EP4227391A1 - Waschmittelzusammensetzung mit reinigungs- und spülfunktion - Google Patents

Waschmittelzusammensetzung mit reinigungs- und spülfunktion Download PDF

Info

Publication number
EP4227391A1
EP4227391A1 EP23176658.5A EP23176658A EP4227391A1 EP 4227391 A1 EP4227391 A1 EP 4227391A1 EP 23176658 A EP23176658 A EP 23176658A EP 4227391 A1 EP4227391 A1 EP 4227391A1
Authority
EP
European Patent Office
Prior art keywords
composition
detergent
glass
compositions
cleaning
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.)
Pending
Application number
EP23176658.5A
Other languages
English (en)
French (fr)
Inventor
Monique ROERDINK-LANDER
Carter M. Silvernail
Erin Jane DAHLQUIST HOWLETT
Kerrie Walters
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 USA Inc
Original Assignee
Ecolab USA Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ecolab USA Inc filed Critical Ecolab USA Inc
Publication of EP4227391A1 publication Critical patent/EP4227391A1/de
Pending legal-status Critical Current

Links

Images

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
    • C11D3/10—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0052—Cast detergent 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • 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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/008—Polymeric surface-active agents
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • the invention relates to an industrial 2-in-1 cleaning composition providing both detergency and rinse aid efficacy in a single cleaning composition.
  • compositions and methods of both making and using the same provide a user-friendly, solid, detergent composition without the need for using a separate rinse aid composition.
  • the compositions and methods are particularly well suited for use in industrial cleaning using alkali metal carbonate compositions that beneficially provide cleaning and rinseability to permit the use of a potable water rinse without the addition of a separate rinse agent.
  • Alkaline detergents are used extensively to clean articles in both consumer and industrial dish machines. Alkaline detergents are extensively used because of their ability to remove and emulsify fatty, oily, hydrophobic soils. However, alkaline detergents have the disadvantage of requiring a rinse aid to prevent the formation of films on glass and other substrate surfaces contacted by the alkaline detergent. Filming is caused in part by using alkaline detergents in combination with certain water types (including hard water), and water temperatures. A solution to the generation of hard water films has been to employ rinse aids to remove such films. However, the need for rinse aids increases the cost associated with alkaline detergents for both the formulation of the cleaning compositions as well as the additional costs associated with heated water for rinsing steps.
  • rinse aids are used in a rinse cycle following the wash cycle to enhance drying time, as well as reduce any cleaning imperfections (including the removal of films). Additional benefits and methods of using rinse aids are described in U.S. Patent No. RE 38262 , which is herein incorporated by reference in its entirety.
  • GRAS generally recognized as safe
  • a further object of the invention is to provide a carbonate-based alkaline detergent employing a combination of surfactants, and optionally polymers, to provide good cleaning performance and rinseability without the use of a rinse aid in the cleaning composition.
  • a further object of the invention is to provide a carbonate-based alkaline detergent employing a combination of surfactants, and optionally polymers, providing at least substantially similar cleaning and rinsing efficacy as a conventional two part detergents and rinse aids.
  • An advantage of the invention is industrial detergent compositions providing both detergency and rinseability in a single cleaning composition, thus eliminating the need for an additional rinse aid composition.
  • the composition of the invention provides thus a user-friendly, solid, 2-in-1 cleaning and rinsing action, beneficially eliminating a distinct rinse aid from the industrial warewashing compositions and methods of use.
  • the alkaline detergent compositions according to the invention beneficially provide both good cleaning performance and rinseability in a potable water rinse without the use of an added rinse aid in the rinse cycle.
  • the present invention provides a composition comprising a carbonate alkalinity source in combination with nonionic surfactants, where the composition replaces the separate use of both a dish machine detergent and a rinse additive due to the superior cleaning and rinseability of the composition.
  • the detergent compositions can also include polymers, such as a polycarboxylic acid polymer, builders, water conditioning agents, neutralizing agents, sanitizers, etc.
  • the present invention provides methods of cleaning articles in an industrial dish machine using a carbonate-based alkaline detergent comprising an alkali metal carbonate and nonionic surfactants.
  • the invention also pertains to a method of cleaning articles in an industrial dish machine using the steps of supplying the alkaline 2-in-1 composition, inserting the composition into a dispenser in a dish machine, forming a wash solution with the composition and water, contacting soil on an article in the dish machine with the wash solution, removing the soil, and rinsing the article using the same alkaline 2-in-1 cleaning composition and no additional rinse aids.
  • the present invention relates to a 2-in-1 industrial alkaline cleaning compositions which provide suitable cleaning and rinseability while employing a carbonate-based alkaline detergent and a combination of surfactants.
  • the nonionic surfactants create an efficacious aqueous rinse with potable water.
  • the embodiments of this invention are not limited to particular alkaline detergents, which can vary and are understood by skilled artisans based upon the disclosure provided herein. It is further to be understood that all terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting in any manner or scope. For example, as used in this specification and the appended claims, the singular forms "a,” “an” and “the” can include plural referents unless the content clearly indicates otherwise. Further, all units, prefixes, and symbols may be denoted in its SI accepted form.
  • range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
  • actives or “percent actives” or “percent by weight actives” or “actives concentration” are used interchangeably herein and refers to the concentration of those ingredients involved in cleaning expressed as a percentage minus inert ingredients such as water or salts.
  • alkyl refers to a straight or branched chain monovalent hydrocarbon group optionally containing one or more heteroatomic substitutions independently selected from S, O, Si, or N.
  • Alkyl groups generally include those with one to twenty atoms. Alkyl groups may be unsubstituted or substituted with those substituents that do not interfere with the specified function of the composition. Substituents include alkoxy, hydroxy, mercapto, amino, alkyl substituted amino, or halo, for example.
  • alkyl examples include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, isopropyl, and C8-C20 alkyl chains and the like.
  • alkyl may include “alkylenes”, “alkenylenes”, or “alkylynes”.
  • alkylene refers to a straight or branched chain divalent hydrocarbon group optionally containing one or more heteroatomic substitutions independently selected from S, O, Si, or N.
  • Alkylene groups generally include those with one to twenty atoms. Alkylene groups may be unsubstituted or substituted with those substituents that do not interfere with the specified function of the composition. Substituents include alkoxy, hydroxy, mercapto, amino, alkyl substituted amino, or halo, for example.
  • Examples of "alkylene” as used herein include, but are not limited to, methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl and the like.
  • alkenylene refers to a straight or branched chain divalent hydrocarbon group having one or more carbon-carbon double bonds and optionally containing one or more heteroatomic substitutions independently selected from S, O, Si, or N.
  • Alkenylene groups generally include those with one to twenty atoms. Alkenylene groups may be unsubstituted or substituted with those substituents that do not interfere with the specified function of the composition. Substituents include alkoxy, hydroxy, mercapto, amino, alkyl substituted amino, or halo, for example.
  • alkylyne refers to a straight or branched chain divalent hydrocarbon group having one or more carbon-carbon triple bonds and optionally containing one or more heteroatomic substitutions independently selected from S, O, Si, or N.
  • Alkylyne groups generally include those with one to twenty atoms. Alkylyne groups may be unsubstituted or substituted with those substituents that do not interfere with the specified function of the composition. Substituents include alkoxy, hydroxy, mercapto, amino, alkyl substituted amino, or halo, for example.
  • alkoxy refers to --O--alkyl groups wherein alkyl is as defined above.
  • cleaning refers to a method used to facilitate or aid in soil removal, bleaching, microbial population reduction, and any combination thereof.
  • GRAS general recognized as safe
  • components classified by the Food and Drug Administration as safe for direct human food consumption or as an ingredient based upon current good manufacturing practice conditions of use, as defined for example in 21 C.F.R. Chapter 1, ⁇ 170.38 and/or 570.38.
  • oil or “stain” refers to a polar or non-polar substances which may or may not contain particulate matter such as, but not limited to mineral clays, sand, natural mineral matter, carbon black, graphite, kaolin, environmental dust and food soils such as polyphenols starches, proteins, oils and fats, etc.
  • the term "substantially free” refers to compositions completely lacking the component or having such a small amount of the component that the component does not affect the performance of the composition.
  • the component may be present as an impurity or as a contaminant and shall be less than 0.5 wt-%. In another embodiment, the amount of the component is less than 0.1 wt-% and in yet another embodiment, the amount of component is less than 0.01 wt-%.
  • substantially similar cleaning performance refers generally to achievement by a substitute cleaning product or substitute cleaning system of generally the same degree (or at least not a significantly lesser degree) of cleanliness or with generally the same expenditure (or at least not a significantly lesser expenditure) of effort, or both.
  • Threshold agent refers to a compound that inhibits crystallization of water hardness ions from solution, but that need not form a specific complex with the water hardness ion.
  • Threshold agents include but are not limited to a polyacrylate, a polymethacrylate, an olefin/maleic copolymer, and the like.
  • ware refers to items such as eating and cooking utensils, and dishes.
  • warewashing refers to washing, cleaning, or rinsing ware. Ware also refers to items made of plastic.
  • Types of plastics that can be cleaned with the compositions according to the invention include but are not limited to, those that include polycarbonate polymers (PC), acrilonitrile-butadiene-styrene polymers (ABS), and polysulfone polymers (PS).
  • PC polycarbonate polymers
  • ABS acrilonitrile-butadiene-styrene polymers
  • PS polysulfone polymers
  • Other exemplary plastics that can be cleaned using the compounds and compositions of the invention include polyethylene terephthalate (PET) and plastics from melamine resin.
  • weight percent refers to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used here, “percent,” “%,” and the like are intended to be synonymous with “weight percent,” “wt-%,” etc.
  • compositions of the present invention may comprise, consist essentially of, or consist of the components and ingredients of the present invention as well as other ingredients described herein.
  • consisting essentially of means that the methods and compositions may include additional steps, components or ingredients, but only if the additional steps, components or ingredients do not materially alter the basic and novel characteristics of the claimed methods and compositions.
  • the alkaline detergent compositions include an alkalinity source.
  • the alkalinity source comprises an alkali metal carbonate.
  • suitable alkalinity sources include but are not limited to: alkali metal carbonates, such as sodium carbonate, potassium carbonate, bicarbonate, sesquicarbonate, and mixtures thereof.
  • the alkaline detergent compositions do not include a hydroxide alkalinity source.
  • the alkalinity source controls the pH of the use solution when water is added to the detergent 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.
  • the pH of the use solution is between about 9 and about 12.
  • the pH of the use solution is between about 9.5 and about 11.5.
  • the alkalinity source may also function as a hydratable salt to form a solid composition.
  • 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.
  • 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 detergent composition will depend on the alkalinity source/hydratable salt.
  • the detergent composition may also have free water which isn't attractively bound to a non-water molecule.
  • the alkaline detergent compositions include from about 10 wt-% - 95 wt-% alkalinity source, from about 25 wt-% - 90 wt-% alkalinity source, from about 40 wt-% - 85 wt-% alkalinity source, preferably from about 45 wt-% - 75 wt-% alkalinity source.
  • all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • the 2-in-1 alkaline compositions according to the invention employ a combination of surfactants to provide good cleanability and rinseability.
  • the surfactants of the alkaline detergent compositions include at least two nonionic surfactants.
  • the nonionic surfactants comprise an alcohol alkoxylate and an alkyl alkoxylate.
  • the nonionic surfactants are selected from the group consisting of an alcohol alkoxylate, an alkyl alkoxylate, an EO/PO copolymer, and combinations thereof.
  • the alkaline detergent compositions include from about 0.1 wt-% - 30 wt-% surfactants, from about 0.1 wt-% - 25 wt-% surfactants, from about 0.1 wt-% - 20 wt-% surfactants, from about 1 wt-% - 15 wt-% surfactants, from about 1 wt-% - 10 wt-% surfactants, and preferably from about 5 wt-% - 10 wt-% surfactants.
  • all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • the ratio of the alcohol alkoxylate to the alkyl alkoxylate is from about 1:5 to about 5:1, from about 1:3 to about 3:1, from about 1:2 to about 2:1, and preferably about 1:1.
  • the nonionic surfactants include an alkyl alkoxylate and alcohol alkoxylate in a ratio of about 1:1, from about 1:5 to about 5:1, from about 1:3 to about 3:1, or from about 1:2 to about 2:1.
  • the alkaline detergent composition includes an alkyl alkoxylate and alcohol alkoxylate in a ratio of about 1:1.
  • the 2-in-1 alkaline compositions according to the invention employ at least two nonionic surfactant comprising an alcohol alkoxylate.
  • suitable alcohol alkoxylates include ethylene oxide, propylene oxide, and butylene oxide groups and mixtures thereof. Particularly, suitable alcohol alkoxylates can have between about 1 and about 30 moles of alkyl oxide and carbon chains between about 4 and about 20 carbons in length.
  • the alcohol ethoxylate may be a C8-C18 alcohol alkoxylate with about 10 to about 40 moles of alkyl oxide.
  • the alcohol alkoxylate may be a C8-C16 alcohol alkoxylate with about 10 to about 30 moles of alkyl oxide.
  • the alcohol alkoxylate may be a C10-C12 alcohol alkoxylate with about 15 to about 25 moles of alkyl oxide.
  • preferred alcohol alkoxylates are available under the brands Surfonic (available from Huntsman), Rhodasurf (available from Rhodia), Novel (available from Sasol), Lutensol (available from BASF).
  • the alkaline detergent compositions include from about 0.1 wt-% to about 15wt-% alcohol alkoxylate, from about 0.1 wt-% to about 10 wt-% alcohol alkoxylate, from about 0.1 wt-% to about 7 wt-%, or from about 1 wt-% to about 49 wt-%.
  • the 2-in-1 alkaline compositions according to the invention employ an alkyl alkoxylate.
  • Alkyl alkoxylates having ethylene oxide and/or propylene oxide derivatives are particularly suitable for the alkaline compositions.
  • the alkyl alkoxylate includes an ethylene oxide, a propylene oxide, a butylene oxide, a pentalene oxide, a hexylene oxide, a heptalene oxide, an octalene oxide, a nonalene oxide, a decylene oxide, and mixtures thereof.
  • the alkyl group can be C8-C18, linear or branched.
  • the alkyl alkoxylate can be an EO/PO copolymer.
  • the EO/PO copolymer may have from about 1 to about 50 moles of EO and from about 1 to about 50 moles of PO.
  • the EO/PO copolymer is a block polymer.
  • the EO/PO copolymer does not contain a C8-18 alkyl group, or even any alkyl groups.
  • these EO/PO copolymer surfactants can include a compact alcohol EO/PO surfactant where the EO and PO groups are in small block form, or random form.
  • the alkyl alkoxylate includes an ethylene oxide, a propylene oxide, a butylene oxide, a pentalene oxide, a hexylene oxide, a heptalene oxide, an octalene oxide, a nonalene oxide, a decylene oxide, and mixtures thereof.
  • the alkyl group can be C10-C18, linear or branched.
  • the EO/PO copolymer surfactants are particularly suitable for use in the 2-in-1 alkaline compositions in combination with an alcohol alkoxylate surfactant.
  • exemplary commercially available surfactants are available, for example, under the tradename Pluronic ® and Pluronic R, (commercially available from BASF), Tetronic (available from Dow) and Surfonic (available from Huntsman).
  • ethylene oxide and/or propylene oxide derivative surfactants that may be used include polyoxyethylene-polyoxypropylene block copolymers, or the like, or derivatives thereof.
  • polyoxyethylene-polyoxypropylene block copolymers include those having the following formulae: (EO)x(PO)y(EO)x (PO)y(EO)x(PO)y (PO) y (EO) x (PO) y (EO) x (PO) y (EO) x (PO) y wherein EO represents an ethylene oxide group, PO represents a propylene oxide group, and x and y reflect the average molecular proportion of each alkylene oxide monomer in the overall block copolymer composition.
  • a preferred EO/PO copolymer is represented by the formula (EO)x(PO)y(EO)x.
  • a preferred EO/PO copolymer is represented by the formula (PO)y(EO)x(PO)y.
  • x is in the range of about 5 to about 50
  • y is in the range of about 1 to about 50
  • x plus y is in the range of about 6 to about 200. It should be understood that each x and y in a molecule can be different.
  • the material can have a molecular weight greater than about 200 and less than about 25,000.
  • the material can have a molecular weight in the range of about 500 to about 25,000, or in the range of about 1000 to about 20,000.
  • the EO/PO surfactants may have between about 1 and about 50 ethylene oxide groups and from about 1 to about 50 propylene oxide groups.
  • the material can have a molecular weight greater than about 400, and in some embodiments, greater than about 500.
  • the material can have a molecular weight (g/mol) in the range of about 500 to about 7000 or more, or in the range of about 950 to about 4000 or more, or in the range of about 1000 to about 3100 or more, or in the range of about 2100 to about 6700 or more, or in the range of about 2500 to about 4200 or more.
  • Nonionic Surfactants edited by Schick, M. J., Vol. 1 of the Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 provides further description of nonionic compounds generally employed in the practice of the present invention.
  • a typical listing of nonionic classes, and species of these surfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975 . Further examples are given in " Surface Active Agents and detergents" (Vol. I and II by Schwartz, Perry and Berch ). Each of these references is herein incorporated by reference in their entirety.
  • the alkaline detergent compositions include from about 0.1 wt-% to about 15 wt-% of the alkyl alkoxylate, from about 0. 1wt-% to about 10 wt-% of the alkyl alkoxylate), or from about 0.1 wt-% to about 7 wt-% the alkyl alkoxylate.
  • the present invention can include a polymer comprised of at least one polycarboxylic acid polymer, copolymer, and/or terpolymer.
  • Particularly suitable polycarboxylic acid polymers of the present invention include, but are not limited to, polyacrylic acid polymers and copolymers, polymaleic polymers and copolymers, and acrylic/maleic copolymers.
  • Other suitable polycarboxylic acid polymers include polymaleic acid homopolymers, polyacrylic acid copolymers, and maleic anhydride/olefin copolymers.
  • the polymer comprises, consists essentially of, or consists of a polyacrylic acid polymer, copolymer, terpolymer and/or salts thereof.
  • the detergent compositions of the present invention can use polyacrylic acid polymers, copolymers, and/or terpolymers.
  • Polyacrylic acids have the following structural formula: where n is any integer.
  • suitable polyacrylic acid polymers, copolymers, and/or terpolymers include but are not limited to, the polymers, copolymers, and/or terpolymers of polyacrylic acids, (C 3 H 4 O 2 ) n or 2-Propenoic acid, acrylic acid, polyacrylic acid, propenoic acid.
  • particularly suitable acrylic acid polymers, copolymers, and/or terpolymers have a molecular weight between about 100 and about 10,000, in a preferred embodiment between about 500 and about 7,000, in an even more preferred embodiment between about 1,000 and about 5,000, and in a most preferred embodiment between about 1,500 and about 4,500.
  • Polymaleic acid (C 4 H 2 O 3 )x or hydrolyzed polymaleic anhydride or cis-2-butenedioic acid homopolymer has the structural formula: where n and m are any integer.
  • Examples of polymaleic acid homopolymers, copolymers, and/or terpolymers (and salts thereof) which may be used for the invention are particularly preferred are those with a molecular weight of about 100 and about 10,000, more preferably between about 500 and about 7,000, in an even more preferred embodiment between about 1,000 and about 5,000, and in a most preferred embodiment between about 1,500 and about 4,500.
  • polymaleic acid homopolymers include the Belclene 200 series of maleic acid homopolymers from BWA TM Water Additives, 979 Lakeside Parkway, Suite 925 Tucker, GA 30084, USA and Aquatreat AR-801 available from AkzoNobel.
  • the polymer is a copolymer of acrylic acid and maleic acid.
  • an acrylic/maleic acid copolymer an acrylic/maleic copolymer has a molecular weight from about 1,000 to about 10,000 g/mol, preferably a molecular weight between about 1,000 to about 5,000 g/mol.
  • An example of a suitable acrylic/maleic acid copolymer includes, but is not limited to, Acusol 448 from The Dow Chemical Company, Wilmington Delaware, USA.
  • compositions will include the polymer in an amount between about 0.1 wt-% and about 50 wt-%, between about 0.1 wt-% and about 40 wt-%, between about 0.1 wt-% and about 30 wt-%, or 1 wt-% and about 20 wt-%. All ranges recited are inclusive of the numbers contained therein.
  • the polymer of the present invention can comprise, consist essentially of, or consist of at least one polyacrylic acid polymer, copolymer, and/or terpolymer. In addition, without being limited according to the invention, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • the 2-in-1 alkaline compositions according to the invention can further be combined with various functional components suitable for use in industrial ware wash applications.
  • the alkaline detergent and rinse aid compositions including the carbonate-based alkalinity source and nonionic surfactants (and/or polymers) make up a large amount or even substantially all of the total weight of the detergent composition. For example, in some embodiments few or no additional functional ingredients are disposed therein.
  • additional functional ingredients may be included in the compositions.
  • the functional ingredients provide desired properties and functionalities to the compositions.
  • the term "functional ingredient” 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.
  • compositions do not include additional alkalinity sources, namely alkali metal hydroxides. In further preferred embodiments, the compositions do not include rinse aids.
  • compositions may include builders, water conditioning agents, stabilizers, defoaming agents, anti-redeposition agents, bleaching agents, sanitizers, solubility modifiers, dispersants, anticorrosion agents and metal protecting agents, stabilizing agents, corrosion inhibitors, enzymes, additional sequestrants and/or chelating agents, fragrances and/or dyes, rheology modifiers or thickeners, hydrotropes or couplers, buffers, solvents, solidifying agents and the like.
  • the alkaline detergent composition can include one or more building agents, also called chelating or sequestering agents (e.g. builders) to treat or soften water and to prevent formation of precipitates or other salts.
  • building agents also called chelating or sequestering agents (e.g. builders) to treat or soften water and to prevent formation of precipitates or other salts.
  • chelating or sequestering agents e.g. builders
  • These may include, but are not limited to: condensed phosphates, alkali metal carbonates, alkali metal silicates and metasilicates, phosphonates, aminocarboxylic acids, and/or polycarboxylic acid polymers.
  • 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, about 5% to about 50% by weight, or about 20% 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, and between approximately 25% to approximately 50% by weight.
  • all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • 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 detergent composition by fixing the free water present in the composition as water of hydration.
  • a preferred builder is sodium tripolyphosphate anhydrous.
  • a preferred phosphonate combination is ATMP and HEDP.
  • 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.
  • the detergent 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), diethylenetriaminepentaacetic acid (DTPA), aspartic acid-N,N-diacetic acid (ASDA), methylglycinediacetic acid (MGDA), glutamic acid-N,N-diacetic acid (GLDA), ethylenediaminesuccinic acid (EDDS), 2-hydroxyethyliminodiacetic acid (HEIDA), iminodisuccinic acid (IDS), 3-hydroxy-2-2'-iminodisuccinic acid (HIDS) and other similar acids or salts thereof having an amino group with a carboxylic acid substituent.
  • the composition is free of
  • Water conditioning polymers can also 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 (-CO 2- ) groups such as polyacrylic acid, maleic acid, maleic/olefin copolymer, sulfonated copolymer or terpolymer, acrylic/maleic copolymer, polymethacrylic acid, acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, and hydrolyzed acrylonitrile-methacrylonitrile copolymers.
  • -CO 2- pendant carboxylate
  • 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, acrylic, methacrylic and itaconic acid or salts thereof.
  • ester functional groups include aryl, cyclic, aromatic and C 1 -C 10 linear, branched or substituted esters.
  • the alkaline detergent compositions can include one or more water conditioning agents.
  • phosphonic acids can be employed.
  • Phosphonic acids can be used in the form of water soluble acid salts, particularly the alkali metal salts, such as sodium or potassium; the ammonium salts; or the alkylol amine salts where the alkylol has 2 to 3 carbon atoms, such as mono-, di-, or triethanolamine salts.
  • Preferred phosphonates include the organic phosphonates.
  • Preferred organic phosphonates include phosphono butane tricarboxylic acid (PBTC) available from Bayer Corp. in Pittsburgh Pa.
  • compositions include from about 0.1 wt-% - 50 wt-% water conditioning agent, from about 1 wt-% - 40 wt-% water conditioning agent, from about 1 wt-% - 30 wt-% water conditioning agent, preferably from about 5 wt-% - 20 wt-% water conditioning agent.
  • all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • the alkaline detergent compositions may also include a neutralizing agent.
  • an alkaline neutralizing agent may be employed to neutralize acidic components, such as a water conditioning agent.
  • Suitable alkaline neutralizing agents may include for example alkali metal hydroxides, including but not limited to: sodium hydroxide, potassium hydroxide, lithium hydroxide, and combinations thereof.
  • An alkali metal hydroxide neutralizing agent 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. Additionally, more than one neutralizing agent may be used according to certain embodiments.
  • the compositions of the invention do not include hydroxides as alkalinity sources but only to neutralize acidic ingredients in the composition, including for example water conditioning agents such as HEDP.
  • the compositions include from about 0.1 wt-% - 50 wt-% neutralizing agent, from about 0.1 wt-% - 30 wt-% neutralizing agent, from about 1 wt-% - 25 wt-% neutralizing agent, preferably from about 10 wt-% - 25 wt-% neutralizing agent.
  • the neutralizing agent comprises alkali metal hydroxide in an amount of up to about 10 wt-%, preferably between about 0.01 wt-% and about 10 wt-%.
  • all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • the alkaline detergent compositions may also include an anti-etch agent capable of preventing etching in glass.
  • suitable anti-etch agents include adding metal ions to the composition such as zinc, zinc chloride, zinc gluconate, aluminum, and beryllium.
  • the corrosion inhibitor can refer to the combination of a source of aluminum ion and a source of zinc ion.
  • the source of aluminum ion and the source of zinc ion provide aluminum ion and zinc ion, respectively, when the solid detergent composition is provided in the form of a use solution.
  • the amount of the corrosion inhibitor is calculated based upon the combined amount of the source of aluminum ion and the source of zinc ion.
  • a source of aluminum ion Anything that provides an aluminum ion in a use solution can be referred to as a source of aluminum ion, and anything that provides a zinc ion when provided in a use solution can be referred to as a source of zinc ion. It is not necessary for the source of aluminum ion and/or the source of zinc ion to react to form the aluminum ion and/or the zinc ion.
  • Aluminum ions can be considered a source of aluminum ion, and zinc ions can be considered a source of zinc ion.
  • the source of aluminum ion and the source of zinc ion can be provided as organic salts, inorganic salts, and mixtures thereof.
  • Exemplary sources of aluminum ion include, but are not limited to: aluminum salts such as sodium aluminate, aluminum bromide, aluminum chlorate, aluminum chloride, aluminum iodide, aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum formate, aluminum tartrate, aluminum lactate, aluminum oleate, aluminum bromate, aluminum borate, aluminum potassium sulfate, aluminum zinc sulfate, and aluminum phosphate.
  • aluminum salts such as sodium aluminate, aluminum bromide, aluminum chlorate, aluminum chloride, aluminum iodide, aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum formate, aluminum tartrate, aluminum lactate, aluminum oleate, aluminum bromate, aluminum borate, aluminum potassium sulfate, aluminum zinc sulfate, and aluminum phosphate.
  • Exemplary sources of zinc ion include, but are not limited to: zinc salts such as zinc chloride, zinc sulfate, zinc nitrate, zinc iodide, zinc thiocyanate, zinc fluorosilicate, zinc dichromate, zinc chlorate, sodium zincate, zinc gluconate, zinc acetate, zinc benzoate, zinc citrate, zinc lactate, zinc formate, zinc bromate, zinc bromide, zinc fluoride, zinc fluorosilicate, and zinc salicylate.
  • zinc salts such as zinc chloride, zinc sulfate, zinc nitrate, zinc iodide, zinc thiocyanate, zinc fluorosilicate, zinc dichromate, zinc chlorate, sodium zincate, zinc gluconate, zinc acetate, zinc benzoate, zinc citrate, zinc lactate, zinc formate, zinc bromate, zinc bromide, zinc fluoride, zinc fluorosilicate, and zinc salicylate.
  • the composition preferably includes from about 0.001 wt-% to about 10 wt-%, more preferably from about 0.01 wt-% to about 7 wt-%, and most preferably from about 0.01 wt-% to about 1 wt-% of an anti-etch agent.
  • all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • the alkaline detergent compositions may optionally include an anticorrosion agent.
  • Anticorrosion agents provide compositions that generate surfaces that are shinier and less prone to biofilm buildup than surfaces that are not treated with compositions having anticorrosion agents.
  • Preferred anticorrosion agents which can be used according to the invention include phosphonates, phosphonic acids, triazoles, organic amines, sorbitan esters, carboxylic acid derivatives, sarcosinates, phosphate esters, zinc, nitrates, chromium, molybdate containing components, and borate containing components.
  • Exemplary phosphates or phosphonic acids are available under the name Dequest (i.e., Dequest 2000, Dequest 2006, Dequest 2010, Dequest 2016, Dequest 2054, Dequest 2060, and Dequest 2066) from Solutia, Inc. of St. Louis, Mo.
  • Exemplary triazoles are available under the name Cobratec (i.e., Cobratec 100, Cobratec TT-50-S, and Cobratec 99) from PMC Specialties Group, Inc. of Cincinnati, Ohio.
  • Exemplary organic amines include aliphatic amines, aromatic amines, monoamines, diamines, triamines, polyamines, and their salts.
  • Exemplary amines are available under the names Amp (i.e. Amp-95) from Angus Chemical Company of Buffalo Grove, Ill.; WGS (i.e., WGS-50) from Jacam Chemicals, LLC of Sterling, Kans.; Duomeen (i.e., Duomeen O and Duomeen C) from Akzo Nobel Chemicals, Inc.
  • sorbitan esters are available under the name Calgene (LA-series) from Calgene Chemical Inc. of Skokie, Ill.
  • Exemplary carboxylic acid derivatives are available under the name Recor (i.e., Recor 12) from Ciba-Geigy Corp. of Tarrytown, N.Y.
  • Exemplary sarcosinates are available under the names Hamposyl from Hampshire Chemical Corp. of Lexington, Mass.; and Sarkosyl from Ciba-Geigy Corp. of Tarrytown, N.Y.
  • the composition optionally includes an anticorrosion agent for providing enhanced luster to the metallic portions of a dish machine and/or providing shinier surfaces.
  • an anticorrosion agent is incorporated into the composition, it is preferably included in an amount of between about 0.01 wt-% and about 7.5 wt-%, between about 0.01 wt-% and about 5 wt-% and between about 0.01 wt-% and about 3 wt-%.
  • the alkaline detergent compositions may also include an antiredeposition agent capable of facilitating sustained suspension of soils in a cleaning solution and preventing the removed soils from being redeposited onto the substrate being cleaned.
  • an antiredeposition agent capable of facilitating sustained suspension of soils in a cleaning solution and preventing the removed soils from being redeposited onto the substrate being cleaned.
  • suitable antiredeposition agents include fatty acid amides, complex phosphate esters, styrene maleic anhydride copolymers, and cellulosic derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and the like.
  • the composition preferably includes from about 0.5 wt-% to about 10 wt-% and more preferably from about 1 wt-% to about 5 wt-% of an antiredeposition agent.
  • the alkaline detergent compositions can include one or more enzymes, which can provide desirable activity for removal of protein-based, carbohydrate-based, or triglyceride-based soils from substrates such as flatware, cups and bowls, and pots and pans.
  • Enzymes suitable for the inventive composition can act by degrading or altering one or more types of soil residues encountered on a surface thus removing the soil or making the soil more removable by a surfactant or other component of the cleaning composition. Both degradation and alteration of soil residues can improve detergency by reducing the physicochemical forces which bind the soil to the surface or textile being cleaned, i.e. the soil becomes more water soluble.
  • one or more proteases can cleave complex, macromolecular protein structures present in soil residues into simpler short chain molecules which are, of themselves, more readily desorbed from surfaces, solubilized, or otherwise more easily removed by detersive solutions containing said proteases.
  • Suitable enzymes include a protease, an amylase, a lipase, a gluconase, a cellulase, a peroxidase, or a mixture thereof of any suitable origin, such as vegetable, animal, bacterial, fungal or yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases. In some embodiments preferably the enzyme is a protease, a lipase, an amylase, or a combination thereof.
  • the composition preferably includes from about 0.001 wt-% to about 10 wt-%, from about 0.01 wt-% to about 10 wt-%, from about 0.05 wt-% to about 5 wt-%, and more preferably from about 0.1 wt-% to about 1 wt-% of enzyme(s).
  • the alkaline detergent compositions may optionally include an antimicrobial agent or preservative.
  • Antimicrobial agents are chemical compositions that can be used in the composition to prevent microbial contamination and deterioration of commercial products material systems, surfaces, etc. Antimicrobial agents may also be sanitizing agents. Generally, these materials fall in specific classes including phenolics, halogen compounds, quaternary ammonium compounds, metal derivatives, amines, alkanol amines, nitro derivatives, analides, organosulfur and sulfur-nitrogen compounds and miscellaneous compounds. The given antimicrobial agent depending on chemical composition and concentration may simply limit further proliferation of numbers of the microbe or may destroy all or a substantial proportion of the microbial population.
  • microbes and “microorganisms” typically refer primarily to bacteria and fungus microorganisms.
  • the antimicrobial agents are formed into the final product that when diluted and dispensed using an aqueous stream forms an aqueous disinfectant or sanitizer composition that can be contacted with a variety of surfaces resulting in prevention of growth or the killing of a substantial proportion of the microbial population.
  • Common antimicrobial agents that may be used include phenolic antimicrobials such as pentachlorophenol, orthophenylphenol; halogen containing antibacterial agents that may be used include sodium trichloroisocyanurate, sodium dichloroisocyanurate (anhydrous or dihydrate), iodine-poly(vinylpyrolidin-onen) complexes, bromine compounds such as 2-bromo-2-nitropropane-1,3-diol; quaternary antimicrobial agents such as benzalconium chloride, cetylpyridiniumchloride; amines and nitro containing antimicrobial compositions such as hexahydro-1,3,5-tris(2-hydr- oxyethyl)-s-triazine, dithiocarbamates such as sodium dimethyldithiocarbamate, and a variety of other materials known in the art for their microbial properties. Antimicrobial agents may be encapsulated to improve stability and/or to reduce re
  • an antimicrobial agent or preservative When incorporated into the composition, it is preferably included in an amount between about 0.01 wt-% to about 5 wt-%, between about 0.01 wt-% to about 2 wt-%, and between about 0.1 wt-% to about 1.0 wt-%.
  • a foam inhibitor may be included in addition to the nonionic surfactants of the alkaline cleaning compositions for reducing the stability of any foam that is formed.
  • foam inhibitors include silicon compounds such as silica dispersed in polydimethylsiloxane, fatty amides, hydrocarbon waxes, fatty acids, fatty esters, fatty alcohols, fatty acid soaps, ethoxylates, mineral oils, polyethylene glycol esters, polyoxyethylene-polyoxypropylene block copolymers, alkyl phosphate esters such as monostearyl phosphate and the like.
  • a discussion of foam inhibitors may be found, for example, in U.S. Pat. No. 3,048,548 to Martin et al ., U.S. Pat.
  • the composition preferably includes from about 0.0001 wt-% to about 5 wt-% and more preferably from about 0.01 wt-% to about 3 wt-% of the foam inhibitor.
  • compositions of invention may include additional surfactants.
  • Particularly suitable surfactants include nonionic surfactants, amphoteric surfactants, and zwitterionic surfactants.
  • the compositions are substantially free of cationic and/or anionic surfactants.
  • the compositions can include from about 0.01 wt-% - 40 wt-% additional surfactants, preferably from about 0.1 wt-% - 30 wt-% additional surfactant, more preferably from about 1 wt-% - 25 wt-% additional surfactant.
  • all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • Suitable nonionic surfactants suitable for use with the compositions of the present invention include alkoxylated surfactants.
  • Suitable alkoxylated surfactants include EO/PO copolymers, capped EO/PO copolymers, alcohol alkoxylates, capped alcohol alkoxylates, mixtures thereof, or the like.
  • Suitable alkoxylated surfactants for use as solvents include EO/PO block copolymers, such as the Pluronic and reverse Pluronic surfactants; alcohol alkoxylates, such as Dehypon LS-54 (R-(EO) 5 (PO) 4 ) and Dehypon LS-36 (R-(EO) 3 (PO) 6 ); and capped alcohol alkoxylates, such as Plurafac LF221 and Tegoten EC 11; mixtures thereof, or the like.
  • EO/PO block copolymers such as the Pluronic and reverse Pluronic surfactants
  • alcohol alkoxylates such as Dehypon LS-54 (R-(EO) 5 (PO) 4 ) and Dehypon LS-36 (R-(EO) 3 (PO) 6 )
  • capped alcohol alkoxylates such as Plurafac LF221 and Tegoten EC 11; mixtures thereof, or the like.
  • the semi-polar type of nonionic surface active agents is another class of nonionic surfactant useful in compositions of the present invention.
  • Semi-polar nonionic surfactants include the amine oxides, phosphine oxides, sulfoxides and their alkoxylated derivatives.
  • Amine oxides are tertiary amine oxides corresponding to the general formula: wherein the arrow is a conventional representation of a semi-polar bond; and, R 1 , R 2 , and R 3 may be aliphatic, aromatic, heterocyclic, alicyclic, or combinations thereof.
  • R 1 is an alkyl radical of from about 8 to about 24 carbon atoms
  • R 2 and R 3 are alkyl or hydroxyalkyl of 1-3 carbon atoms or a mixture thereof
  • R 2 and R 3 can be attached to each other, e.g.
  • R 4 is an alkylene or a hydroxyalkylene group containing 2 to 3 carbon atoms; and n ranges from 0 to about 20.
  • An amine oxide can be generated from the corresponding amine and an oxidizing agent, such as hydrogen peroxide.
  • Useful water soluble amine oxide surfactants are selected from the octyl, decyl, dodecyl, isododecyl, coconut, or tallow alkyl di-(lower alkyl) amine oxides, specific examples of which are octyldimethylamine oxide, nonyldimethylamine oxide, decyldimethylamine oxide, undecyldimethylamine oxide, dodecyldimethylamine oxide, iso-dodecyldimethyl amine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylamine oxide, heptadecyldimethylamine oxide, octadecyldimethylaine oxide, dodecyldipropylamine oxide, tetradecyldipropylamine oxide, hexadecyl
  • Amphoteric, or ampholytic, surfactants contain both a basic and an acidic hydrophilic group and an organic hydrophobic group. These ionic entities may be any of anionic or cationic groups described herein for other types of surfactants.
  • a basic nitrogen and an acidic carboxylate group are the typical functional groups employed as the basic and acidic hydrophilic groups.
  • surfactants sulfonate, sulfate, phosphonate or phosphate provide the negative charge.
  • Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphate, or phosphono.
  • Amphoteric surfactants are subdivided into two major classes known to those of skill in the art and described in " Surfactant Encyclopedia” Cosmetics & Toiletries, Vol. 104 (2) 69-71 (1989 ), which is herein incorporated by reference in its entirety.
  • the first class includes acyl/dialkyl ethylenediamine derivatives (e.g. 2-alkyl hydroxyethyl imidazoline derivatives) and their salts.
  • the second class includes N-alkylamino acids and their salts.
  • Amphoteric surfactants can be synthesized by methods known to those of skill in the art. For example, 2-alkyl hydroxyethyl imidazoline is synthesized by condensation and ring closure of a long chain carboxylic acid (or a derivative) with dialkyl ethylenediamine. Commercial amphoteric surfactants are derivatized by subsequent hydrolysis and ring-opening of the imidazoline ring by alkylation -- for example with chloroacetic acid or ethyl acetate. During alkylation, one or two carboxy-alkyl groups react to form a tertiary amine and an ether linkage with differing alkylating agents yielding different tertiary amines.
  • Long chain imidazole derivatives having application in the present invention generally have the general formula: wherein R is an acyclic hydrophobic group containing from about 8 to 18 carbon atoms and M is a cation to neutralize the charge of the anion, generally sodium.
  • Commercially prominent imidazoline-derived amphoterics that can be employed in the present compositions include for example: Cocoamphopropionate, Cocoamphocarboxypropionate, Cocoamphoglycinate, Cocoamphocarboxy-glycinate, Cocoamphopropylsulfonate, and Cocoamphocarboxy-propionic acid.
  • Amphocarboxylic acids can be produced from fatty imidazolines in which the dicarboxylic acid functionality of the amphodicarboxylic acid is diacetic acid and/or dipropionic acid.
  • Betaines are a special class of amphoteric discussed herein below in the section entitled, Zwitterion Surfactants.
  • Examples of commercial N-alkylamino acid ampholytes having application in this invention include alkyl beta-amino dipropionates, RN(C 2 H 4 COOM) 2 and RNHC 2 H 4 COOM.
  • R can be an acyclic hydrophobic group containing from about 8 to about 18 carbon atoms, and M is a cation to neutralize the charge of the anion.
  • Suitable amphoteric surfactants include those derived from coconut products such as coconut oil or coconut fatty acid. Additional suitable coconut derived surfactants include as part of their structure an ethylenediamine moiety, an alkanolamide moiety, an amino acid moiety, e.g., glycine, or a combination thereof; and an aliphatic substituent of from about 8 to 18 ( e.g., 12) carbon atoms. Such a surfactant can also be considered an alkyl amphodicarboxylic acid.
  • amphoteric surfactants can include chemical structures represented as: C 12 -alkyl-C(O)-NH-CH 2 -CH 2 -N + (CH 2 -CH 2 -CO 2 Na) 2 -CH 2 -CH 2 -OH or C 12 -alkyl-C(O)-N(H)-CH 2 -CH 2 -N + (CH 2 -CO 2 Na) 2 -CH 2 -CH 2 -OH.
  • Disodium cocoampho dipropionate is one suitable amphoteric surfactant and is commercially available under the tradename Miranol TM FBS from Rhodia Inc., Cranbury, N.J.
  • Another suitable coconut derived amphoteric surfactant with the chemical name disodium cocoampho diacetate is sold under the tradename Mirataine TM JCHA, also from Rhodia Inc., Cranbury, N.J.
  • Zwitterionic surfactants can be thought of as a subset of the amphoteric surfactants and can include an anionic charge.
  • Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
  • a zwitterionic surfactant includes a positive charged quaternary ammonium or, in some cases, a sulfonium or phosphonium ion; a negative charged carboxyl group; and an alkyl group.
  • Zwitterionics generally contain cationic and anionic groups which ionize to a nearly equal degree in the isoelectric region of the molecule and which can develop strong" inner-salt" attraction between positive-negative charge centers.
  • zwitterionic synthetic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • a general formula for these compounds is: wherein R 1 contains an alkyl, alkenyl, or hydroxyalkyl radical of from 8 to 18 carbon atoms having from 0 to 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety; Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R 2 is an alkyl or monohydroxy alkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom, R 3 is an alkylene or hydroxy alkylene or hydroxy alkylene of from 1 to 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
  • zwitterionic surfactants having the structures listed above include: 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate; 5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate; 3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane-1-phosphate; 3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propane-1-phosphonate; 3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate; 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy-propane-1-sulfonate;
  • the zwitterionic surfactant suitable for use in the present compositions includes a betaine of the general structure: These surfactant betaines typically do not exhibit strong cationic or anionic characters at pH extremes nor do they show reduced water solubility in their isoelectric range. Unlike “external" quaternary ammonium salts, betaines are compatible with anionics.
  • betaines examples include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C 12-14 acylamidopropylbetaine; C 8-14 acylamidohexyldiethyl betaine; 4-C 14-16 acylmethylamidodiethylammonio-1-carboxybutane; C 16-18 acylamidodimethylbetaine; C 12-16 acylamidopentanediethylbetaine; and C 12-16 acylmethylamidodimethylbetaine.
  • Sultaines useful in the present invention include those compounds having the formula (R(R 1 ) 2 N + R 2 SO 3- , in which R is a C 6 -C 18 hydrocarbyl group, each R 1 is typically independently C 1 -C 3 alkyl, e.g. methyl, and R 2 is a C 1 -C 6 hydrocarbyl group, e.g. a C 1 -C 3 alkylene or hydroxyalkylene group.
  • compositions of the present invention include a betaine.
  • the compositions can include cocoamido propyl betaine.
  • Exemplary ranges of the 2-in-1 alkaline detergent compositions according to the invention are shown in Tables 1A and 1B in weight percentage of the solid detergent compositions.
  • Tables 1A and 1B Exemplary ranges of the 2-in-1 alkaline detergent compositions according to the invention are shown in Tables 1A and 1B in weight percentage of the solid detergent compositions.
  • TABLE 1A Material First Exemplary Range wt-% Second Exemplary Range wt-% Third Exemplary Range wt-% Fourth Exemplary Range wt-% Alkalinity Source 10-95 25-90 40-85 45-75 Builders 0.1-50 1-50 5-45 10-35 Surfactants 0.01-30 0.
  • the detergent compositions may include concentrate compositions or may be diluted to form use compositions.
  • a concentrate refers to a composition that is intended to be diluted with water to provide a use solution that contacts an object to provide the desired cleaning, rinsing, or the like.
  • the detergent composition that contacts the articles to be washed can be referred to as a concentrate or a use composition (or use solution) dependent upon the formulation employed in methods according to the invention. It should be understood that the concentration of the aminocarboxylate, water conditioning agent, alkalinity, water and other optional functional ingredients in the detergent composition will vary depending on whether the detergent composition is provided as a concentrate or as a use solution.
  • a use solution may be prepared from the concentrate by diluting the concentrate with water at a dilution ratio that provides a use solution 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 diluent, 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 1:10,000 concentrate to water.
  • the concentrate is diluted at a ratio of between about 1:100 and about 1:5,000 concentrate to water. More particularly, the concentrate is diluted at a ratio of between about 1:250 and about 1 :2,000 concentrate to water.
  • methods of the present invention involve using the steps of providing an alkaline 2-in-1 detergent composition as disclosed herein.
  • methods of use preferably employ a solid alkaline 2-in-1 detergent composition, wherein a solid composition is inserted into a dispenser in or associated with an dish machine, particularly an industrial warewash machine.
  • the solid composition may be provided as a multiple-use dosage having between about 10 and about 10,000 doses per solid composition.
  • the solid composition can be formulated in a single-use composition, where it is used one time in a wash.
  • the methods also include forming a wash solution with the alkaline 2-in-1 detergent composition and water, contacting a soil on an article in the dish machine with the wash solution, removing the soil, and rinsing the article with potable water without requiring the use of a separate rinse aid composition.
  • the rinse is with potable water only.
  • the methods of the present invention may involve providing the individual components of the 2-in-1 detergent composition separately and mixing the individual components in situ with water to form a desired wash solution.
  • the 2-in-1 detergent compositions described above are inserted into a dispenser of a dish machine.
  • the dispenser may be selected from a variety of different dispensers depending of the physical form of the composition.
  • a liquid composition may be dispensed using a pump, either peristaltic or bellows for example, syringe/plunger injection, gravity feed, siphon feed, aspirators, unit dose, for example using a water soluble packet such as polyvinyl alcohol, or a foil pouch, evacuation from a pressurized chamber, or diffusion through a membrane or permeable surface.
  • the composition may be dispensed using a pump such as a peristaltic or bellows pump, syringe/plunger injection, caulk gun, unit dose, for example using a water soluble packet such as polyvinyl alcohol or a foil pouch, evacuation from a pressurized chamber, or diffusion through a membrane or permeable surface.
  • a pump such as a peristaltic or bellows pump, syringe/plunger injection, caulk gun
  • unit dose for example using a water soluble packet such as polyvinyl alcohol or a foil pouch, evacuation from a pressurized chamber, or diffusion through a membrane or permeable surface.
  • the composition may be dispensed using a spray, flood, auger, shaker, tablet-type dispenser, unit dose using a water soluble packet such as polyvinyl alcohol or foil pouch, or diffusion through a membrane or permeable surface.
  • the dispenser may also be a dual dispenser in which one component, is dispensed on one side and another component is dispensed on another side.
  • These exemplary dispensers may be located in or associated with a variety of dish machines including under the counter dish machines, bar washers, door machines, conveyor machines, or flight machines.
  • the dispenser may be located inside the dish machine, remote, or mounted outside of the dishwasher.
  • a single dispenser may feed one or more dish machines.
  • the wash solution comprises the alkaline 2-in-1 detergent composition and water from the dish machine.
  • the water may be any type of water including hard water, soft water, clean water, or dirty water.
  • the most preferred wash solution is one that maintains the preferred pH ranges of about 7 to about 11.5, more preferably about 9.5 to about 11.5, as measured by a pH probe based on a solution of the composition in a 16 gallon dish machine. The same probe may be used to measure millivolts if the probe allows for both functions, simply by switching the probe from pH to millivolts.
  • the dispenser or the dish machine may optionally include a pH probe to measure the pH of the wash solution throughout the wash cycle.
  • concentration or water to detergent ratio depends on the particular surfactant used. Exemplary concentration ranges may include up to 3000 ppm, preferably 1 to 3000 ppm, more preferably 100 to 3000 ppm and most preferably 300 to 2000 ppm. Again, the actual concentration used depends on the surfactant chosen.
  • a use solution can have an elevated temperature (i.e. heated to an elevated temperature when used according to the methods of the invention.
  • a use solution having a temperature between approximately 120°F and about 185°F, between about 140°F and approximately 185°F is contacted with the substrate to be cleaned.
  • a use solution having a temperature between approximately 150°F and approximately 160°F is contacted with the substrate to be cleaned.
  • the wash solution contacts a soil on an article in the dish machine.
  • soils include soils typically encountered with food such as proteinaceous soils, hydrophobic fatty soils, starchy and sugary soils associated with carbohydrates and simple sugars, soils from milk and dairy products, fruit and vegetable soils, and the like.
  • Soils can also include minerals, from hard water for example, such as potassium, calcium, magnesium, and sodium.
  • Articles that may be contacted include articles made of glass, plastic, aluminum, steel, copper, brass, silver, rubber, wood, ceramic, and the like.
  • Articles include things typically found in a dish machine such as glasses, bowls, plates, cups, pots and pans, bakeware such as cookie sheets, cake pans, muffin pans etc., silverware such as forks, spoons, knives, cooking utensils such as wooden spoons, spatulas, rubber scrapers, utility knives, tongs, grilling utensils, serving utensils, etc.
  • the wash solution may contact the soil in a number of ways including spraying, dipping, sump-pump solution, misting and fogging.
  • the soil is removed from the article.
  • the removal of the soil from the article is accomplished by the chemical reaction between the wash solution and the soil as well as the mechanical action of the wash solution on the article depending on how the wash solution is contacting the article.
  • the articles are rinsed as part of the dish machine wash cycle employing potable water without the use of a separate or additional rinse aid composition.
  • the methods can include more steps or fewer steps than laid out here.
  • the method can include additional steps normally associated with a dish machine wash cycle.
  • the method can also optionally include the use of an acidic detergent.
  • the method can optionally include alternating the acidic detergent with an alkaline detergent as described.
  • compositions of the present invention may include liquid products, thickened liquid products, gelled liquid products, paste, granular and pelletized solid compositions, powders, solid block compositions, cast solid block compositions, extruded solid block composition and others.
  • Solid particulate materials can be made by merely blending the dry solid ingredients in appropriate ratios or agglomerating the materials in appropriate agglomeration systems.
  • Pelletized materials can be manufactured by compressing the solid granular or agglomerated materials in appropriate pelletizing equipment to result in appropriately sized pelletized materials.
  • Solid block and cast solid block materials can be made by introducing into a container either a prehardened block of material or a castable liquid that hardens into a solid block within a container.
  • Preferred containers include disposable plastic containers or water soluble film containers.
  • Other suitable packaging for the composition includes flexible bags, packets, shrink wrap, and water soluble film such as polyvinyl alcohol.
  • the solid detergent 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 components 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 detergent composition hardens to a solid form.
  • the structure of the matrix may be characterized according to its hardness, melting point, material distribution, crystal structure, and other like properties according to known methods in the art.
  • a solid detergent 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.
  • the liquid and solid components are introduced into final mixing system and are continuously mixed until the components form a substantially homogeneous semi-solid mixture in which the components are distributed throughout its mass.
  • the mixture is then discharged from the mixing system into, or through, a die or other shaping means.
  • the product is then packaged.
  • the formed composition begins to harden to a solid form in between approximately 1 minute and approximately 3 hours.
  • 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.
  • the liquid and solid components are introduced into the final mixing system and are continuously mixed until the components form a substantially homogeneous liquid mixture in which the components are distributed throughout its mass.
  • the components are mixed in the mixing system for at least approximately 60 seconds.
  • 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.
  • 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.
  • a flowable solid such as granular solids or other particle solids including binding agents (e.g. hydrated chelating agent, such as a hydrated aminocarboxylate, a hydrated polycarboxylate or hydrated anionic polymer, a hydrated citrate salt or a hydrated tartrate salt, or the like together with an alkali metal carbonate) are combined under pressure.
  • binding agents e.g. hydrated chelating agent, such as a hydrated aminocarboxylate, a hydrated polycarboxylate or hydrated anionic polymer, a hydrated citrate salt or a hydrated tartrate salt, or the like together with an alkali metal carbonate
  • a form e.g., a mold or container
  • the method can include gently pressing the flowable solid in the form to produce the solid cleaning composition. Pressure may be applied by a block machine or a turntable press, or the like.
  • Pressure may be applied at about 1 to about 2000 psi, about 1 to about 300 psi, about 5 psi to about 200 psi, or about 10 psi to about 100 psi.
  • the methods can employ pressures as low as greater than or equal to about 1 psi, greater than or equal to about 2, greater than or equal to about 5 psi, or greater than or equal to about 10 psi.
  • the term "psi" or “pounds per square inch” refers to the actual pressure applied to the flowable solid being pressed and does not refer to the gauge or hydraulic pressure measured at a point in the apparatus doing the pressing.
  • the method can include a curing step to produce the solid cleaning composition.
  • an uncured composition including the flowable solid is compressed to provide sufficient surface contact between particles making up the flowable solid that the uncured composition will solidify into a stable solid cleaning composition.
  • a sufficient quantity of particles (e.g. granules) in contact with one another provides binding of particles to one another effective for making a stable solid composition.
  • Inclusion of a curing step may include allowing the pressed solid to solidify for a period of time, such as a few hours, or about 1 day (or longer).
  • the methods could include vibrating the flowable solid in the form or mold, such as the methods disclosed in U.S. Patent No. 8,889,048 , which is herein incorporated by reference in its entirety.
  • Pressed solids overcome such various limitations of other solid formulations for which there is a need for making solid cleaning compositions. Moreover, pressed solid compositions retain its shape under conditions in which the composition may be stored or handled.
  • 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.
  • a solid may be in various forms such as a powder, a flake, a granule, a pellet, a tablet, a lozenge, a puck, a briquette, a brick, a solid block, a unit dose, or another solid form known to those of skill in the art.
  • the degree of hardness of the solid cast composition and/or a pressed solid 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 detergent composition under the expected conditions of storage and use of the solid detergent composition. In general, it is expected that the detergent 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 detergent 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; pressed solid; 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 approximately 10 kilograms.
  • 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 solution.
  • 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.
  • Liquid compositions can typically be made by forming the ingredients in an aqueous liquid or aqueous liquid solvent system. Such systems are typically made by dissolving or suspending the active ingredients in water or in compatible solvent and then diluting the product to an appropriate concentration, either to form a concentrate or a use solution thereof. Gelled compositions can be made similarly by dissolving or suspending the active ingredients in a compatible aqueous, aqueous liquid or mixed aqueous organic system including a gelling agent at an appropriate concentration.
  • Embodiments of the present invention are further defined in the following nonlimiting Examples. It should be understood that these Examples, while indicating certain embodiments of the invention, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the embodiments of the invention to adapt it to various usages and conditions. Thus, various modifications of the embodiments of the invention, in addition to those shown and described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.
  • Additional materials commercially-available from multiple sources include: sodium carbonate, ash monohydrate, sodium tripolyphosphate (anhydrous), zinc chloride, HEDP, and KOH.
  • Examples 1-4 an exemplary 2-in-1 detergent was prepared and is shown in Table 2. Throughout Examples 1-4, the formulation is referred to as Experimental Formula 1 (Exp. 1). TABLE 2 Raw material Exp. 1 Alkalinity source 45-75 Builder 10-30 Alkyl alkoxylate (EO/PO copolymer) 1-10 Alcohol alkoxylate 1-10 Sanitizing agent 1-10 Corrosion inhibitor 0.01-0.5 Phosphonate builder, 60% 1-10 KOH, 45% 1-10 Total 100
  • Detergent Control 1 and Detergent Control 2 are commercially available detergents (phosphate-based detergents).
  • Rinse Aid Control 1 and Rinse Aid Control 2 are two commercially available rinse aids (employing higher amounts of active ingredients and surfactants of at least two ionic categories (e.g. nonionic and cationic)).
  • the use concentrations for all experiments described below are provided in the following table: TABLE 3 Sample Use concentration [ppm] DI water N/A Detergent Control 1 1500 Detergent Control 2 1000 Rinse Aid Control 1 536 Rinse Aid Control 2 536 Exp. 1 1415
  • the SITA science line t60 measures the dynamic surface tension of liquids up to the semi-static range. Air bubbles are generated from a capillary with known radius. The bubble pressure is measured as a function of bubble life time, which can be correlated to the surface tension according to the Young-Laplace equation. Dynamic surface tension provides insight into the dynamic behavior of surfactants and other surface active compounds under dynamic conditions, i.e. how quick surfactants can reach a surface. The dynamic surface tension is a function of concentration, temperature and type of surfactant. The dynamic surface tension behavior of surfactants is particularly important in applications where a quick response of surfactants is required, for example, in the short rinse cycles of automated dishwashing.
  • the SITA science line t60 was calibrated with DI water. Clean water samples after calibration should have a surface tension of 72.0 ⁇ 1.0mN/m (depending on water quality and temperature). Following calibration, the SITA was programmed to take readings at the desired time intervals (i.e., 0.3, 1.6, 3.0, and 9.1 seconds). Three separate solutions at the desired ppm were prepared for each composition (described as Samples A-C) to be tested (e.g., three samples of Exp. 1, three samples of Detergent Control 1). 10-15 mL were transferred into 20 mL vials and immersed in a heated oil bath to 72 °C (160 °F) ⁇ 2°C. The samples were equilibrated for 10-15 minutes.
  • the detergent was dispensed such that when the detergent was mixed with water during the cycle to form a use solution, the detergent concentration in the use solution was 750 parts per million (ppm).
  • the solution in the wash tank was titrated to verify detergent concentration.
  • the warewash machine had a washbath volume of 58 liters, a rinse volume of 2.8 liters, a wash time of 50 seconds, and a rinse time of 9 seconds.
  • the 100 cycle test was then started. At the beginning of each wash cycle, the appropriate amount of detergent was automatically dispensed into the warewash machine to maintain the initial detergent concentration. The detergent concentration was controlled by conductivity.
  • the light box test used a digital camera, a light box, a light source, a light meter and a control computer employing "Spot Advance” and "Image Pro Plus” commercial software.
  • a glass to be evaluated was placed on its side on the light box, and the intensity of the light source was adjusted to a predetermined value using the light meter.
  • a photographic image of the glass was taken and saved to the computer.
  • the software was then used to analyze the upper half of the glass, and the computer displayed a histogram graph with the area under the graph being proportional to the thickness of the film.
  • a lower light box score indicates that more light was able to pass through the tumbler.
  • the lower the light box score the more effective the composition was at preventing scale on the surface of the tumbler.
  • a clean, unused glass tumbler has a light box score of approximately 12,000, which corresponds to a score of 72,000 for the six glass tumblers
  • a clean, unused plastic tumbler has a light box score of approximately 25,500, which corresponds to a light box score of approximately 102,000 for the four plastic tumblers.
  • the minimum obtainable light box score i.e., sum of six clean glass tumblers and four clean plastic tumblers
  • a detergent composition is considered effective for controlling hard water scale if the sum of the light box scores for six glass tumblers and four plastic tumblers is approximately 360,000 or less.
  • compositions according to the invention and controls were further evaluated using a 50 cycle redeposition experiment for institutional ware wash detergents.
  • a 50 cycle redeposition experiment for institutional ware wash detergents.
  • 6 10 oz. Libby heat resistant glass tumblers and 1 plastic tumblers were used. The glass tumblers were cleaned prior to use. New plastic tumblers were used for each experiment.
  • a food soil solution was prepared using a 50/50 combination of beef stew and hot point soil and employed at 2000 ppm soil.
  • the soil included two cans of Dinty Moore Beef Stew (1360 grams), one large can of tomato sauce (822 grams), 15.5 sticks of Blue Bonnet Margarine (1746 grams) and powered milk (436.4 grams).
  • the hot point soil was added to the machine to maintain a sump concentration of about 2000 ppm.
  • the heaters were turned on.
  • the wash temperature was adjusted to about 150-160°F.
  • the final rinse temperature was adjusted to about 175-190°F.
  • the controller was set to disclose the amount of detergent in the wash tank.
  • the dishmachine was then started and run through an automatic cycle. At the beginning of each cycle the appropriate amount of hot point sol was added to maintain the sump concentration of 2000 ppm.
  • the detergent concentration is controlled by conductivity.
  • the glasses were allowed to dry overnight. Thereafter they were graded for spots and film accumulation (visual).
  • the glass and plastic tumblers were then graded for protein accumulation using Commassie Brilliant Blue R stain followed by destaining with an aqueous acetic acid/methanol solution.
  • the Commassie Brilliant Blue R stain was prepared by combining 1.25 g of Commassie Brilliant Blue R dye with 45 mL of acetic acid and 455 mL of 50% methanol in distilled water.
  • the destaining solution consisted of 45% methanol and 10% acetic acid in distilled water.
  • the amount of protein remaining on the glass and plastic tumblers after destaining was rated visually on a scale of 1 to 5.
  • a rating of 1 indicated no protein was present after destaining - no spots/no film.
  • a rating of 2 indicated that random areas (barely perceptible) were covered with protein after destaining - spots at random (or about 20% surface covered in film).
  • a rating of 3 indicated that about a quarter to half of the surface was covered with protein after destaining (or about 40% surface covered in film).
  • a rating of 4 indicated that about half of the glass/plastic surface was covered with protein after destaining (or about 60% surface covered in film).
  • a rating of 5 indicated that the entire surface was coated with protein after destaining (or at least about 80% surface covered in film).
  • the ratings of the glass tumblers tested for soil removal were averaged to determine an average soil removal rating from glass surfaces and the ratings of the plastic tumblers tested for soil removal were averaged to determine an average soil removal rating from plastic surfaces.
  • the ratings of the glass tumblers tested for redeposition were averaged to determine an average redeposition rating for glass surfaces and the ratings of the plastic tumblers tested for redeposition were averaged to determine an average redeposition rating for plastic surfaces.
  • a food soil solution was prepared using a 50/50 combination of beef stew and hot point soil.
  • the concentration of the solution was about 2000 ppm.
  • the soil included two cans of Dinty Moore Beef Stew (1360 grams), one large can of tomato sauce (822 grams), 15.5 sticks of Blue Bonnet Margarine (1746 grams) and powered milk (436.4 grams).
  • the dishmachine was then filled with an appropriate amount of water. After filling the dishmachine with the water, the heaters were turned on. The final rinse temperature was adjusted to about 180.degree. F.
  • the glasses and plastic tumblers were soiled by rolling the glasses in a 1:1 (by volume) mixture of Campbell's Cream of Chicken Soup: Kemp's Whole Milk three times. The glasses were then placed in an oven at about 160.degree. F. for about 8 minutes. While the glasses were drying, the dishmachine was primed with about 120 grams of the food soil solution, which corresponds to about 2000 ppm of food soil in the pump.
  • the dishmachine was then started and run through an automatic cycle.
  • the cycle ended the top of the glass and plastic tumblers were mopped with a dry towel.
  • the glass and plastic tumblers being tested for soil removal were removed and the soup/milk soiling procedure was repeated.
  • the redeposition glass and plastic tumblers were not removed.
  • the glass and plastic tumblers were then graded for protein accumulation using Coommassie Brilliant Blue R stain followed by destaining with an aqueous acetic acid/methanol solution.
  • the Coommassie Brilliant Blue R stain was prepared by combining about 1.25 g of Coommassie Brilliant Blue R dye with about 45 mL of acetic acid and about 455 mL of 50% methanol in distilled water.
  • the destaining solution consisted of 45% methanol and 10% acetic acid in distilled water.
  • the amount of protein remaining on the glass and plastic tumblers after destaining was rated visually on a scale of 1 to 5. A rating of 1 indicated no protein was present after destaining.
  • a rating of 2 indicated that random areas (barely perceptible) were covered with protein after destaining.
  • a rating of 3 indicated that about a quarter of the surface was covered with protein after destaining.
  • a rating of 4 indicated that about half of the glass/plastic surface was covered with protein after destaining.
  • a rating of 5 indicated that the entire surface was coated with protein after destaining.
  • the ratings of the glass tumblers tested for protein removal were averaged to determine an average protein removal rating from glass surfaces and the ratings of the plastic tumblers tested for protein removal were averaged to determine an average protein removal rating from plastic surfaces.
  • the ratings of the glass tumblers tested for redeposition were averaged to determine an average protein redeposition rating for glass surfaces and the ratings of the plastic tumblers tested for protein redeposition were averaged to determine an average protein redeposition rating for plastic surfaces.
  • Glasses are rated visually in the glass viewing area against a black background. Rate each set of glasses as a set, i.e., all redeposition glasses for all products tested. An overall average can be determined for each set. The rating scale used is shown in Table 12. TABLE 12 Rating Spots Film Protein 1 No spots No Film No Protein 2 Spots at random 20% of surface covered in film 20% remains 3 1/4 glass spotted 40% of the surface covered in film 40% remains 4 1/2 glass spotted 60% of the surface covered in film 80% remains 5 Whole glass spotted At least 80% of the surface covered in film 100% remains
  • Protein Glass Score 1 1.0 (0.0) 1.0 (0.0) 1.0 (0.0) 1.0 (0.0) 1.0 (0.0) 2 1.0 (0.0) 3 1.0 (0.0) Avg. Protein Plastic Score 1 1.0 (0.0) 1.0 (0.0) 1.0 (0.0) 1.0 (0.0) 1.0 (0.0) 2 1.5 (0.5) 3 1.0 (0.0) TABLE 14 7-cycle Soil removal Exp. Detergent Control 1 Detergent Control 2 Detergent Control 1 + Rinse Aid Control 2 Detergent Control 2 + Rinse Aid Control 1 Exp. 1 Avg. Glass Score Spots 1 5.0 (0.0) 4.8 (0.2) 1.0 (0.0) 4.2 (1.1) 3.5 (1.2) 2 4.1 (0.9) 3 1.5 (0.7) Avg.
  • Additional materials commercially-available from multiple sources include: sodium carbonate, ash monohydrate, sodium tripolyphosphate (anhydrous), zinc chloride, HEDP, and KOH.
  • Detergent Control 1 and Detergent Control 2 are commercially available detergents (phosphate-based detergents).
  • Rinse Aid Control 1 and rinse Aid Control are two commercially available rinse aids (employing higher amounts of active ingredients surfactants of at least two ionic categories (e.g., nonionic and cationic)).
  • the use concentrations for all experiments described below are provided in Table 16: TABLE 16 Sample Use concentration [ppm] DI water N/A Detergent Control 1 1500 Detergent Control 2 1000 Rinse Aid Control 1 536 Rinse Aid Control 2 536 Exp. 2 1415
  • the SITA science line t60 measures the dynamic surface tension of liquids up to the semi-static range. Air bubbles are generated from a capillary with known radius. The bubble pressure is measured as a function of bubble life time, which can be correlated to the surface tension according to the Young-Laplace equation. Dynamic surface tension provides insight into the dynamic behavior of surfactants and other surface active compounds under dynamic conditions, i.e. how quick surfactants can reach a surface. The dynamic surface tension is a function of concentration, temperature and type of surfactant. The dynamic surface tension behavior of surfactants is particularly important in applications where a quick response of surfactants is required, for example, in the short rinse cycles of automated dishwashing.
  • the SITA science line t60 was calibrated with DI water. Clean water samples after calibration should have a surface tension of 72.0 ⁇ 1.0mN/m (depending on water quality and temperature). Following calibration, the SITA was programmed to take readings at the desired time intervals (i.e., 0.3, 1.6, 3.0, and 9.1 seconds). Three separate solutions at the desired ppm were prepared for each composition (described as A-C) to be tested (e.g., three samples of Exp. 2, three samples of Detergent Control 1). 10-15 mL were transferred into 20 mL vials and immersed in a heated oil bath to 72 °C (160 °F) ⁇ 2°C. The samples were equilibrated for 10-15 minutes.
  • the detergent was dispensed such that when the detergent was mixed with water during the cycle to form a use solution, the detergent concentration in the use solution was 750 parts per million (ppm).
  • the solution in the wash tank was titrated to verify detergent concentration.
  • the warewash machine had a washbath volume of 58 liters, a rinse volume of 2.8 liters, a wash time of 50 seconds, and a rinse time of 9 seconds.
  • the 100 cycle test was then started. At the beginning of each wash cycle, the appropriate amount of detergent was automatically dispensed into the warewash machine to maintain the initial detergent concentration. The detergent concentration was controlled by conductivity.
  • the light box test used a digital camera, a light box, a light source, a light meter and a control computer employing "Spot Advance” and "Image Pro Plus” commercial software.
  • a glass to be evaluated was placed on its side on the light box, and the intensity of the light source was adjusted to a predetermined value using the light meter.
  • a photographic image of the glass was taken and saved to the computer.
  • the software was then used to analyze the upper half of the glass, and the computer displayed a histogram graph with the area under the graph being proportional to the thickness of the film.
  • a lower light box score indicates that more light was able to pass through the tumbler.
  • the lower the light box score the more effective the composition was at preventing scale on the surface of the tumbler.
  • a clean, unused glass tumbler has a light box score of approximately 12,000, which corresponds to a score of 72,000 for the six glass tumblers
  • a clean, unused plastic tumbler has a light box score of approximately 25,500, which corresponds to a light box score of approximately 102,000 for the four plastic tumblers.
  • the minimum obtainable light box score i.e., sum of six clean glass tumblers and four clean plastic tumblers
  • a detergent composition is considered effective for controlling hard water scale if the sum of the light box scores for six glass tumblers and four plastic tumblers is approximately 360,000 or less.
  • compositions according to the invention and controls were further evaluated using a 50 cycle redeposition experiment for institutional ware wash detergents.
  • a 50 cycle redeposition experiment for institutional ware wash detergents.
  • 6 10 oz. Libby heat resistant glass tumblers and 1 plastic tumblers were used. The glass tumblers were cleaned prior to use. New plastic tumblers were used for each experiment.
  • a food soil solution was prepared using a 50/50 combination of beef stew and hot point soil and employed at 2000 ppm soil.
  • the soil included two cans of Dinty Moore Beef Stew (1360 grams), one large can of tomato sauce (822 grams), 15.5 sticks of Blue Bonnet Margarine (1746 grams) and powered milk (436.4 grams).
  • the hot point soil was added to the machine to maintain a sump concentration of about 2000 ppm.
  • the heaters were turned on.
  • the wash temperature was adjusted to about 150-160°F.
  • the final rinse temperature was adjusted to about 175-190°F.
  • the controller was set to disclose the amount of detergent in the wash tank.
  • the dishmachine was then started and run through an automatic cycle. At the beginning of each cycle the appropriate amount of hot point sol was added to maintain the sump concentration of 2000 ppm.
  • the detergent concentration is controlled by conductivity.
  • the glasses were allowed to dry overnight. Thereafter they were graded for spots and film accumulation (visual).
  • the glass and plastic tumblers were then graded for protein accumulation using Commassie Brilliant Blue R stain followed by destaining with an aqueous acetic acid/methanol solution.
  • the Commassie Brilliant Blue R stain was prepared by combining 1.25 g of Commassie Brilliant Blue R dye with 45 mL of acetic acid and 455 mL of 50% methanol in distilled water.
  • the destaining solution consisted of 45% methanol and 10% acetic acid in distilled water.
  • the amount of protein remaining on the glass and plastic tumblers after destaining was rated visually on a scale of 1 to 5.
  • a rating of 1 indicated no protein was present after destaining - no spots/no film.
  • a rating of 2 indicated that random areas (barely perceptible) were covered with protein after destaining - spots at random (or about 20% surface covered in film).
  • a rating of 3 indicated that about a quarter to half of the surface was covered with protein after destaining (or about 40% surface covered in film).
  • a rating of 4 indicated that about half of the glass/plastic surface was covered with protein after destaining (or about 60% surface covered in film).
  • a rating of 5 indicated that the entire surface was coated with protein after destaining (or at least about 80% surface covered in film).
  • the ratings of the glass tumblers tested for soil removal were averaged to determine an average soil removal rating from glass surfaces and the ratings of the plastic tumblers tested for soil removal were averaged to determine an average soil removal rating from plastic surfaces.
  • the ratings of the glass tumblers tested for redeposition were averaged to determine an average redeposition rating for glass surfaces and the ratings of the plastic tumblers tested for redeposition were averaged to determine an average redeposition rating for plastic surfaces.
  • a food soil solution was prepared using a 50/50 combination of beef stew and hot point soil.
  • the concentration of the solution was about 2000 ppm.
  • the soil included two cans of Dinty Moore Beef Stew (1360 grams), one large can of tomato sauce (822 grams), 15.5 sticks of Blue Bonnet Margarine (1746 grams) and powered milk (436.4 grams).
  • the dishmachine was then filled with an appropriate amount of water. After filling the dishmachine with the water, the heaters were turned on. The final rinse temperature was adjusted to about 180.degree. F.
  • the glasses and plastic tumblers were soiled by rolling the glasses in a 1:1 (by volume) mixture of Campbell's Cream of Chicken Soup: Kemp's Whole Milk three times. The glasses were then placed in an oven at about 160.degree. F. for about 8 minutes. While the glasses were drying, the dishmachine was primed with about 120 grams of the food soil solution, which corresponds to about 2000 ppm of food soil in the pump.
  • the dishmachine was then started and run through an automatic cycle.
  • the cycle ended the top of the glass and plastic tumblers were mopped with a dry towel.
  • the glass and plastic tumblers being tested for soil removal were removed and the soup/milk soiling procedure was repeated.
  • the redeposition glass and plastic tumblers were not removed.
  • the glass and plastic tumblers were then graded for protein accumulation using Coommassie Brilliant Blue R stain followed by destaining with an aqueous acetic acid/methanol solution.
  • the Coommassie Brilliant Blue R stain was prepared by combining about 1.25 g of Coommassie Brilliant Blue R dye with about 45 mL of acetic acid and about 455 mL of 50% methanol in distilled water.
  • the destaining solution consisted of 45% methanol and 10% acetic acid in distilled water.
  • the amount of protein remaining on the glass and plastic tumblers after destaining was rated visually on a scale of 1 to 5. A rating of 1 indicated no protein was present after destaining.
  • a rating of 2 indicated that random areas (barely perceptible) were covered with protein after destaining.
  • a rating of 3 indicated that about a quarter of the surface was covered with protein after destaining.
  • a rating of 4 indicated that about half of the glass/plastic surface was covered with protein after destaining.
  • a rating of 5 indicated that the entire surface was coated with protein after destaining.
  • the ratings of the glass tumblers tested for protein removal were averaged to determine an average protein removal rating from glass surfaces and the ratings of the plastic tumblers tested for protein removal were averaged to determine an average protein removal rating from plastic surfaces.
  • the ratings of the glass tumblers tested for redeposition were averaged to determine an average protein redeposition rating for glass surfaces and the ratings of the plastic tumblers tested for protein redeposition were averaged to determine an average protein redeposition rating for plastic surfaces.
  • Glasses are rated visually in the glass viewing area against a black background. Rate each set of glasses as a set, i.e., all redeposition glasses for all products tested. An overall average can be determined for each set. The rating scale used is shown in Table 25. TABLE 25 Rating Spots Film Protein 1 No spots No Film No Protein 2 Spots at random 20% of surface covered in film 20% remains 3 1/4 glass spotted 40% of the surface covered in film 40% remains 4 1/2 glass spotted 60% of the surface covered in film 80% remains 5 Whole glass spotted At least 80% of the surface covered in film 100% remains
  • Protein Glass Score 1 1.0 (0.0) 1.0 (0.0) 1.0 (0.0) 1.0 (0.0) 1.0 (0.0) 2 1.0 (0.0) 3 1.0 (0.0) Avg. Protein Plastic Score 1 1.0 (0.0) 1.0 (0.0) 1.0 (0.0) 1.0 (0.0) 1.0 (0.0) 2 1.0 (0.0) 3 1.0 (0.0) TABLE 27. 7-cycle Soil removal Exp. Detergent Control 1 Detergent Control 2 Detergent Control 1 + Rinse Aid Control 2 Detergent Control 2 + Rinse Aid Control 1 Exp. 2 Avg. Glass Score Spots 1 5.0 (0.0) 4.8 (0.2) 1.0 (0.0) 4.2 (1.1) 2.1 (0.6) 2 2.4 (0.6) 3 5.0 (0.0) Avg.
  • compositions of the present invention provided similar, substantially similar, or better performance when compared with existing detergents and existing detergents and rinse aids in most categories of cleaning and antiredeposition in a traditional warewash procedure.

Landscapes

  • 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)
EP23176658.5A 2014-03-07 2015-03-02 Waschmittelzusammensetzung mit reinigungs- und spülfunktion Pending EP4227391A1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201461949387P 2014-03-07 2014-03-07
US201461949377P 2014-03-07 2014-03-07
EP15759090.2A EP3114197B1 (de) 2014-03-07 2015-03-02 Waschmittelzusammensetzung mit reinigungs- und spülfunktion
PCT/US2015/018352 WO2015134404A1 (en) 2014-03-07 2015-03-02 Detergent composition that performs both a cleaning and rinsing function

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP15759090.2A Division EP3114197B1 (de) 2014-03-07 2015-03-02 Waschmittelzusammensetzung mit reinigungs- und spülfunktion

Publications (1)

Publication Number Publication Date
EP4227391A1 true EP4227391A1 (de) 2023-08-16

Family

ID=54055764

Family Applications (2)

Application Number Title Priority Date Filing Date
EP15759090.2A Active EP3114197B1 (de) 2014-03-07 2015-03-02 Waschmittelzusammensetzung mit reinigungs- und spülfunktion
EP23176658.5A Pending EP4227391A1 (de) 2014-03-07 2015-03-02 Waschmittelzusammensetzung mit reinigungs- und spülfunktion

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP15759090.2A Active EP3114197B1 (de) 2014-03-07 2015-03-02 Waschmittelzusammensetzung mit reinigungs- und spülfunktion

Country Status (10)

Country Link
EP (2) EP3114197B1 (de)
JP (3) JP2017507236A (de)
KR (2) KR101982707B1 (de)
CN (2) CN106103679A (de)
AU (1) AU2015225441B2 (de)
BR (1) BR112016020336B1 (de)
CA (1) CA2941511C (de)
ES (1) ES2949191T3 (de)
MX (1) MX2016011249A (de)
WO (1) WO2015134404A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106701351A (zh) * 2015-11-12 2017-05-24 艺康美国股份有限公司 低起泡器皿清洗清洁剂，含增强含油污垢除去的混合的阳离子/非离子表面活性剂体系
CN111936609A (zh) * 2018-03-13 2020-11-13 埃科莱布美国股份有限公司 包括三元共聚物的器皿清洗碱性洗涤剂组合物
US11193096B2 (en) * 2019-08-22 2021-12-07 Henkel IP & Holding GmbH Unit dose packs with anti-efflorescence formulations
CN116096846A (zh) * 2020-08-04 2023-05-09 宝洁公司 自动盘碟洗涤方法
JP2023547853A (ja) * 2020-11-17 2023-11-14 ザ プロクター アンド ギャンブル カンパニー アルカリ性すすぎによる自動食器洗浄方法

Citations (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3048548A (en) 1959-05-26 1962-08-07 Economics Lab Defoaming detergent composition
US3334147A (en) 1962-02-28 1967-08-01 Economics Lab Defoaming and surface active compositions
US3442242A (en) 1967-06-05 1969-05-06 Algonquin Shipping & Trading Stopping and manoeuvering means for large vessels
US3929678A (en) 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
US4233171A (en) * 1978-09-11 1980-11-11 Desoto, Inc. Dishwashing detergent effective at low temperature
US4595520A (en) 1984-10-18 1986-06-17 Economics Laboratory, Inc. Method for forming solid detergent compositions
US4680134A (en) 1984-10-18 1987-07-14 Ecolab Inc. Method for forming solid detergent compositions
USRE32763E (en) 1978-02-07 1988-10-11 Ecolab Inc. Cast detergent-containing article and method of making and using
USRE32818E (en) 1978-02-07 1989-01-03 Ecolab Inc. Cast detergent-containing article and method of using
US5078301A (en) 1987-10-02 1992-01-07 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5198198A (en) 1987-10-02 1993-03-30 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5234615A (en) 1987-10-02 1993-08-10 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5316688A (en) 1991-05-14 1994-05-31 Ecolab Inc. Water soluble or dispersible film covered alkaline composition
EP0687720A2 (de) * 1994-06-14 1995-12-20 Basf Corporation Eine Mischung von nichtionischen Tensiden enthaltende Zusammensetzung zum maschinellen Reinigen und Spülen von Geschirr
US5612305A (en) * 1995-01-12 1997-03-18 Huntsman Petrochemical Corporation Mixed surfactant systems for low foam applications
US5858299A (en) 1993-05-05 1999-01-12 Ecolab, Inc. Process for consolidating particulate solids
DE19732689A1 (de) * 1997-07-30 1999-02-04 Basf Ag Feste Textilwaschmittel-Formulierung auf Basis von Glycin-N,N-diessigsäure-Derivaten mit stark reduziertem Anteil an weiteren anionischen Tensiden
US6034044A (en) * 1996-09-11 2000-03-07 The Procter & Gamble Company Low foaming automatic dishwashing compositions
DE20014919U1 (de) * 2000-03-28 2000-11-30 Henkel KGaA, 40589 Düsseldorf Teilchenförmige maschinelle Geschirrspülmittel mit Klarspüleffekt
US6156715A (en) 1997-01-13 2000-12-05 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US6177392B1 (en) 1997-01-13 2001-01-23 Ecolab Inc. Stable solid block detergent composition
US6258765B1 (en) 1997-01-13 2001-07-10 Ecolab Inc. Binding agent for solid block functional material
US6436893B1 (en) 1997-01-13 2002-08-20 Ecolab Inc. Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal
USRE38262E1 (en) 1997-01-23 2003-10-07 Ecolab Inc. Warewashing system containing nonionic surfactant that performs both a cleaning and sheeting function and a method of warewashing
US6730653B1 (en) 2000-06-01 2004-05-04 Ecolab Inc. Method for manufacturing a molded detergent composition
US20040167049A1 (en) * 2001-07-24 2004-08-26 Arnd Kessler Machine dishwashing detergents containing surfactants with specific diffusion coefficients
US20040254090A1 (en) * 1993-12-30 2004-12-16 Ecolab Inc. Combination of a nonionic silicone surfactant and a nonionic surfactant in a solid block detergent
US7037886B2 (en) 2000-06-01 2006-05-02 Ecolab Inc. Method for manufacturing a molded detergent composition
US7153820B2 (en) 2001-08-13 2006-12-26 Ecolab Inc. Solid detergent composition and method for solidifying a detergent composition
US20070082836A1 (en) * 2005-09-14 2007-04-12 Sabine Both Mixture of surface-active compounds for use in cleaning preparations
US20100065090A1 (en) * 2007-04-25 2010-03-18 Basf Se Dishwasher detergent with excellent rinsing power
US20100311633A1 (en) * 2007-02-15 2010-12-09 Ecolab Usa Inc. Detergent composition for removing fish soil
US20110232692A1 (en) * 2008-12-05 2011-09-29 Henkel Ag & Co. Kgaa Automatic dishwashing agent
US20120167922A1 (en) * 2009-09-21 2012-07-05 Henkel Ag & Co. Kgaa Dishwasher detergent
US8889048B2 (en) 2007-10-18 2014-11-18 Ecolab Inc. Pressed, self-solidifying, solid cleaning compositions and methods of making them

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6484734B1 (en) 1999-07-14 2002-11-26 Ecolab Inc. Multi-step post detergent treatment method
DE50304955D1 (de) 2003-06-28 2006-10-19 Dalli Werke Gmbh & Co Kg Alpha Olefin- und Alpha Olefin-Cellulose Granulate als Sprengmittel
JP5031309B2 (ja) * 2005-09-30 2012-09-19 花王株式会社 食器洗浄機用洗浄剤組成物
JP4767658B2 (ja) * 2005-11-08 2011-09-07 花王株式会社 食器洗浄機用粉体洗浄剤組成物
US8093200B2 (en) 2007-02-15 2012-01-10 Ecolab Usa Inc. Fast dissolving solid detergent
DE102007042860A1 (de) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102007042907A1 (de) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Reinigungsmittel
US7491362B1 (en) * 2008-01-28 2009-02-17 Ecolab Inc. Multiple enzyme cleaner for surgical instruments and endoscopes
JP2012025928A (ja) * 2010-07-22 2012-02-09 Ecolab Inc 魚油関連適用のための洗剤組成物
JP5656702B2 (ja) * 2011-03-11 2015-01-21 株式会社日本触媒 （メタ）アクリル酸系共重合体およびその製造方法
EP2766462B1 (de) * 2011-05-20 2019-08-28 Ecolab USA Inc. Säureformulierungen zur verwendung in einem waschsystem
JP5863562B2 (ja) * 2012-05-16 2016-02-16 株式会社Adeka 食器洗浄機用洗浄剤組成物
US9011610B2 (en) 2012-06-22 2015-04-21 Ecolab Usa Inc. Solid fast draining/drying rinse aid for high total dissolved solid water conditions

Patent Citations (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3048548A (en) 1959-05-26 1962-08-07 Economics Lab Defoaming detergent composition
US3334147A (en) 1962-02-28 1967-08-01 Economics Lab Defoaming and surface active compositions
US3442242A (en) 1967-06-05 1969-05-06 Algonquin Shipping & Trading Stopping and manoeuvering means for large vessels
US3929678A (en) 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
USRE32763E (en) 1978-02-07 1988-10-11 Ecolab Inc. Cast detergent-containing article and method of making and using
USRE32818E (en) 1978-02-07 1989-01-03 Ecolab Inc. Cast detergent-containing article and method of using
US4233171A (en) * 1978-09-11 1980-11-11 Desoto, Inc. Dishwashing detergent effective at low temperature
US4680134A (en) 1984-10-18 1987-07-14 Ecolab Inc. Method for forming solid detergent compositions
US4595520A (en) 1984-10-18 1986-06-17 Economics Laboratory, Inc. Method for forming solid detergent compositions
US5078301A (en) 1987-10-02 1992-01-07 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5198198A (en) 1987-10-02 1993-03-30 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5234615A (en) 1987-10-02 1993-08-10 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5316688A (en) 1991-05-14 1994-05-31 Ecolab Inc. Water soluble or dispersible film covered alkaline composition
US5858299A (en) 1993-05-05 1999-01-12 Ecolab, Inc. Process for consolidating particulate solids
US20040254090A1 (en) * 1993-12-30 2004-12-16 Ecolab Inc. Combination of a nonionic silicone surfactant and a nonionic surfactant in a solid block detergent
EP0687720A2 (de) * 1994-06-14 1995-12-20 Basf Corporation Eine Mischung von nichtionischen Tensiden enthaltende Zusammensetzung zum maschinellen Reinigen und Spülen von Geschirr
US5612305A (en) * 1995-01-12 1997-03-18 Huntsman Petrochemical Corporation Mixed surfactant systems for low foam applications
US6034044A (en) * 1996-09-11 2000-03-07 The Procter & Gamble Company Low foaming automatic dishwashing compositions
US6177392B1 (en) 1997-01-13 2001-01-23 Ecolab Inc. Stable solid block detergent composition
US7094746B2 (en) 1997-01-13 2006-08-22 Ecolab Inc. Stable solid block detergent composition
US6156715A (en) 1997-01-13 2000-12-05 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US6258765B1 (en) 1997-01-13 2001-07-10 Ecolab Inc. Binding agent for solid block functional material
US6410495B1 (en) 1997-01-13 2002-06-25 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US6436893B1 (en) 1997-01-13 2002-08-20 Ecolab Inc. Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal
US6583094B1 (en) 1997-01-13 2003-06-24 Ecolab Inc. Stable solid block detergent composition
US7087569B2 (en) 1997-01-13 2006-08-08 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US6653266B2 (en) 1997-01-13 2003-11-25 Ecolab Inc. Binding agent for solid block functional material
US6660707B2 (en) 1997-01-13 2003-12-09 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US6831054B2 (en) 1997-01-13 2004-12-14 Ecolab Inc. Stable solid block detergent composition
USRE38262E1 (en) 1997-01-23 2003-10-07 Ecolab Inc. Warewashing system containing nonionic surfactant that performs both a cleaning and sheeting function and a method of warewashing
DE19732689A1 (de) * 1997-07-30 1999-02-04 Basf Ag Feste Textilwaschmittel-Formulierung auf Basis von Glycin-N,N-diessigsäure-Derivaten mit stark reduziertem Anteil an weiteren anionischen Tensiden
DE20014919U1 (de) * 2000-03-28 2000-11-30 Henkel KGaA, 40589 Düsseldorf Teilchenförmige maschinelle Geschirrspülmittel mit Klarspüleffekt
US6730653B1 (en) 2000-06-01 2004-05-04 Ecolab Inc. Method for manufacturing a molded detergent composition
US7037886B2 (en) 2000-06-01 2006-05-02 Ecolab Inc. Method for manufacturing a molded detergent composition
US20040167049A1 (en) * 2001-07-24 2004-08-26 Arnd Kessler Machine dishwashing detergents containing surfactants with specific diffusion coefficients
US7153820B2 (en) 2001-08-13 2006-12-26 Ecolab Inc. Solid detergent composition and method for solidifying a detergent composition
US20070082836A1 (en) * 2005-09-14 2007-04-12 Sabine Both Mixture of surface-active compounds for use in cleaning preparations
US20100311633A1 (en) * 2007-02-15 2010-12-09 Ecolab Usa Inc. Detergent composition for removing fish soil
US20100065090A1 (en) * 2007-04-25 2010-03-18 Basf Se Dishwasher detergent with excellent rinsing power
US8889048B2 (en) 2007-10-18 2014-11-18 Ecolab Inc. Pressed, self-solidifying, solid cleaning compositions and methods of making them
US20110232692A1 (en) * 2008-12-05 2011-09-29 Henkel Ag & Co. Kgaa Automatic dishwashing agent
US20120167922A1 (en) * 2009-09-21 2012-07-05 Henkel Ag & Co. Kgaa Dishwasher detergent

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Surfactant Encyclopedia", COSMETICS & TOILETRIES, vol. 104, no. 2, 1989, pages 69 - 71
KIRK-OTHMER: "Encyclopedia of Chemical Technology", vol. 9, 1980, JOHN WILEY & SONS, article "Kirk-Othmer Encyclopedia of Chemical Technology", pages: 173 - 224
SCHICK, M. J: "Surfactant Science Series", vol. 1, 1983, MARCEL DEKKER, INC

Also Published As

Publication number Publication date
KR101982707B1 (ko) 2019-05-27
EP3114197A1 (de) 2017-01-11
EP3114197B1 (de) 2023-06-07
CA2941511A1 (en) 2015-09-11
CN106103679A (zh) 2016-11-09
EP3114197A4 (de) 2017-08-30
EP3114197C0 (de) 2023-06-07
KR20160119862A (ko) 2016-10-14
BR112016020336B1 (pt) 2022-12-13
JP6871452B2 (ja) 2021-05-12
CN113736588A (zh) 2021-12-03
BR112016020336A2 (pt) 2021-08-03
JP2017507236A (ja) 2017-03-16
KR20180071422A (ko) 2018-06-27
ES2949191T3 (es) 2023-09-26
JP6835774B2 (ja) 2021-02-24
WO2015134404A1 (en) 2015-09-11
JP2020109193A (ja) 2020-07-16
JP2018188653A (ja) 2018-11-29
AU2015225441B2 (en) 2017-12-21
AU2015225441A1 (en) 2016-09-01
CA2941511C (en) 2019-01-29
MX2016011249A (es) 2016-11-30

Similar Documents

Publication Publication Date Title
US10392584B2 (en) Detergent composition comprising a polymer that performs both a cleaning and rinsing function
US10501708B2 (en) Detergent composition that performs both a cleaning and rinsing function
US11905493B2 (en) Concentrated 2 in 1 dishmachine detergent and rinse aid
US9255242B2 (en) Solidification matrix comprising phosphinosuccinic acid derivatives
JP6871452B2 (ja) 洗浄機能とすすぎ機能の両方を行う洗剤組成物
JP2022544134A (ja) マレイン酸テトラポリマーを含有する洗剤組成物
WO2021062632A1 (en) Ware washing solution containing oxidized starch
US20240336874A1 (en) Solid 2-in-1 detergent rinse formula for under-counter machine ware wash

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AC Divisional application: reference to earlier application

Ref document number: 3114197

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20240214

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20240425