuccinic acid
  • HIDS 3-hydroxy- 2-2'-iminodisuccinic acid
  • the composition is free of aminocarboxylates.
  • Water conditioning polymers can be used as non-phosphorus containing builders.
  • Exemplary water conditioning polymers include, but are not limited to:
  • polycarboxylates Exemplary polycarboxylates that can be used as builders and/or water conditioning polymers include, but are not limited to: those having pendant carboxylate (-C0 2 ⁇ ) groups such as polyacrylic acid, maleic acid, maleic/olefin polymer, sulfonated polymer or terpolymer, acrylic/maleic polymer, polymethacrylic acid, acrylic acid-methacrylic acid polymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide- methacrylamide polymers, hydrolyzed polyacrylonitrile, hydrolyzed
  • pendant carboxylate (-C0 2 ⁇ ) groups such as polyacrylic acid, maleic acid, maleic/olefin polymer, sulfonated polymer or terpolymer, acrylic/maleic polymer, polymethacrylic acid, acrylic acid-methacrylic acid polymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydro
  • polymethacrylonitrile and hydrolyzed acrylonitrile-methacrylonitrile polymers.
  • Other suitable water conditioning polymers include starch, sugar or polyols comprising carboxylic acid or ester functional groups.
  • carboxylic acids include but are not limited to maleic acid, acrylic, methacrylic and itaconic acid or salts thereof.
  • ester functional groups include aryl, cyclic, aromatic and C Cio linear, branched or substituted esters.
  • chelating agents/sequestrants see Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, volume 5, pages 339-366 and volume 23, pages 319-320, the disclosure of which is incorporated by reference herein. These materials may also be used at substoichiometric levels to function as crystal modifiers Hardening Agents
  • the cleaning compositions can also include a hardening agent in addition to, or in the form of, the builder.
  • a hardening agent is a compound or system of compounds, organic or inorganic, which significantly contributes to the uniform solidification of the composition.
  • the hardening agents are compatible with the cleaning agent and other active ingredients of the composition and are capable of providing an effective amount of hardness and/or aqueous solubility to the processed composition.
  • the hardening agents should also be capable of forming a
  • the amount of hardening agent included in the cleaning composition will vary according to factors including, but not limited to: the type of cleaning composition being prepared, the ingredients of the cleaning composition, the intended use of the composition, the quantity of dispensing solution applied to the solid composition over time during use, the temperature of the dispensing solution, the hardness of the dispensing solution, the physical size of the cleaning composition, the concentration of the other ingredients, and the concentration of the cleaning agent in the composition. It is preferred that the amount of the hardening agent included in the cleaning composition is effective to combine with the cleaning agent and other ingredients of the composition to form a homogeneous mixture under continuous mixing conditions and a temperature at or below the melting temperature of the hardening agent.
  • the hardening agent form a matrix with the cleaning agent and other ingredients which will harden to a solid form under ambient temperatures of approximately 30° C to approximately 50° C, particularly approximately 35° C to approximately 45° C, after mixing ceases and the mixture is dispensed from the mixing system, within approximately 1 minute to approximately 3 hours, particularly approximately 2 minutes to approximately 2 hours, and particularly approximately 5 minutes to approximately 1 hour.
  • a minimal amount of heat from an external source may be applied to the mixture to facilitate processing of the mixture.
  • the amount of the hardening agent included in the cleaning composition is effective to provide a desired hardness and desired rate of controlled solubility of the processed composition when placed in an aqueous medium to achieve a desired rate of dispensing the cleaning agent from the solidified composition during use.
  • the hardening agent may be an organic or an inorganic hardening agent.
  • a preferred organic hardening agent is a polyethylene glycol (PEG) compound.
  • PEG polyethylene glycol
  • the solidification rate of cleaning compositions comprising a polyethylene glycol hardening agent will vary, at least in part, according to the amount and the molecular weight of the polyethylene glycol added to the composition.
  • suitable polyethylene glycols include, but are not limited to: solid polyethylene glycols of the general formula H(OCH 2 CH 2 ) n OH, where n is greater than 15, particularly approximately 30 to approximately 1700.
  • the polyethylene glycol is a solid in the form of a free-flowing powder or flakes, having a molecular weight of approximately 1,000 to approximately 100,000, particularly having a molecular weight of at least approximately 1,450 to approximately 20,000, more particularly between approximately 1,450 to approximately 8,000.
  • the polyethylene glycol is present at a concentration of from approximately 1% to 75% by weight and particularly approximately 3% to approximately 15% by weight.
  • Suitable polyethylene glycol compounds include, but are not limited to: PEG 4000, PEG 1450, and PEG 8000 among others, with PEG 4000 and PEG 8000 being most preferred.
  • An example of a commercially available solid polyethylene glycol includes, but is not limited to: CARBOWAX, available from Union Carbide
  • Preferred inorganic hardening agents are hydratable inorganic salts, including, but not limited to: sulfates and bicarbonates.
  • the inorganic hardening agents are present at concentrations of up to approximately 50% by weight, particularly approximately 5% to approximately 25% by weight, and more particularly approximately 5% to approximately 15% by weight. In one embodiment, however, the solid composition if free of sulfates and carbonates including soda ash.
  • Urea particles can also be employed as hardeners in the cleaning compositions.
  • the solidification rate of the compositions will vary, at least in part, to factors including, but not limited to: the amount, the particle size, and the shape of the urea added to the composition.
  • a particulate form of urea can be combined with a cleaning agent and other ingredients, and preferably a minor but effective amount of water.
  • the amount and particle size of the urea is effective to combine with the cleaning agent and other ingredients to form a homogeneous mixture without the application of heat from an external source to melt the urea and other ingredients to a molten stage.
  • the amount of urea included in the cleaning composition is effective to provide a desired hardness and desired rate of solubility of the composition when placed in an aqueous medium to achieve a desired rate of dispensing the cleaning agent from the solidified composition during use.
  • the composition includes between approximately 5% to
  • urea approximately 90% by weight urea, particularly between approximately 8% and approximately 40% by weight urea, and more particularly between approximately 10% and approximately 30% by weight urea.
  • the urea may be in the form of prilled beads or powder. Prilled urea is generally available from commercial sources as a mixture of particle sizes ranging from about 8-15 U.S. mesh, as for example, from Arcadian Sohio Company, Nitrogen
  • a prilled form of urea is preferably milled to reduce the particle size to about 50 U.S. mesh to about 125 U.S. mesh, particularly about 75- 100 U.S. mesh, preferably using a wet mill such as a single or twin-screw extruder, a Teledyne mixer, a Ross emulsifier, and the like.
  • Bleaching agents suitable for use in the cleaning composition for lightening or whitening a substrate include bleaching compounds capable of liberating an active halogen species, such as Cl 2 , Br 2 , -OC1 " and/or -OBr " , under conditions typically encountered during the cleansing process.
  • Suitable bleaching agents for use in the cleaning compositions include, but are not limited to: chlorine-containing compounds such as chlorine, hypochlorites, or chloramines.
  • Exemplary halogen- releasing compounds include, but are not limited to: the alkali metal
  • a bleaching agent may also be a peroxygen or active oxygen source such as hydrogen peroxide, perborates, sodium carbonate peroxyhydrate, potassium permonosulfate, and sodium perborate mono and tetrahydrate, with and without activators such as tetraacetylethylene diamine.
  • a bleaching agent it can be included in an amount of between approximately 0.1% and approximately 60% by weight, between approximately 1% and approximately 20% by weight, between approximately 3% and approximately 8% by weight, and between approximately 3% and
  • the cleaning composition can include an effective amount of cleaning fillers which do not perform as a cleaning agent per se, but cooperates with the cleaning agent to enhance the overall cleaning capacity of the composition.
  • cleaning fillers suitable for use in the present cleaning compositions include, but are not limited to: sodium sulfate and sodium chloride.
  • the concentrate includes a cleaning filler, it can be included in an amount up to approximately 50% by weight, between approximately 1% and approximately 30% by weight, or between approximately 1.5% and approximately 25% by weight.
  • a defoaming agent for reducing the stability of foam may also be included in the cleaning composition.
  • defoaming agents include, but are not limited to: ethylene oxide/propylene block polymers such as those available under the name Pluronic® N-3 available from BASF Corporation, Florham Park, NJ; silicone compounds such as silica dispersed in polydimethylsiloxane, polydimethylsiloxane, and functionalized polydimethylsiloxane such as those available under the name Abil® B9952 available from Goldschmidt Chemical Corporation, Hopewell, VA; fatty amides, hydrocarbon waxes, fatty acids, fatty esters, fatty alcohols, fatty acid soaps, ethoxylates, mineral oils, polyethylene glycol esters, and alkyl phosphate esters such as monostearyl phosphate.
  • defoaming agents may be found, for example, in U.S. Patent No. 3,048,548 to Martin et al., U.S. Patent No. 3,334,147 to Brunelle et al., and U.S. Patent No. 3,442,242 to Rue et al., the disclosures of which are incorporated herein by reference.
  • the defoaming agent can be provided in an amount of between approximately 0.0001% and approximately 10% by weight, between approximately 0.001% and approximately 5% by weight, or between approximately 0.01% and approximately 1.0% by weight.
  • the cleaning composition can include an anti-redeposition agent for facilitating sustained suspension of soils in a cleaning solution and preventing the removed soils from being redeposited onto the substrate being cleaned.
  • suitable anti-redeposition agents include, but are not limited to: polyacrylates, styrene maleic anhydride polymers, cellulosic derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose.
  • the anti-redeposition agent can be included in an amount of between approximately 0.5% and approximately 10% by weight, and between approximately 1% and approximately 5% by weight.
  • the cleaning composition may also include stabilizing agents.
  • suitable stabilizing agents include, but are not limited to: borate, calcium/magnesium ions, propylene glycol, and mixtures thereof.
  • the concentrate need not include a stabilizing agent, but when the concentrate includes a stabilizing agent, it can be included in an amount that provides the desired level of stability of the concentrate. Exemplary ranges of the stabilizing agent include up to approximately 20% by weight, between approximately 0.5% and approximately 15% by weight, and between approximately 2% and approximately 10% by weight.
  • the cleaning composition may also include dispersants.
  • suitable dispersants that can be used in the cleaning composition include, but are not limited to: maleic acid/olefin polymers, polyacrylic acid, and mixtures thereof.
  • the concentrate need not include a dispersant, but when a dispersant is included it can be included in an amount that provides the desired dispersant properties. Exemplary ranges of the dispersant in the concentrate can be up to approximately 20% by weight, between approximately 0.5% and approximately 15% by weight, and between approximately 2% and approximately 9% by weight.
  • Enzymes that can be included in the cleaning composition include those enzymes that aid in the removal of starch and/or protein stains.
  • Exemplary types of enzymes include, but are not limited to: proteases, alpha-amylases, and mixtures thereof.
  • Exemplary proteases that can be used include, but are not limited to: those derived from Bacillus licheniformix, Bacillus lenus, Bacillus alcalophilus, and Bacillus amyloliquefacins.
  • Exemplary alpha-amylases include Bacillus subtilis, Bacillus amyloliquefaceins and Bacillus licheniformis.
  • the concentrate need not include an enzyme, but when the concentrate includes an enzyme, it can be included in an amount that provides the desired enzymatic activity when the cleaning composition is provided as a use composition.
  • Exemplary ranges of the enzyme in the concentrate include up to approximately 15% by weight, between approximately 0.5% to approximately 10% by weight, and between approximately 1% to approximately 5% by weight. Fragrances and Dyes
  • Suitable dyes that may be included to alter the appearance of the composition, include, but are not limited to: Direct Blue 86, available from Mac Dye-Chem Industries, Ahmedabad, India; Fastusol Blue, available from Mobay Chemical Corporation, Pittsburgh, PA; Acid Orange 7, available from American Cyanamid Company, Wayne, NJ; Basic Violet 10 and Sandolan Blue/ Acid Blue 182, available from Sandoz, Princeton, NJ; Acid Yellow 23, available from Chemos GmbH, Regenstauf, Germany; Acid Yellow 17, available from Sigma Chemical, St.
  • Fragrances or perfumes that may be included in the compositions include, but are not limited to: terpenoids such as citronellol, aldehydes such as amyl
  • cinnamaldehyde a jasmine such as CIS-jasmine or jasmal, and vanillin.
  • the cleaning compositions can include a rheology modifier or a thickener.
  • the rheology modifier may provide the following functions: increasing the viscosity of the compositions; increasing the particle size of liquid use compositions when dispensed through a spray nozzle; providing the use compositions with vertical cling to surfaces; providing particle suspension within the use compositions; or reducing the evaporation rate of the use compositions.
  • the rheology modifier may provide a use composition that is pseudo plastic, in other words the use composition or material when left undisturbed (in a shear mode), retains a high viscosity. However, when sheared, the viscosity of the material is substantially but reversibly reduced. After the shear action is removed, the viscosity returns. These properties permit the application of the material through a spray head. When sprayed through a nozzle, the material undergoes shear as it is drawn up a feed tube into a spray head under the influence of pressure and is sheared by the action of a pump in a pump action sprayer.
  • the viscosity can drop to a point such that substantial quantities of the material can be applied using the spray devices used to apply the material to a soiled surface.
  • the materials can regain high viscosity to ensure that the material remains in place on the soil.
  • the material can be applied to a surface resulting in a substantial coating of the material that provides the cleaning components in sufficient concentration to result in lifting and removal of the hardened or baked-on soil. While in contact with the soil on vertical or inclined surfaces, the thickeners in conjunction with the other components of the cleaner minimize dripping, sagging, slumping or other movement of the material under the effects of gravity.
  • the material should be formulated such that the viscosity of the material is adequate to maintain contact between substantial quantities of the film of the material with the soil for at least a minute, particularly five minutes or more.
  • suitable thickeners or rheology modifiers are polymeric thickeners including, but not limited to: polymers or natural polymers or gums derived from plant or animal sources. Such materials may be polysaccharides such as large polysaccharide molecules having substantial thickening capacity. Thickeners or rheology modifiers also include clays.
  • a substantially soluble polymeric thickener can be used to provide increased viscosity or increased conductivity to the use compositions.
  • polymeric thickeners for the aqueous compositions of the invention include, but are not limited to: carboxylated vinyl polymers such as polyacrylic acids and sodium salts thereof, ethoxylated cellulose, polyacrylamide thickeners, cross-linked, xanthan
  • compositions sodium alginate and algin products, hydroxypropyl cellulose, hydroxyethyl cellulose, and other similar aqueous thickeners that have some substantial proportion of water solubility.
  • suitable commercially available thickeners include, but are not limited to: Acusol, available from Rohm & Haas Company, Philadelphia, PA; and Carbopol, available from B.F. Goodrich, Charlotte, NC.
  • suitable polymeric thickeners include, but not limited to:
  • polysaccharides include, but is not limited to, Diutan, available from Kelco Division of Merck, San Diego, CA.
  • Thickeners for use in the cleaning compositions further include polyvinyl alcohol thickeners, such as, fully hydrolyzed (greater than 98.5 mol acetate replaced with the -OH function).
  • a particularly suitable polysaccharide includes, but is not limited to, xanthans. Such xanthan polymers are preferred due to their high water solubility, and great thickening power.
  • Xanthan is an extracellular polysaccharide of xanthomonas campestras. Xanthan may be made by fermentation based on corn sugar or other corn sweetener by-products. Xanthan comprises a poly beta-(l-4)-D- Glucopyranosyl backbone chain, similar to that found in cellulose.
  • Aqueous dispersions of xanthan gum and its derivatives exhibit novel and remarkable rheological properties. Low concentrations of the gum have relatively high viscosities which permit it to be used economically.
  • Xanthan gum solutions exhibit high pseudo plasticity, i.e. over a wide range of concentrations, rapid shear thinning occurs that is generally understood to be instantaneously reversible.
  • Non-sheared materials have viscosities that appear to be independent of the pH and independent of temperature over wide ranges.
  • Preferred xanthan materials include crosslinked xanthan materials.
  • Xanthan polymers can be crosslinked with a variety of known covalent reacting crosslinking agents reactive with the hydroxyl functionality of large polysaccharide molecules and can also be crosslinked using divalent, trivalent or polyvalent metal ions. Such crosslinked xanthan gels are disclosed in U.S. Patent No. 4,782,901, which is herein incorporated by reference.
  • Suitable crosslinking agents for xanthan materials include, but are not limited to: metal cations such as A 1+3, Fe+3, Sb+3, Zr+4 and other transition metals.
  • suitable commercially available xanthans include, but are not limited to: KELTROL®, KELZAN® AR, KELZAN® D35, KELZAN® S, KELZAN® XZ, available from Kelco Division of Merck, San Diego, CA.
  • Known organic crosslinking agents can also be used.
  • a preferred crosslinked xanthan is KELZAN® AR, which provides a pseudo plastic use composition that can produce large particle size mist or aerosol when sprayed.
  • the cleaning composition of the present invention can be created by combining the alkalinity source, the surfactant, the polymer including maleic acid, vinyl acetate and ethyl acrylate segments, any secondary polymer sources, and any additional functional components and allowing the components to interact.
  • the alkalinity source, the surfactant, the polymer including maleic acid, vinyl acetate and ethyl acrylate segments, any secondary polymer sources, and any additional functional components can harden into solid form.
  • the solidification process may last from a few minutes to about six hours, depending on factors including, but not limited to: the size of the formed or cast composition, the ingredients of the composition, and the temperature of the composition.
  • the solid cleaning compositions may be formed using a batch or continuous mixing system.
  • a single- or twin-screw extruder is used to combine and mix one or more cleaning agents at high shear to form a homogeneous mixture.
  • the processing temperature is at or below the melting temperature of the components.
  • the processed mixture may be dispensed from the mixer by forming, casting or other suitable means, whereupon the cleaning composition hardens to a solid form.
  • the structure of the matrix may be
  • a solid cleaning composition processed according to the method of the invention is substantially homogeneous with regard to the distribution of ingredients throughout its mass and is dimensionally stable.
  • liquid and solid components are introduced into final mixing system and are continuously mixed until the components form a
  • the formed composition begins to harden to a solid form in between approximately 1 minute and approximately 3 hours. Particularly, the formed composition begins to harden to a solid form in between approximately 1 minute and approximately 2 hours. More particularly, the formed composition begins to harden to a solid form in between approximately 1 minute and approximately 20 minutes.
  • liquid and solid components are introduced into the final mixing system and are continuously mixed until the components form a
  • the components are mixed in the mixing system for at least approximately 60 seconds. Once the mixing is complete, the product is transferred to a packaging container where solidification takes place.
  • the cast composition begins to harden to a solid form in between approximately 1 minute and approximately 3 hours. Particularly, the cast composition begins to harden to a solid form in between approximately 1 minute and approximately 2 hours. More particularly, the cast composition begins to harden to a solid form in between approximately 1 minute and approximately 20 minutes.
  • solid By the term “solid”, it is meant that the hardened composition will not flow and will substantially retain its shape under moderate stress or pressure or mere gravity.
  • the degree of hardness of the solid cast composition may range from that of a fused solid product which is relatively dense and hard, for example, like concrete, to a consistency characterized as being a hardened paste.
  • solid refers to the state of the cleaning composition under the expected conditions of storage and use of the solid cleaning composition. In general, it is expected that the cleaning composition will remain in solid form when exposed to temperatures of up to approximately 100° F and particularly up to approximately 120° F.
  • the resulting solid cleaning composition may take forms including, but not limited to: a cast solid product; an extruded, molded or formed solid pellet, block, tablet, powder, granule, flake; or the formed solid can thereafter be ground or formed into a powder, granule, or flake.
  • extruded pellet materials formed by the solidification matrix have a weight of between approximately 50 grams and approximately 250 grams
  • extruded solids formed by the composition have a weight of approximately 100 grams or greater
  • solid block detergents formed by the composition have a mass of between approximately 1 and
  • the solid compositions provide for a stabilized source of functional materials.
  • the solid composition may be dissolved, for example, in an aqueous or other medium, to create a concentrated and/or use composition.
  • the solution may be directed to a storage reservoir for later use and/or dilution, or may be applied directly to a point of use.
  • the solid cleaning composition is provided in the form of a unit dose.
  • a unit dose refers to a solid cleaning composition unit sized so that the entire unit is used during a single washing cycle.
  • the solid cleaning composition is typically provided as a cast solid, an extruded pellet, or a tablet having a size of between approximately 1 gram and approximately 50 grams.
  • the solid cleaning composition is provided in the form of a multiple-use solid, such as a block or a plurality of pellets, and can be repeatedly used to generate aqueous cleaning compositions for multiple washing cycles.
  • the solid cleaning composition is provided as a cast solid, an extruded block, or a tablet having a mass of between approximately 5 grams and approximately 10 kilograms.
  • a multiple-use form of the solid cleaning composition has a mass between approximately 1 kilogram and approximately 10 kilograms.
  • a multiple-use form of the solid cleaning composition has a mass of between approximately 5 kilograms and about approximately 8 kilograms.
  • a multiple-use form of the solid cleaning composition has a mass of between about approximately 5 grams and approximately 1 kilogram, or between approximately 5 grams and approximately 500 grams.
  • the cleaning composition may also be provided in the form of a paste or liquid.
  • the concentrate is provided in the form of a paste, enough water is added to the cleaning composition such that complete solidification of the cleaning composition is precluded.
  • dispersants and other components may be incorporated into the cleaning composition in order to maintain a desired
  • the cleaning compositions can include concentrate compositions or can be diluted to form use compositions.
  • a concentrate refers to a composition that is intended to be diluted with water to provide a use composition that contacts an object to provide the desired cleaning, rinsing, or the like.
  • the cleaning composition that contacts the articles to be washed can be referred to as the use composition.
  • the use composition can include additional functional ingredients at a level suitable for cleaning, rinsing, or the like.
  • a use composition may be prepared from the concentrate by diluting the concentrate with water at a dilution ratio that provides a use composition having desired detersive properties.
  • the water that is used to dilute the concentrate to form the use composition can be referred to as water of dilution or a dilutent, and can vary from one location to another.
  • the typical dilution factor is between approximately 1 and approximately 10,000 but will depend on factors including water hardness, the amount of soil to be removed and the like.
  • the concentrate is diluted at a ratio of between about 1:10 and about 1:1000 concentrate to water.
  • the concentrate is diluted at a ratio of between about 1:100 and about 1:5000 concentrate to water. More particularly, the concentrate is diluted at a ratio of between about 1:250 and 1:2000 concentrate to water.
  • a suitable concentration range of the components in the use composition includes between about 10 and 4,000 parts-per- million (ppm) alkalinity source, and between about 1 and 2,000 ppm of the polymer containing maleic acid, vinyl acetate and alkyl acrylate monomers.
  • a particularly suitable concentration range of components in the use composition includes between about 100 and 6,000 ppm alkalinity source, and between about 10 and 1000 ppm of the polymer containing the maleic acid, vinyl acetate and alkyl acrylate monomers.
  • a more particularly suitable concentration range of the components in the use composition includes between about 10 and 4,000 parts-per- million (ppm) alkalinity source, and between about 1 and 2,000 ppm of the polymer containing maleic acid, vinyl acetate and alkyl acrylate monomers.
  • a particularly suitable concentration range of components in the use composition includes between about 100 and 6,000 ppm alkalinity source, and between about 10 and 1000 ppm of the polymer containing the maleic acid, vinyl acetate
  • concentration range of components in the use composition includes between about 250 and 4,000 ppm alkalinity source, and between about 10 and 500 ppm of the polymer containing the maleic acid, vinyl acetate and alkyl acrylate monomers.
  • a suitable concentration range of the components in the use composition includes between about 1 and 8,000 ppm alkalinity source, and between about 5 and 2,000 ppm of the polymer (which includes at least the polymer containing maleic acid, vinyl acetate and alkyl acrylate monomers and at least one secondary polymer source).
  • the use composition can be used at elevated temperature.
  • the use composition is used at a temperature between approximately 70°F and
  • a use composition is used at a temperature between approximately 100°F and approximately 170°F to contact the substrate to be cleaned.
  • the use composition contains an effective concentration of the alkalinity source so that the use composition has a pH of between about 7 and about 13.
  • the use composition can be brought into contact with soiled articles to clean the articles.
  • the maleic acid, vinyl acetate and ethyl acrylate polymer of the use composition may function as a scale inhibitor.
  • the maleic acid, vinyl acetate and ethyl acrylate polymer of the use composition may also reduce encrustation for textiles.
  • Alcosperse® 125 a methacrylate polymer available from Akzo Nobel Surfactants, Chicago, IL
  • Belclene® 283 a maleic acid, ethyl acrylate and vinyl acetate terpolymer available from BWA Water Additives, Tucker, GA
  • Belclene® 810 a maleic acid, ethyl acrylate and vinyl acetate terpolymer available from BWA Water Additives, Tucker, GA
  • Acusol ® 445N a polyacrylate homopolymer available from Rohm and Haas, Philadelphia, PA
  • Acusol 944 an acrylic acid homopolymer available from Dow Chemical Cycle Automatic Dishwashing Test
  • Libbey glasses were prepared by removing all film and foreign material from the surfaces of the glasses.
  • the dishmachine was then filled with an appropriate amount of water and the water was tested for hardness. After recording the value, the tank heaters were turned on.
  • the dishmachine was then turned on and wash/rinse cycles were run through the machine until a wash temperature of between about 150 °F and about 170°F was reached.
  • the controller was then set to dispense an appropriate amount of cleaning into the wash tank.
  • the solution in the wash tank was titrated to verify cleaning concentration.
  • the 6 clean glasses were placed diagonally in a Raburn rack and four plastic tumblers were placed off-diagonally in the Raburn rack (see figure below for arrangement) and the rack was placed inside the dishmachine.
  • P plastic tumbler
  • G glass tumbler
  • the 100 cycle test was then started. At the beginning of each wash cycle, the appropriate amount of cleaning was automatically dispensed into the warewash machine to maintain the initial cleaning concentration.
  • the cleaning concentration was controlled by conductivity.
  • the proper amount of cleaning was dispensed into the warewash machine to maintain the initial concentration.
  • the rack was removed from the warewash machine and the glasses and plastic tumbles were allowed to dry overnight. The glasses were rated using the light box evaluation test.
  • the light box test standardizes the evaluation of the glasses run on the 100 cycle test using an analytical method.
  • the light box test is based on the use of an optical system including a photographic camera, a lightbox, a light source and a light meter.
  • the system is controlled by a computer program (Spot Advance and Image Pro Plus).
  • each glass was placed on the light box resting on its side and the intensity of the light source was adjusted to a predetermined value using a light meter.
  • the conditions of the 100 cycle test were entered into the computer.
  • a picture of the glass was taken with the camera and saved on the computer for analysis by the program.
  • the picture was analyzed using the upper half of the glass in order to avoid the gradient of darkness on the film from the top of the glass to the bottom of the glass, based on the shape of the glass.
  • a lower light box rating indicates that more light was able to pass through the glass.
  • the lower the light box rating the more effective the cleaning composition was at preventing scale on the surface of the glass.
  • Control #2 (Commercial Products A) is commercially available by Ecolab Inc., Saint Paul, MN.
  • Control 1 was considered a negative control because the cleaning composition did not include a polymer source, whereas, Control 2 was considered a positive control because the cleaning composition included a synthetic polymer.
  • the alkalinity source and surfactant source were held constant for Controls 1 and 2, and Examples 1-9.
  • the cleaning composition of Example 1 only included Belclene 810 as a biodegradable terpolymer source and did not include a secondary additional polymer source.
  • the cleaning composition for Examples 2-9 included less and less of a terpolymer source and greater and greater amounts of an additional synthetic polymer, specifically Alcosperse 125, until the cleaning composition in Example 9 only included a synthetic polymer source without the addition of a biodegradable terpolymer. The purpose of this test to determine if adding a terpolymer with a secondary synthetic polymer source to a detergent composition is effective in preventing scale formation on the surface of the glass.
  • Examples 1-9 have lower light box scores than Control 1 which means that more light passed through the glass and so it was conclusive that the addition of a terpolymer and an additional synthetic polymer to a detergent composition is effective in preventing scale formation on the surface of the glass.
  • Examples 10-17 have lower light box scores than Control 1 which means that more light passed through the glass and so it was conclusive that the addition of a terpolymer and an additional synthetic polymer to a detergent composition is effective in preventing scale formation on the surface of the glass. Examples 10-17
  • the cleaning compositions used for Examples 10-17 were very similar to the cleaning compositions used for Examples 1-9, except that Acusol 445N was used as the secondary synthetic polymer source.
  • Acusol 445N was used as the secondary synthetic polymer source.
  • the raw materials identified for each of Controls 3 and 4, and Examples 18- 20 in Table 6 below were combined and mixed to form concentrate cleaning compositions.
  • the Belclene 810 Premix is a source of a terpolymer and includes 71.4% Belclene 810 and 28.6% of a caustic such as sodium hydroxide, which helps in neutralizing the terpolymer source.
  • Control 4 (Commercially Available Product B) is commercially available under the name Apex LP by Ecolab Inc., in Saint Paul, MN.
  • Control #3 did not include any additional polymer source, but a different source of alkalinity was used, specifically Control #3 is for an ash based formulation.
  • Control 4 is considered a positive control, because it is an ash based formulation with the addition of a secondary synthetic polymer.
  • Example 18 is also for an ash based formulation but with the addition of a biodegradable terpolymer.
  • Examples 19 and 20 are for an ash based formulation with the addition of both a biodegradable terpolymer and Alcosperse 125, a secondary synthetic polymer. The purpose of these examples was to determine if adding a terpolymer alone or in addition to a secondary synthetic polymer source to an ash based formulation was effective in preventing scale formulation on the surface of the glass.
  • Examples 18-20 have significantly lower light box scores than Control 3 and lower light box scores than Control 4 which means that more light passed through the glass and so it was conclusive that the addition of a terpolymer or the combination of a terpolymer with a secondary synthetic polymer source to an ash based formulation is very effective in preventing scale formation on the surface of the glass.
  • Examples 21 and 22
  • Example 21 and 22 the same control was used as in Example 18-20. However, in Examples 21 and 22 a different synthetic polymer was used in the ash based formulation, specifically Acusol 445N which is a secondary polyacrylate source.
  • Acusol 445N as a secondary synthetic polymer source in ash based formulations is very effective in preventing scale formulation on the surface of the glasses.
  • Control #4 and Examples 23 and 24 the alkalinity source was held constant and no additional polymer sources were added. Control 4 didn't include a terpolymer source, while Example 23 used Belclene 810 as a polymer source and Example 24 used Belclene 283 as a terpolymer source. The purpose of this test was to determine if adding a terpolymer to a cleaning composition is effective in preventing scale formation on the surface of the glass.
  • Examples 23 and 24 have lower light box scores which mean that more light passed through the glass and so it was conclusive that addition of a terpolymer to a cleaning composition is effective in preventing scale formation on the surface of the glass.
  • Control #5 and Examples 25 and 26 The raw materials identified for each of Control #5 and Examples 25 and 26 in Table 12 below were combined and mixed to form concentrate cleaning
  • Examples 25 and 26 have lower light box scores which mean that more light passed through the glass and so it was conclusive that addition of a terpolymer to a cleaning composition with a higher alkalinity concentration is effective in preventing scale formation on the surface of the glass.
  • the raw materials identified for each of Control #6 and Examples 27-30 in Table 14 below were combined and mixed to form concentrate cleaning compositions.
  • the Belclene 810 Premix is a source of a terpolymer and includes 71.4% Beleclene 810 and 28.6% of a caustic such as sodium hydroxide, which helps in neutralizing the terpolymer source.
  • the detergent formula for Control 6 did not include any additional polymer source, while the detergent formula for Example included a terpolymer source and
  • Examples 28-30 included both a terpolymer source and a secondary polymer source, specifically a polyacrylate.
  • the detergent formula for Example 28 included a greater percentage of the terpolymer source than the secondary polymer source, whereas the detergent formula for Example 29 included relatively equal amounts of both polymers, and the detergent formula for Example 30 included a greater percentage of the secondary polymer relative to the terpolymer source.
  • the purpose of these examples was to determine if adding a secondary polymer source, specifically a polyacylate or a synthetic polymer, was effective in preventing scale formulation on the surface of the glass.
  • Examples 27-30 have lower light box scores than Control 6 which means that more light passed through the glass and so it was conclusive that the addition of a terpolymer or the combination of a terpolymer with a secondary synthetic polymer source is effective in preventing scale formation on the surface of the glass.
  • Control #7 and Examples 31-34 The raw materials identified for each of Control #7 and Examples 31-34 in Table 16 below were combined and mixed to form concentrate cleaning compositions.
  • Examples 31-34 the same control was used as in Examples 28-30. However, in Examples 31-34 a different synthetic polymer was used in the detergent formulations, specifically Acusol 445N which is a secondary polyacrylate source. A warewash test was conducted with the compositions of Control 7 and Examples 31-34 according to the 5 cycle dishwashing test described above. The results of the light box test are presented below in Table 17.
  • Acusol 445N as a secondary synthetic polymer source is very effective in preventing scale formulation on the surface of the glasses.
  • Example 35-38 the same control was used as in Examples 28-30. Moreover, the detergent formulations used in Examples 35-38 are very similar to the detergent formulations in Examples 28-30, except that the formulations in Examples 35-38 include higher concentrations of the biodegradable terpolymer source. The purpose of these tests was to determine if a higher concentration of the biodegradable terpolymer source makes the detergent formulation more effective in preventing scale formulation on the glasses.
  • a tergotometer was then used to determine encrustation. Each well of the tergotometer was filled with 1 liter of 17 grain water and allowed to heat to 140F. Four terry cloth swatches were added to each well followed by lOg of 10% solution of detergent. Each cleaning composition was run in duplicate. The wash time was 10 minutes. When the cycle was complete, each swatch was rinsed with 17 grain water. After the completion of 5 cycles, one terry cloth swatch was removed from each well. After an additional 5 cycles was complete, another terry cloth swatch was removed from each well. This was repeated for a total of 20 cycles.
  • the terry cloth swatches were dried overnight.
  • the calcium carbonate buildup on the test fabric was measured by eluting with 75 mL of a solution containing 0.1M HC1 and 0.1M H 2 S0 4 in a 125 mL Erlenmeyer flask.
  • the values for calcium were determined by ICP expressed as ppm of calcium carbonate.
  • a positive formulation was tested with the addition of Acusol 445N, as a synthetic polymer source to a laundry cleaning composition or detergent formulation.
  • Examples 39-41 included varying amounts of the addition of Belclene 810, a biodegradable terpolymer source, and Alcosperse 125, a synthetic polymer source, to a laundry cleaning composition formulation.
  • Example 42 included only the addition of Belclene 810 to the laundry cleaning composition formulation. The purpose of these tests were to determine if the addition of a biodegradable polymer alone or in conjunction with a synthetic polymer to a laundry cleaning composition or detergent formulation is effective in preventing calcium carbonate encrustation on textiles.
  • Encrustation tests were performed to measure the level of mineral deposits on linen after extended washing with a detergent, which included a builder and a surfactant system. There are two main components to the test: the treatment of the linen during the extended wash cycles and the ashing procedure to measure the level of encrustation.
  • HX35PVXU60001 was charged with 28 pounds of cotton towels (including test pieces) as ballast.
  • the wash water temperature was 40°C, and the water contained 17 grains of hardness or the equivalent of 1100 mg of calcium carbonate per 3.79 litters.
  • the detergent was dose was 52.5 grams per load. The ballast cotton towels and cotton test pieces were thoroughly washed and dried prior to use to remove any residual finishes from manufacturing.
  • the set of three circles cut from the 20 cycle washed towels was added to a tared 100 mL beaker.
  • the beaker was heated overnight in an oven at 600°F.
  • Each beaker was re-weighed after cooling to establish a final weight.
  • the final total weight minus the initial beaker weight is equal to the mass of the inorganic residue or ash. Dividing the weight of the ash amount by the weight of the initial towels (e.g., 10 grams) yields the ash percent value for one towel.
  • the reported value is the average of the six towels for each condition.
  • Solid Surge Plus is a solid institutional laundry detergent comprising high levels of alkalinity (sodium hydroxide) and water conditioners, including 5 wt Acusol 944 and 12.82 wt Acusol 445N.
  • Example 43 was a detergent identical to SSP except that in Example 43 the Acusol 445N was replaced with 7 wt Belclene 810 .
  • Example 44 was a detergent identical to SSP except that in Example 44 the Acusol 445N was replaced with 4 wt Belclene 810.
  • the water conditioners of Examples 43 and 44 and SSP are listed in Table 26. All other components of Examples 43 and 44 were the same as SSP.
  • Example 43 Twenty cycle encrustation tests were run using the SSP, Example 43 and Example 44 detergents. The test samples were ashed as described. The ash percent value of Table 27 is the average ash value of the six test towels. Also shown is the P value for the T test comparing each Example mean with the mean value for the control Solid Surge Plus.
  • Table 27 The values of Table 27 clearly show that the use of Belclene 810 polymer in place of acrylic acid homopolymer results in statistically significant reductions in linen encrustation. Additionally Table 27 shows that the addition of a polymer including maleic acid, vinyl acetate and alkyl acrylate to a laundry detergent formulation along with a synthetic polymer including acrylic acid is highly effective in preventing calcium carbonate buildup or encrustation in textiles. Examples 45 and 46
  • Example 45 was a detergent identical to Solid Surge Plus except that in Example 45 the Acusol 445N was replaced with 5 wt% Belclene 810.
  • Example 46 was a detergent identical to SSP except that in Example 46 the Acusol 445N was replaced with 3.6 wt% Belclene 810, and the Acusol 944 level was increased to 6%.
  • the water conditioners of Examples 45 and 46, and SSP are listed in Table 28. All other components of Examples 45 and 46 were the same as SSP.
  • Example 45 Twenty cycle encrustation tests were run using the SSP, Example 45 and Example 46 detergents.
  • the test towels were ashed as described above to give the average encrustation or ash values shown in Table 29. These values are the average of the six test towels.
  • Table 29 also shows the P value for the T test comparing each Example mean with the mean value for the control Solid Surge Plus.
  • Example 45 The values for Example 45 in Table 29 clearly show that the use of Belclene 810 polymer in place of acrylic acid homopolymer results in a statistically significant reduction in linen encrustation.
  • Example 46 the reduced level of Belclene 810 and increased level of Acusol 944 was not sufficient to provide an encrustation level that was statistically different from the SSP control, but the Belclene 810 was still effective enough that just 3.6% of the Belclene polymer was as effective as 12.8% of Acusol 445N polymer.
  • Samples 45 and 46 illustrate that the addition of a polymer including maleic acid, vinyl acetate and alkyl acrylate to a laundry detergent formulation along with a synthetic polymer comprising acrylic acid is highly effective at preventing calcium carbonate buildup or encrustation in textiles.

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Abstract

La présente invention porte sur une composition de nettoyage comprenant au moins une source d'alcalinité et un terpolymère biodégradable comprenant des segments d'acide maléique, d'acétate de vinyle et d'acrylate d'aldéhyde ou des monomères acide maléique, acétate de vinyle et acrylate d'alkyle pour un effet antitartre accru. La solution diluée destinée à être utilisée a une plage de pH comprise entre environ 7 et environ 14.
PCT/US2013/032895 2012-03-23 2013-03-19 Composition de nettoyage comprenant un terpolymère contenant des monomères acide maléique, acétate de vinyle et acrylate d'alkyle pour un effet antitartre accru WO2013142457A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US13/428,622 2012-03-23
US13/428,643 US20130252870A1 (en) 2012-03-23 2012-03-23 Cleaning composition including a terpolymer containing maleic acid, vinyl acetate, and alkyl acrylate monomers for enhanced scale control
US13/428,632 2012-03-23
US13/428,632 US8740993B2 (en) 2012-03-23 2012-03-23 Method for reduced encrustation of textiles using a polymer comprising maleic acid, vinyl acetate, and alkyl acrylate
US13/428,637 US20130252871A1 (en) 2012-03-23 2012-03-23 Cleaning composition including a terpolymer containing maleic acid, vinyl acetate, and alkyl acrylate monomers for enhanced scale control
US13/428,622 US8623151B2 (en) 2012-03-23 2012-03-23 Terpolymer containing maleic acid, vinyl acetate, and alkyl acrylate monomers for aluminum protection
US13/428,637 2012-03-23
US13/428,643 2012-03-23

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PCT/US2013/032895 WO2013142457A1 (fr) 2012-03-23 2013-03-19 Composition de nettoyage comprenant un terpolymère contenant des monomères acide maléique, acétate de vinyle et acrylate d'alkyle pour un effet antitartre accru

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020200838A1 (fr) * 2019-04-04 2020-10-08 Chemetall Gmbh Agent de nettoyage sans phosphate pour surfaces métalliques à enlèvement par décapage réduit
RU2815091C2 (ru) * 2019-04-04 2024-03-11 Хеметалл Гмбх Бесфосфатное чистящее средство для металлических поверхностей, обеспечивающее пониженную эрозию при травлении

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106318653A (zh) * 2016-08-19 2017-01-11 桂林福冈新材料有限公司 一种清洗后无痕迹的玻璃洗涤剂

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0774507A2 (fr) * 1995-11-20 1997-05-21 Rohm And Haas Company Concentrés nettoyant et procédé de préparation
US6291600B1 (en) * 1989-12-28 2001-09-18 Mitsui Chemicals, Inc. Method of preventing scale adhesion to the surfaces of a polymerization tank
US20090062175A1 (en) * 2007-08-31 2009-03-05 Laura Cermenati Liquid acidic hard surface cleaning composition
US20110071065A1 (en) * 2009-01-30 2011-03-24 Ecolab USA High alkaline detergent composition with enhanced scale control
US20120053106A1 (en) * 2009-09-15 2012-03-01 Regine Labeque Detergent composition comprising surfactant boosting polymers
US20120053105A1 (en) * 2010-08-27 2012-03-01 Ecolab Usa Inc. Detergent compositions with combinations of acrylic and maleic acid homopolymers and/or salts thereof for aluminum protection

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3887480A (en) * 1972-09-08 1975-06-03 Economics Lab Detergent compositions and methods of making and using them
AU677658B2 (en) * 1993-06-01 1997-05-01 Ecolab Inc. Foam surface cleaner
JP2006002229A (ja) * 2004-06-18 2006-01-05 Nippon Parkerizing Co Ltd アルミニウム又はアルミニウム合金用洗浄剤及び洗浄方法
CN102762708B (zh) * 2009-07-06 2015-03-04 布拉斯通产品公司 清洁具有铝组件的传热系统的方法和组合物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6291600B1 (en) * 1989-12-28 2001-09-18 Mitsui Chemicals, Inc. Method of preventing scale adhesion to the surfaces of a polymerization tank
EP0774507A2 (fr) * 1995-11-20 1997-05-21 Rohm And Haas Company Concentrés nettoyant et procédé de préparation
US20090062175A1 (en) * 2007-08-31 2009-03-05 Laura Cermenati Liquid acidic hard surface cleaning composition
US20110071065A1 (en) * 2009-01-30 2011-03-24 Ecolab USA High alkaline detergent composition with enhanced scale control
US20120053106A1 (en) * 2009-09-15 2012-03-01 Regine Labeque Detergent composition comprising surfactant boosting polymers
US20120053105A1 (en) * 2010-08-27 2012-03-01 Ecolab Usa Inc. Detergent compositions with combinations of acrylic and maleic acid homopolymers and/or salts thereof for aluminum protection

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020200838A1 (fr) * 2019-04-04 2020-10-08 Chemetall Gmbh Agent de nettoyage sans phosphate pour surfaces métalliques à enlèvement par décapage réduit
CN113646467A (zh) * 2019-04-04 2021-11-12 凯密特尔有限责任公司 具有降低酸洗侵蚀的用于金属表面的无磷酸盐清洗剂
RU2815091C2 (ru) * 2019-04-04 2024-03-11 Хеметалл Гмбх Бесфосфатное чистящее средство для металлических поверхностей, обеспечивающее пониженную эрозию при травлении

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