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EP3039107B1 - Composition d'aide au rinçage solide et son procédé de fabrication - Google Patents

Composition d'aide au rinçage solide et son procédé de fabrication Download PDF

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Publication number
EP3039107B1
EP3039107B1 EP13892591.2A EP13892591A EP3039107B1 EP 3039107 B1 EP3039107 B1 EP 3039107B1 EP 13892591 A EP13892591 A EP 13892591A EP 3039107 B1 EP3039107 B1 EP 3039107B1
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EP
European Patent Office
Prior art keywords
composition
solid
rinse aid
rinse
sulfonate
Prior art date
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Application number
EP13892591.2A
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German (de)
English (en)
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EP3039107A1 (fr
EP3039107A4 (fr
Inventor
Xin Sun
Derrick Anderson
Kelsey West
Janel Marie Kieffer
Victor Fuk-Pong Man
Melissa HUNTER
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Ecolab USA Inc
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Ecolab USA Inc
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Priority claimed from US14/010,815 external-priority patent/US9567551B2/en
Application filed by Ecolab USA Inc filed Critical Ecolab USA Inc
Publication of EP3039107A1 publication Critical patent/EP3039107A1/fr
Publication of EP3039107A4 publication Critical patent/EP3039107A4/fr
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    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • C11D3/042—Acids
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
    • 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

Definitions

  • the present invention relates to solid rinse aid compositions, and methods for manufacturing and using the same.
  • the rinse aid compositions generally include a novel solidification system and surfactants designed for use in pressed or extruded solid formation.
  • the rinse aids can be used in aqueous use solutions on articles including, for example, cookware, dishware, flatware, glasses, cups, hard surfaces, healthcare surfaces, glass surfaces, vehicle surfaces, etc. but are particularly useful for metal surfaces.
  • Rinse agents may also be used in healthcare environments, typically for cleaning a medical cart, cage, instrument, or device.
  • cleaning a medical cart, cage, instrument, or device includes contacting the medical cart, cage, instrument, or device with an aqueous cleaning composition and, rinsing or contacting the same with a rinse solution comprising a dissolved rinse aid.
  • the method can also involve antimicrobial treatment of the medical cart, cage, instrument, or device by contacting with an aqueous antimicrobial composition formed by dissolving or suspending a solid antimicrobial composition, preferably a solid quaternary ammonium or solid halogen antimicrobial composition.
  • rinse agents to reduce the formation of spotting have been, commonly been added to water to form an aqueous rinse that is sprayed on the hard surfaces after cleaning is complete.
  • the precise mechanism through which rinse agents work is not established.
  • One theory holds that the surfactant in the rinse agent is absorbed on the surface at temperatures at or above its cloud point, and thereby reduces the solid-liquid interfacial energy and contact angle. This leads to the formation of a continuous sheet which drains evenly from the surface and minimizes the formation of spots.
  • high foaming surfactants have cloud points above the temperature of the rinse water, and, according to this theory, would not promote sheet formation, thereby resulting in spots.
  • high foaming materials are known to interfere with the operation of warewashing machines.
  • the document US 8 383 570 B2 discloses a GRAS preservative system including sodium bisulfate and a combination of specific organic acids that act in a synergistic capacity.
  • the preservative further has the benefit of a higher melting point of approximately 110° or higher making it particularly suited for solid wash applications.
  • a combination of sodium bisulfate, sorbic acid, and benzoic acid produced better preservative properties than other organic acid combinations or each acid by itself.
  • a rinse aid composition may generally include an effective amount of a sheeting agent component, and an effective amount of a defoamer component.
  • the sheeting agent component may include one or more alcohol ethoxylate compounds that include an alkyl group that includes 12 or fewer carbon atoms.
  • the defoamer component may include an ethylene oxide containing surfactant configured for reducing the stability of foam that may be created by the one or more alcohol ethoxylate compounds of the sheeting agent in an aqueous solution.
  • US 6 432 906 A1 discloses that a stable, substantially homogeneous, solid block cleaning composition can be made for general purpose cleaning and for cleaning hard surfaces such as floors of varying surface composition.
  • Unique solid block materials contain substantially useful concentrations of liquid acid materials, but are in the form of a stable solid.
  • the acidic solid detergent can be dispensed using a water spray creating a concentrate which can then be diluted in proper ratio to form the use-solution.
  • Such use-solutions may be applied to remove a variety of soils subject to acid cleaning including soils containing water hardness components, inorganic soils, and the like.
  • the acid cleaners can be used alone or in combination with other cleaners in a cleaning protocol for a variety of hospitality, industrial or institutional cleaning locations having a broad spectrum of contaminated soil residue.
  • US 2011/126858 A1 discloses a method of rinsing cleaned dishware comprising the steps of: (a) cleaning dishware in an automatic dishwasher; and (b) during the rinse cycle of said automatic dishwasher, rinsing said dishware with a rinse aid composition comprising: at least one a graft polymer comprising an acrylic acid backbone and alkoxylated side chains, said polymer comprising a molecular weight of from about 2,000 to about 20,000, said graft polymer comprising from about 20 wt % to about 50 wt % of an alkylene oxide; an acid; a non-ionic surfactant; and optionally at least one component selected from the group consisting of dispersant polymer, perfume, hydrotrope, binder, carrier medium, antibacterial active, dye, zinc carbonate, zinc chloride, and mixtures thereof.
  • a rinse aid composition comprising: at least one a graft polymer comprising an acrylic acid backbone and alkoxylated side chains, said polymer comprising a mo
  • rinse aids are currently known, each having certain advantages and disadvantages.
  • alternative rinse aid compositions especially alternative rinse aid compositions that are environmentally friendly (e.g., biodegradable), non-corrosive to metal, can handle high total dissolved solids, can handle high water hardness and are easily manufactured as solids.
  • the invention includes a solid rinse aid that is particularly designed for pressed or extrusion solid formation and which is effective for leaving spotless surfaces after rinsing, especially rinsing metals without corrosion.
  • a solid acid is combined with a short-chain alkylbenzene and alkyl naphthalene sulfonate class of hydrotopes, selected from the group consisting of sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkyl naphthalene sulfonate, and/or sodium butylnaphthalene sulfonate.
  • Said short-chain alkylbenzene and alkyl naphthalene sulfonate class of hydrotopes act as a solidification agent as well as
  • a solid rinse agent composition of the present invention thus includes a solid acid for hardness control, from 50 wt.% to 80 wt.% of a short chain alkyl benzene and/or alkyl naphthalene according to claim 1, preferably sodium xylene sulfonate (SXS) or sodium cumene sulfonate, and a surfactant system.
  • the surfactant is a non-ionic surfactant.
  • composition of the invention is particularly beneficial for use with hard water and also high total dissolved solid (TDS) conditions.
  • the rinse aid concentrate is provided in a solid form. This is typically prepared by the steps of combining the solid materials then mixing preservative, additional surfactant, water, and dyes. The material is then pressed or extruded to form a solid. In general, it is expected that the solid concentrate will be diluted with water to provide the use solution that is then supplied to the surface of a substrate.
  • the use solution preferably contains an effective amount of active material to provide spotless surfaces by rinse water. It should be appreciated that the term "active materials" refers to the nonaqueous portion of the use solution that functions to reduce spotting and filming.
  • Some example methods for using the rinse aid generally include the step of providing the rinse aid, mixing the rinse aid into an aqueous use solution, and applying the aqueous use solution to a substrate surface.
  • the solid acid is present in an amount of from 5 wt.% to 40 wt. %.
  • the short chain alkyl benzene or alkyl naphthalene sulfonate is present 50wt % to 80 wt % and the nonionic surfactant is present from 5 wt. % to 20 wt. % for pressed solid and from 5 wt. % to 30 wt. % for an extruded solid.
  • the solid rinse aid can also in some embodiments and as enumerated hereinafter, include an additional surfactant, a processing aids such as polyethylene glycol or urea, as well as other components such as a chelant, preservative, fragrant, or dye.
  • the present invention is related to methods for rinsing surfaces in a warewashing application or surfaces involved in healthcare.
  • the methods comprise providing an aqueous rinse aid composition, diluting the rinse aid composition with water to form an aqueous use solution; and applying the aqueous use solution to the surfaces.
  • the present invention relates to rinse aid compositions, and methods for making and using rinse aid compositions.
  • the present invention provides rinse aid compositions including an acid which is naturally or treated to be in solid form at room temperature, from 50 wt.% to 80 wt.% of a short-chain alkylbenzene and alkyl naphthalene sulfonate, selected from the group consisting of sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkyl naphthalene sulfonate, and/or sodium butylnaphthalene sulfonate, and at least one additional nonionic surfactant.
  • a short-chain alkylbenzene and alkyl naphthalene sulfonate selected from the
  • compositions of the present invention can be used to reduce spotting and filming on a variety of surfaces including, but not limited to, plasticware, cookware, dishware, flatware, glasses, cups, hard surfaces, glass surfaces, healthcare surfaces and vehicle surfaces. So that the invention may be understood more clearly, certain terms are first defined.
  • ware refers to items such as eating, cooking, and serving utensils.
  • Exemplary items of ware include, but are not limited to: dishes, e.g., plates and bowls; silverware, e.g., forks, knives, and spoons; cups and glasses, e.g., drinking cups and glasses; serving dishes, e.g., fiberglass trays, insulated plate covers.
  • warewashing refers to washing, cleaning, or rinsing ware.
  • the items of ware that can be contacted, e.g., washed, or rinsed, with the compositions of the invention can be made of any material.
  • ware includes items made of wood, metal, ceramics, glass, etc.
  • Ware also refers to items made of plastic.
  • Types of plastics that can be cleaned or rinsed 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
  • Another exemplary plastic that can be cleaned using the methods and compositions of the invention include polyethylene terephthalate (PET).
  • hard surface includes showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, floors, and the like.
  • health care surface refers to a surface of an instrument, a device, a cart, a cage, furniture, a structure, a building, or the like that is employed as part of a health care activity.
  • health care surfaces include surfaces of medical or dental instruments, of medical or dental devices, of autoclaves and sterilizers, of electronic apparatus employed for monitoring patient health, and of floors, walls, or fixtures of structures in which health care occurs.
  • Health care surfaces are found in hospital, surgical, infirmity, birthing, mortuary, and clinical diagnosis rooms.
  • These surfaces can be those typified as "hard surfaces” (such as walls, floors, bed-pans, etc.,), or fabric surfaces, e.g., knit, woven, and non-woven surfaces (such as surgical garments, draperies, bed linens, bandages, etc.,), or patient-care equipment (such as respirators, diagnostic equipment, shunts, body scopes, wheel chairs, beds, etc.,), or surgical and diagnostic equipment.
  • Health care surfaces include articles and surfaces employed in animal health care.
  • instrument refers to the various medical or dental instruments or devices that can benefit from cleaning using water treated according to the methods of the present invention.
  • the phrases "medical instrument,” “dental instrument,” “medical device,” “dental device,” “medical equipment,” or “dental equipment” refer to instruments, devices, tools, appliances, apparatus, and equipment used in medicine or dentistry. Such instruments, devices, and equipment can be cold sterilized, soaked or washed and then heat sterilized, or otherwise benefit from cleaning using water treated according to the present invention. These various instruments, devices and equipment include, but are not limited to: diagnostic instruments, trays, pans, holders, racks, forceps, scissors, shears, saws (e.g.
  • hemostats knives, chisels, rongeurs, files, nippers, drills, drill bits, rasps, burrs, spreaders, breakers, elevators, clamps, needle holders, carriers, clips, hooks, gouges, curettes, retractors, straightener, punches, extractors, scoops, keratomes, spatulas, expressors, trocars, dilators, cages, glassware, tubing, catheters, cannulas, plugs, stents, scopes (e.g., endoscopes, stethoscopes, and arthoscopes) and related equipment, and the like, or combinations thereof.
  • scopes e.g., endoscopes, stethoscopes, and arthoscopes
  • solid as used with reference to the composition of the invention, it is meant that the hardened composition will not flow perceptibly and will substantially retain its shape under moderate stress or pressure or mere gravity, as for example, the shape of a mold when removed from the mold, the shape of an article as formed upon extrusion from an extruder, and the like.
  • the degree of hardness of the solid composition can range from that of a fused solid block which is relatively dense and hard, for example, like concrete, to a consistency characterized as being malleable and sponge-like, similar to caulking material.
  • the "cloud point" of a surfactant rinse or sheeting agent is defined as the temperature at which a 1 wt. % aqueous solution of the surfactant turns cloudy when warmed.
  • health care surface refers to a surface of an instrument, a device, a cart, a cage, furniture, a structure, a building, or the like that is employed as part of a health care activity.
  • Examples of health care surfaces include surfaces of medical or dental instruments, of medical or dental devices, of electronic apparatus employed for monitoring patient health, and of floors, walls, or fixtures of structures in which health care occurs. Health care surfaces are found in hospital, surgical, infirmity, birthing, mortuary, and clinical diagnosis rooms.
  • These surfaces can be those typified as "hard surfaces” (such as walls, floors, bed-pans, etc.,), or fabric surfaces, e.g., knit, woven, and non-woven surfaces (such as surgical garments, draperies, bed linens, bandages, etc.,), or patient-care equipment (such as respirators, diagnostic equipment, shunts, body scopes, wheel chairs, beds, etc.,), or surgical and diagnostic equipment.
  • Health care surfaces include articles and surfaces employed in animal health care.
  • medical cart refers to a cart employed in a health care environment to transport one or more medical instruments, devices, or equipment and that can benefit from cleaning with a use composition of a solid cleaning composition, rinsing with a use composition of a solid rinse composition, and/or antimicrobial treatment with a use composition of a solid antimicrobial composition.
  • Medical carts include carts for transporting medical or dental devices or instruments or other medical or dental equipment in a health care environment, such as a hospital, clinic, dental or medical office, nursing home, extended care facility, or the like.
  • the phrase "medical cage” refers to a cage employed in a health care environment to house and/or transport one or more animals employed in experiments, in clinical or toxicological testing, in diagnostics, or the like. Such animals include a rodent (e.g. a mouse or a rat), a rabbit, a dog, a cat, or the like.
  • a medical cage typically includes an animal cage that actually houses the animal and which can be mounted on a wheeled rack.
  • the medical cage can also include one or more containers or dispensers for animal food, one or more vessels or dispensers for water, and/or one or more systems for identifying the cart or animals.
  • Medical cages can benefit from cleaning with a use composition of a solid alkaline cleaning composition, rinsing with a use composition of a solid rinse composition, and/or antimicrobial treatment with a use composition of a solid antimicrobial composition.
  • instrument refers to the various medical or dental instruments or devices that can benefit from cleaning with a use composition of a solid alkaline cleaning composition, rinsing with a use composition of a solid rinse composition, and/or antimicrobial treatment with a use composition of a solid antimicrobial composition.
  • the phrases "medical instrument,” “dental instrument,” “medical device,” “dental device,” “medical equipment,” or “dental equipment” refer to instruments, devices, tools, appliances, apparatus, and equipment used in medicine or dentistry. Such instruments, devices, and equipment can be cold sterilized, soaked or washed and then heat sterilized, or otherwise benefit from cleaning in a composition of the present invention. These various instruments, devices and equipment include, but are not limited to: diagnostic instruments, trays, pans, holders, racks, forceps, scissors, shears, saws (e.g.
  • hemostats knives, chisels, rongeurs, files, nippers, drills, drill bits, rasps, burrs, spreaders, breakers, elevators, clamps, needle holders, carriers, clips, hooks, gouges, curettes, retractors, straightener, punches, extractors, scoops, keratomes, spatulas, expressors, trocars, dilators, cages, glassware, tubing, catheters, cannulas, plugs, stents, scopes (e.g., endoscopes, stethoscopes, and arthoscopes) and related equipment, and the like, or combinations thereof.
  • scopes e.g., endoscopes, stethoscopes, and arthoscopes
  • alkyl refers to a straight or branched chain monovalent hydrocarbon radical 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, and isopropyl, and the like.
  • alkyl may include “alylenes”, “alkenylenes”, or “alkylynes”.
  • alkylene refers to a straight or branched chain divalent hydrocarbon radical 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 radical 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. Examples of “alkenylene” as used herein include, but are not limited to, ethene-1,2-diyl, propene-1,3-diyl, and the like.
  • alkylyne refers to a straight or branched chain divalent hydrocarbon radical 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.
  • halogen or halo shall include iodine, bromine, chlorine and fluorine.
  • mercapto and “sulfhydryl” refer to the substituent -SH.
  • hydroxy refers to the substituent -OH.
  • amino refers to the substituent -NH 2 .
  • compositions of the present invention can comprise, consist of, or consist essentially of the listed steps or ingredients.
  • the term "consisting essentially of' shall be construed to mean including the listed ingredients or steps and such additional ingredients or steps which do not materially affect the basic and novel properties of the composition or method.
  • a composition in accordance with embodiments of the present invention that "consists essentially of' the recited ingredients does not include any additional ingredients that alter the basic and novel properties of the composition, e.g., the drying time, sheeting ability, spotting or filming properties of the composition.
  • weight percent (wt%) As used herein, “weight percent (wt%),” “percent by weight,” “% by weight,” and the like are synonyms that refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100.
  • the term "about" modifying the quantity of an ingredient in the compositions of the invention or employed in the methods of the invention refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or carry out the methods; and the like.
  • the term about also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture.
  • a solid rinse agent composition of the present invention includes a solid acid, from 50 wt.% to 80 wt.% of a short-chain alkylbenzene or alkyl naphthalene sulfonate, selected from the group consisting of sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkyl naphthalene sulfonate, and/or sodium butylnaphthalene sulfonate, and a one or more nonionic surfactant.
  • the solid rinse aid composition is advantageously formulated to give spotless surfaces after rinsing, especially in high hardness and high total dissolved solids (TDS) situations.
  • the rinse aid is also particularly useful for metal surfaces and avoids corrosion of the same.
  • the invention includes one or more solid acids.
  • the solid acid of the composition includes any acid which is naturally or treated to be in solid form at room temperature.
  • the term solid includes forms such as powdered, particulate, or granular solid forms.
  • Acidic substances include, but are not limited to, pharmaceutically acceptable organic or inorganic acids, hydroxyl-acids, amino acids, Lewis acids, mono- or di-alkali or ammonium salts of molecules containing two or more acid groups, and monomers or polymeric molecules containing at least one acid group.
  • suitable acid groups include carboxylic, hydroxamic, amide, phosphates (e.g., mono-hydrogen phosphates and di-hydrogen phosphates), sulfates, and bi-sulfites.
  • the acids are organic acids with 2-18 carbon atoms, including, but not limited to, short, medium, or long chain fatty acids, hydroxyl acids, inorganic acids, amino acids, and mixtures thereof.
  • the acid is selected from the group consisting of lactic acid, gluconic acid, citric acid, tartaric acid, hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, maleic acid, monosodium citrate, disodium citrate, potassium citrate, monosodium tartrate, disodium tartrate, potassium tartrate, aspartic acid, carboxymethylcellulose, acrylic polymers, methacrylic polymers, and mixtures thereof.
  • organic acids are crystalline solids in pure form (and at room temperature), e.g. citric acid, oxalic acid, benzoic acid.
  • Sulphamic acid in an example of an inorganic acid that is solid a room temperature.
  • the solid acid or combination of one or more solid acids is present in the rinse aid compositions of the invention in an amount of from 5 wt. % to 40 wt. %, preferably from 7.5 wt. % to 27.5 wt. % and more preferably from 10 wt. % to 25 wt. %.
  • the class of short chain alkyl benzene or alkyl naphthalene sulfonates work as both a hardening agent and as a hydrotrope and TDS control active in the composition.
  • the group includes alkyl benzene sulfonates based on toluene, xylene, and cumene , and alkyl naphthalene sulfonates.
  • Sodium toluene sulfonate and sodium xylene sulfonate are the best known hydrotopes. These have the general formula below:
  • This group includes but is not limited to sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkyl naphthalene sulfonate, and sodium butylnaphthalene sulfonate.
  • the solidification agent is SXS.
  • the invention provides a solid rinse aid composition including from 50 wt.% to 80 wt.% of one or more of a short chain alkyl benzene or alkyl naphthalene sulfonates. Surprisingly, this class of hydrotopes has been found to add to performance of the solid rinse aid as well as functioning as solidification agent.
  • the short chain alkyl benzene or alkyl naphthalene sulfonate may also function as a builder.
  • the solid rinse aid composition typically has a melt point greater than 43.33° C (110°F) and is dimensionally stable.
  • the hardening agent of a short chain alkyl benzene or alkyl naphthalene sulfonate is present in an amount of from 40 wt. % to 90 wt. %, and preferably from 45 wt. % to 85 wt. % . According to the invention, the hardening agent of a short chain alkyl benzene or alkyl naphthalene sulfonate is present in an amount of 50 wt. % to 80 wt. %.
  • the solid rinse aid can also in some embodiments and as enumerated hereinafter, include an additional processing aids, such as polyethylene glycol, or urea.
  • additional processing aids such as polyethylene glycol, or urea.
  • the additional processing aids if used is present in an amount of from. 1 wt % to 10 wt %.
  • Nonionic surfactants useful in the invention are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic, alkyl aromatic or polyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxide moiety which in common practice is ethylene oxide or a polyhydration product thereof, polyethylene glycol.
  • any hydrophobic compound having a hydroxyl, carboxyl, amino, or amido group with a reactive hydrogen atom can be condensed with ethylene oxide, or its polyhydration adducts, or its mixtures with alkoxylenes such as propylene oxide to form a nonionic surface-active agent.
  • hydrophilic polyoxyalkylene moiety which is condensed with any particular hydrophobic compound can be readily adjusted to yield a water dispersible or water soluble compound having the desired degree of balance between hydrophilic and hydrophobic properties.
  • useful nonionic surfactants in the present invention include: Examples of suitable nonionic surfactants include alkoxylated surfactants, 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 Genepol from Clariant, Tegoten EC11; mixtures thereof, or the like.))
  • nonionic surfactants that can used include:
  • Nonionic Surfactants edited by Schick, M. J., Vol. 1 of the Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is an excellent reference on the wide variety 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 ).
  • the solid rinse aid composition can in some embodiments includes water. Water many be independently added to the solid rinse aid composition or may be provided in the solid rinse aid composition as a result of its presence in a material that is added to the solid rinse aid composition.
  • materials added to the solid rinse aid composition include water or may be prepared in an aqueous premix available for reaction with the solidification agent component(s).
  • water is introduced into the solid rinse aid composition to provide the composition with a desired viscosity prior to solidification, and to provide a desired rate of solidification.
  • water may be present as a processing aid and may be removed or become water of hydration. It is expected that water may be present in the solid composition. In the solid composition, it is expected that the water will be present in the solid rinse aid composition in the range of between 0 wt.% and 5wt.%. For example, water is present in embodiments of the solid rinse aid composition in the range of between .1 wt.% to 5 wt.%, or further embodiments in the range of between .5 wt.% and 4 wt.%, or yet further embodiments in the range of between 1 wt.% and 3 wt.%. It should be additionally appreciated that the water may be provided as deionized water or as softened water.
  • the components used to form the solid composition can include water as hydrates or hydrated forms of the binding agent, hydrates or hydrated forms of any of the other ingredients, and/or added aqueous medium as an aid in processing. It is expected that the aqueous medium will help provide the components with a desired viscosity for processing. In addition, it is expected that the aqueous medium may help in the solidification process when is desired to form the concentrate as a solid.
  • the solid rinse aid may contain other functional materials that provide the desired properties and functionality to the solid composition.
  • Functional materials include a material that when dispersed or dissolved in a use solution, provides a beneficial property in a particular use. Examples of such a functional material include preservatives, chelating/sequestering agents; bleaching agents or activators; sanitizers/anti-microbial agents; activators; builder or fillers; anti-redeposition agents; optical brighteners; dyes; odorants or perfumes; stabilizers; processing aids; corrosion inhibitors; fillers; solidifiers; additional hardening agent; additional surfactants, solubility modifiers; pH adjusting agents; humectants; hydrotropes; or a broad variety of other functional materials, depending upon the desired characteristics and/or functionality of the composition.
  • the functional materials, or ingredients are optionally included within the solidification matrix for their functional properties. Some more particular examples of functional materials are discussed in more detail below.
  • the solid rinse aid composition may also include effective amounts of preservatives. Often, overall acidity and/or acids in the solid rinse aid composition and the use solution serves a preservative and stabilizing function.
  • the inventive solid rinse aid composition also include a preservative system for acidification of the solid rinse aid including sodium bisulfate and organic acids.
  • the solid rinse aid has pH of 2.0 or less and the use solution of the solid rinse aid has a pH of at least pH 4.0.
  • sodium bisulfate is included in the solid rinse aid composition as an acid source.
  • an effective amount of sodium bisulfate and one or more other acids are included in the solid rinse aid composition as a preservative system.
  • Suitable acids include for example, inorganic acids, such as HCl and organic acids.
  • an effective amount of sodium bisulfate and one or more organic acids are included in the solid rinse aid composition as a preservative system.
  • Suitable organic acids include sorbic acid, benzoic acid, ascorbic acid, erythorbic acid, citric acid, etc.
  • Preferred organic acids include benzoic and ascorbic acid.
  • effective amounts of sodium bisulfate with or without additional acids are included such that a use solution of the solid rinse aid composition has a pH that shall be less than pH 4.0, often less pH 3.0, and may be even less than pH 2.0.
  • the solid rinse aid composition includes sanitizers/anti-microbial agents, in addition to or in alternative the preservative system described above. Suitable sanitizers/anti-microbial agents are described below.
  • the preservative component if present is typically an amount of the solid rinse aid component in an amount of from 0.05 to 20 wt % preferably 0.1 to 15 wt % and most preferably 1 wt % to 10 wt %.
  • the solid rinse aid composition may also include effective amounts of chelating/sequestering agents, also referred to as builders.
  • the rinse aid may optionally include one or more additional builders as a functional ingredient.
  • a chelating agent is a molecule capable of coordinating (i.e., binding) the metal ions commonly found in water sources to prevent the metal ions from interfering with the action of the other ingredients of a rinse aid or other cleaning composition.
  • the chelating/sequestering agent may also function as a threshold agent when included in an effective amount.
  • the solid rinse aid composition is also phosphate-free and/or aminocarboxylate-free.
  • the additional functional materials, including builders exclude phosphorous-containing compounds such as condensed phosphates and phosphonates.
  • Suitable additional builders include polycarboxylates.
  • polymeric polycarboxylates suitable for use as sequestering agents include those having a pendant carboxylate (--CO 2 ) groups and include, for example, polyacrylic acid, maleic/olefin copolymer, acrylic/maleic copolymer, polymethacrylic acid, acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrile copolymers, and the like.
  • the solid rinse aid composition which are not aminocarboxylate-free may include added chelating/sequestering agents which are aminocarboxylates.
  • aminocarboxylic acids include, N-hydroxyethyliminodiacetic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA) (in addition to the HEDTA used in the binder), diethylenetriaminepentaacetic acid (DTPA), and the like.
  • added chelating/sequestering agents may include, for example a condensed phosphate, a phosphonate, and the like.
  • condensed phosphates include sodium and potassium orthophosphate, sodium and potassium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, and the like.
  • a condensed phosphate may also assist, to a limited extent, in solidification of the composition by fixing the free water present in the composition as water of hydration.
  • the composition may include a phosphonate such as 1-hydroxyethane-1,1-diphosphonic acid CH 3 C(OH)[PO(OH) 2 ] 2 ; aminotri(methylenephosphonic acid) N[CH 2 PO(OH) 2 ] 3 ; aminotri(methylenephosphonate), sodium salt
  • a phosphonate such as 1-hydroxyethane-1,1-diphosphonic acid CH 3 C(OH)[PO(OH) 2 ] 2 ; aminotri(methylenephosphonic acid) N[CH 2 PO(OH) 2 ] 3 ; aminotri(methylenephosphonate), sodium salt
  • the chelant/sequestering agent if present may be in an amount of from 0.1 wt. % to 30 wt. %, preferably from 1 wt. % to 25 wt. % and more preferably from 5 wt. % to 20 wt. %.
  • the solid acid may also perform as a chelant.
  • the solid rinse aid composition can include additional processing aids.
  • processing aids include an amide such as stearic monoethanolamide or lauric diethanolamide, or an alkylamide, and the like; a solid polyethylene glycol, or a solid EO/PO block copolymer, urea and the like; starches that have been made water-soluble through an acid or alkaline treatment process; various inorganics that impart solidifying properties to a heated composition upon cooling, and the like.
  • processing aids include an amide such as stearic monoethanolamide or lauric diethanolamide, or an alkylamide, and the like; a solid polyethylene glycol, or a solid EO/PO block copolymer, urea and the like; starches that have been made water-soluble through an acid or alkaline treatment process; various inorganics that impart solidifying properties to a heated composition upon cooling, and the like.
  • Such compounds may also vary the solubility of the composition in an aqueous medium during use such that the rinse aid
  • the composition may include a secondary hardening agent in an amount in the range of up to 10 wt%.
  • secondary hardening agents are may be present in an amount in the range of 0-10 wt%, often in the range of 0 to 5 wt% and sometimes in the range of 0 to.5 wt-%.
  • composition may also include other surfactants as enumerated hereinafter.
  • Anionic surfactants are surface active substances which are categorized as anionics because the charge on the hydrophobe is negative; or surfactants in which the hydrophobic section of the molecule carries no charge unless the pH is elevated to neutrality or above (e.g. carboxylic acids).
  • Carboxylate, sulfonate, sulfate and phosphate are the polar (hydrophilic) solubilizing groups found in anionic surfactants.
  • sodium, lithium and potassium impart water solubility; ammonium and substituted ammonium ions provide both water and oil solubility; and, calcium, barium, and magnesium promote oil solubility.
  • anionics are excellent detersive surfactants and are therefore traditionally favored additions to heavy duty detergent compositions as well as rinse aids.
  • anionics have high foam profiles which are useful for the present foaming cleaning compositions.
  • Anionic surface active compounds are useful to impart special chemical or physical properties other than detergency within the composition.
  • the first class includes acylamino acids (and salts), such as acylgluamates, acyl peptides, sarcosinates (e.g. N-acyl sarcosinates), taurates (e.g. N-acyl taurates and fatty acid amides of methyl tauride), and the like.
  • the second class includes carboxylic acids (and salts), such as alkanoic acids (and alkanoates), ester carboxylic acids (e.g. alkyl succinates), ether carboxylic acids, and the like.
  • the third class includes sulfonic acids (and salts), such as isethionates (e.g.
  • acyl isethionates alkylaryl sulfonates, alkyl sulfonates, sulfosuccinates (e.g. monoesters and diesters of sulfosuccinate), and the like.
  • a particularly preferred anionic surfactant is alpha olefin sulfonate.
  • the fourth class includes sulfonic acids (and salts), such as isethionates (e.g. acyl isethionates), alkylaryl sulfonates, alkyl sulfonates, sulfosuccinates (e.g. monoesters and diesters of sulfosuccinate), and the like.
  • the fifth class includes sulfuric acid esters (and salts), such as alkyl ether sulfates, alkyl sulfates, and the like.
  • the fifth class includes sulfuric acid esters (and salts), such as alkyl ether sulfates, alkyl sulfates, and the like.
  • a particularly preferred anionic surfactant is sodium laurel ether sulfate.
  • Anionic sulfate surfactants suitable for use in the present compositions include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C 5 -C 17 acyl-N--(C 1 -C 4 alkyl) and --N--(C 1 -C 2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Ammonium and substituted ammonium such as mono-, di- and triethanolamine
  • alkali metal such as sodium, lithium and potassium
  • salts of the alkyl mononuclear aromatic sulfonates such as the alkyl benzene sulfonates containing from 5 to 18 carbon atoms in the alkyl group in a straight or branched chain, e.g., the salts of alkyl benzene sulfonates or of alkyl toluene, xylene, cumene and phenol sulfonates; alkyl naphthalene sulfonate, diamyl naphthalene sulfonate, and dinonyl naphthalene sulfonate and alkoxylated derivatives.
  • Suitable synthetic, water soluble anionic surfactant compounds include the ammonium and substituted ammonium (such as mono-, di- and triethanolamine) and alkali metal (such as sodium, lithium and potassium) salts of the alkyl mononuclear aromatic sulfonates such as the alkyl benzene sulfonates containing from 5 to 18 carbon atoms in the alkyl group in a straight or branched chain, e.g., the salts of alkyl benzene sulfonates or of alkyl toluene, xylene, cumene and phenol sulfonates; alkyl naphthalene sulfonate, diamyl naphthalene sulfonate, and dinonyl naphthalene sulfonate and alkoxylated derivatives.
  • ammonium and substituted ammonium such as mono-, di- and triethanolamine
  • alkali metal such as sodium
  • Anionic carboxylate surfactants suitable for use in the present compositions include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps (e.g. alkyl carboxyls).
  • Secondary soap surfactants (e.g. alkyl carboxyl surfactants) useful in the present compositions include those which contain a carboxyl unit connected to a secondary carbon.
  • the secondary carbon can be in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl-substituted cyclohexyl carboxylates.
  • the secondary soap surfactants typically contain no ether linkages, no ester linkages and no hydroxyl groups. Further, they typically lack nitrogen atoms in the head-group (amphiphilic portion).
  • Suitable secondary soap surfactants typically contain 11-13 total carbon atoms, although more carbons atoms (e.g., up to 16) can be
  • anionic surfactants suitable for use in the present compositions include olefin sulfonates, such as long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkenesulfonates and hydroxyalkane-sulfonates. Also included are the alkyl sulfates, alkyl poly(ethyleneoxy)ether sulfates and aromatic poly(ethyleneoxy)sulfates such as the sulfates or condensation products of ethylene oxide and nonyl phenol (usually having 1 to 6 oxyethylene groups per molecule). Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • anionic surfactants are given in " Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch ). A variety of such surfactants are also generally disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
  • Zwitterionic surfactants can be thought of as a subset of the amphoteric surfactants.
  • 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.
  • Examples of such 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.
  • R1 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
  • 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-car- boxylate; 5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sul- fate; 3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane- -1-phosphate; 3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propan-e-1-phosphonate; 3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate; 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy-propane-1-sulf
  • the zwitterionic surfactant suitable for use in the present compositions includes a betaine of the general structure:
  • 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(R1) 2 N.sup.+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.
  • Betaines and sultaines and other such zwitterionic surfactants are present in an amount of from Anionic surfactants are present in the composition in any detersive amount which can range typically from 0.01 wt. % to 75 wt. % of the rinse aid composition. In a preferred embodiment, 10 wt. % to 30 wt. % and more preferably from 15 wt. % to 25 wt. %.
  • the semi-polar type of nonionic surface active agents is another class of nonionic surfactant useful in compositions of the present invention.
  • semi-polar nonionics are high foamers and foam stabilizers, which can limit their application in CIP systems. However, within compositional embodiments of this invention designed for high foam cleaning methodology, semi-polar nonionics would have immediate utility.
  • the 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 8 to 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. through an oxygen or nitrogen atom, to form a ring structure
  • R 4 is an alkaline or a hydroxyalkylene group containing 2 to 3 carbon atoms
  • n ranges from 0 to 20.
  • Useful water soluble amine oxide surfactants are selected from the coconut or tallow alkyl di-(lower alkyl) amine oxides, specific examples of which are dodecyldimethylamine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylamine oxide, heptadecyldimethylamine oxide, octadecyldimethylamine oxide, dodecyldipropylamine oxide, tetradecyldipropylamine oxide, hexadecyldipropylamine oxide, tetradecyldibutylamine oxide, octadecyldibutylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide, dimethyl
  • Useful semi-polar nonionic surfactants also include the water soluble phosphine oxides having the following structure: wherein the arrow is a conventional representation of a semi-polar bond; and R 1 is an alkyl, alkenyl or hydroxyalkyl moiety ranging from 10 to 24 carbon atoms in chain length; and R 2 and R 3 are each alkyl moieties separately selected from alkyl or hydroxyalkyl groups containing 1 to 3 carbon atoms.
  • Examples of useful phosphine oxides include dimethyldecylphosphine oxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphine oxide, dimethylhexadecylphosphine oxide, diethyl-2-hydroxyoctyldecylphosp- hine oxide, bis(2-hydroxyethyl)dodecylphosphine oxide, and bis(hydroxymethyl)tetradecylphosphine oxide.
  • Semi-polar nonionic surfactants useful herein also include the water soluble sulfoxide compounds which have the structure: wherein the arrow is a conventional representation of a semi-polar bond; and, R 1 is an alkyl or hydroxyalkyl moiety of 8 to 28 carbon atoms, from 0 to 5 ether linkages and from 0 to 2 hydroxyl substituents; and R 2 is an alkyl moiety consisting of alkyl and hydroxyalkyl groups having 1 to 3 carbon atoms.
  • sulfoxides include dodecyl methyl sulfoxide; 3-hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methyl sulfoxide; and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.
  • anionic surfactants are given in " Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch ). A variety of such surfactants are also generally disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
  • cationic surfactants may be synthesized from any combination of elements containing an "onium" structure RnX+Y-- and could include compounds other than nitrogen (ammonium) such as phosphorus (phosphonium) and sulfur (sulfonium).
  • ammonium such as phosphorus (phosphonium) and sulfur (sulfonium).
  • the cationic surfactant field is dominated by nitrogen containing compounds, probably because synthetic routes to nitrogenous cationics are simple and straightforward and give high yields of product, which can make them less expensive.
  • Cationic surfactants preferably include, more preferably refer to, compounds containing at least one long carbon chain hydrophobic group and at least one positively charged nitrogen.
  • the long carbon chain group may be attached directly to the nitrogen atom by simple substitution; or more preferably indirectly by a bridging functional group or groups in so-called interrupted alkylamines and amido amines.
  • Such functional groups can make the molecule more hydrophilic and/or more water dispersible, more easily water solubilized by co-surfactant mixtures, and/or water soluble.
  • additional primary, secondary or tertiary amino groups can be introduced or the amino nitrogen can be quaternized with low molecular weight alkyl groups.
  • the nitrogen can be a part of branched or straight chain moiety of varying degrees of unsaturation or of a saturated or unsaturated heterocyclic ring.
  • cationic surfactants may contain complex linkages having more than one cationic nitrogen atom.
  • the surfactant compounds classified as amine oxides, amphoterics and zwitterions are themselves typically cationic in near neutral to acidic pH solutions and can overlap surfactant classifications.
  • Polyoxyethylated cationic surfactants generally behave like nonionic surfactants in alkaline solution and like cationic surfactants in acidic solution.
  • R represents a long alkyl chain
  • R', R" and R'" may be either long alkyl chains or smaller alkyl or aryl groups or hydrogen and X represents an anion.
  • the amine salts and quaternary ammonium compounds are preferred for practical use in this invention due to their high degree of water solubility.
  • the majority of large volume commercial cationic surfactants can be subdivided into four major classes and additional sub-groups known to those of skill in the art and described in " Surfactant Encyclopedia," Cosmetics & Toiletries, Vol. 104 (2) 86-96 (1989 ).
  • the first class includes alkylamines and their salts.
  • the second class includes alkyl imidazolines.
  • the third class includes ethoxylated amines.
  • the fourth class includes quaternaries, such as alkylbenzyldimethylammonium salts, alkyl benzene salts, heterocyclic ammonium salts, tetra alkylammonium salts, and the like.
  • Cationic surfactants are known to have a variety of properties that can be beneficial in the present compositions. These desirable properties can include detergency in compositions of or below neutral pH, antimicrobial efficacy, thickening or gelling in cooperation with other agents, and the like.
  • Cationic surfactants useful in the compositions of the present invention include those having the formula R 1 m R 2 x YLZ wherein each R 1 is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to three phenyl or hydroxy groups and optionally interrupted by up to four of the following structures: or an isomer or mixture of these structures, and which contains from 8 to 22 carbon atoms.
  • the R 1 groups can additionally contain up to 12 ethoxy groups.
  • m is a number from 1 to 3.
  • no more than one R 1 group in a molecule has 16 or more carbon atoms when m is 2, or more than 12 carbon atoms when m is 3.
  • Each R 2 is an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl group with no more than one R 2 in a molecule being benzyl, and x is a number from 0 to 11, preferably from 0 to 6. The remainder of any carbon atom positions on the Y group is filled by hydrogens.
  • Y can be a group including, but not limited to: or a mixture thereof.
  • L is 1 or 2
  • the Y groups being separated by a moiety selected from R 1 and R 2 analogs (preferably alkylene or alkenylene) having from 1 to 22 carbon atoms and two free carbon single bonds when L is 2.
  • Z is a water soluble anion, such as sulfate, methylsulfate, hydroxide, or nitrate anion, particularly preferred being sulfate or methyl sulfate anions, in a number to give electrical neutrality of the cationic component.
  • 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 the 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 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, 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 ).
  • 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 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 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, Cocoamphocarboxy-propionate, Cocoamphoglycinate, Cocoamphocarboxyglycinate, Cocoamphopropyl-sulfonate, and Cocoamphocarboxy-propionic acid.
  • Preferred amphocarboxylic acids are 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.
  • N-alkylamino acids are readily prepared by reacting RNH2, in which R.dbd.C 8 -C 18 straight or branched chain alkyl, fatty amines with halogenated carboxylic acids. Alkylation of the primary amino groups of an amino acid leads to secondary and tertiary amines. Alkyl substituents may have additional amino groups that provide more than one reactive nitrogen center. Most commercial N-alkylamine acids are alkyl derivatives of beta-alanine or beta-N(2-carboxyethyl) alanine.
  • 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 is preferably an acyclic hydrophobic group containing from 8 to 18 carbon atoms
  • M is a cation to neutralize the charge of the anion.
  • Preferred amphoteric surfactants include those derived from coconut products such as coconut oil or coconut fatty acid.
  • the more preferred of these coconut derived surfactants include as part of their structure an ethylenediamine moiety, an alkanolamide moiety, an amino acid moiety, preferably glycine, or a combination thereof; and an aliphatic substituent of from 8 to 18 (preferably 12) carbon atoms.
  • Such a surfactant can also be considered an alkyl amphodicarboxylic acid.
  • Disodium cocoampho dipropionate is one most preferred amphoteric surfactant and is commercially available under the tradename MiranolTM FBS from Rhodia Inc., Cranbury, N.J.
  • Another most preferred coconut derived amphoteric surfactant with the chemical name disodium cocoampho diacetate is sold under the tradename Miranol C2M-SF Conc., also from Rhodia Inc., Cranbury, N.J.
  • Additional surfactant may be present in the compositions in any detersive amount so long as they do not interfere with the electrostatic, ionic interactions that provide for foam stabilization.
  • the rinse aid can optionally include bleaching agent.
  • Bleaching agent can be used for lightening or whitening a substrate, and can include bleaching compounds capable of liberating an active halogen species, such as Cl 2 , Br 2 , -OCl - and/or -OBr - , or the like, under conditions typically encountered during the cleansing process.
  • Suitable bleaching agents for use can include, for example, chlorine-containing compounds such as a chlorine, a hypochlorite, chloramines, of the like.
  • halogen-releasing compounds include the alkali metal dichloroisocyanurates, chlorinated trisodium phosphate, the alkali metal hypochlorites, monochloramine and dichloroamine, and the like.
  • Encapsulated chlorine sources may also be used to enhance the stability of the chlorine source in the composition (see, for example, U.S. Pat. Nos. 4,618,914 and 4,830,773 ).
  • a bleaching agent may also include an agent containing or acting as a source of active oxygen.
  • the active oxygen compound acts to provide a source of active oxygen, for example, may release active oxygen in aqueous solutions.
  • An active oxygen compound can be inorganic or organic, or can be a mixture thereof. Some examples of active oxygen compound include peroxygen compounds, or peroxygen compound adducts.
  • a rinse aid composition may include a minor but effective amount of a bleaching agent, for example, in some embodiments, in the range of up to 10 wt. %, and in some embodiments, in the range of 0.1 to 6 wt. %.
  • the antimicrobial activity or bleaching activity of the rinse aid can be enhanced by the addition of a material which, when the composition is placed in use, reacts with the active oxygen to form an activated component.
  • a peracid or a peracid salt is formed.
  • tetraacetylethylene diamine can be included within the composition to react with the active oxygen and form a peracid or a peracid salt that acts as an antimicrobial agent.
  • active oxygen activators include transition metals and their compounds, compounds that contain a carboxylic, nitrile, or ester moiety, or other such compounds known in the art.
  • the activator includes tetraacetylethylene diamine; transition metal; compound that includes carboxylic, nitrile, amine, or ester moiety; or mixtures thereof.
  • an activator component can include in the range of up to 75 % by wt. of the composition, in some embodiments, in the range of 0.01 to 20% by wt, or in some embodiments, in the range of 0.05 to 10% by weight of the composition.
  • an activator for an active oxygen compound combines with the active oxygen to form an antimicrobial agent.
  • the rinse aid composition includes a solid, such as a solid flake, pellet, or block, and an activator material for the active oxygen is coupled to the solid.
  • the activator can be coupled to the solid by any of a variety of methods for coupling one solid composition to another.
  • the activator can be in the form of a solid that is bound, affixed, glued or otherwise adhered to the solid of the rinse aid composition.
  • the solid activator can be formed around and encasing the solid rinse aid composition.
  • the solid activator can be coupled to the solid rinse aid composition by the container or package for the composition, such as by a plastic or shrink wrap or film.
  • the rinse aid can optionally include a minor but effective amount of one or more of a filler which does not necessarily perform as a rinse and/or cleaning agent per se, but may cooperate with a rinse agent to enhance the overall capacity of the composition.
  • suitable fillers may include sodium chloride, starch, sugars, C 1 -C 10 alkylene glycols such as propylene glycol, and the like.
  • a filler can be included in an amount in the range of up to 20 wt. %, and in some embodiments, in the range of 1-15 wt. %.
  • Sodium sulfate is conventionally used as inert filler.
  • the rinse aid composition can optionally include an anti-redeposition agent capable of facilitating sustained suspension of soils in a rinse solution and preventing removed soils from being redeposited onto the substrate being rinsed.
  • suitable anti-redeposition agents can include fatty acid amides, fluorocarbon surfactants, complex phosphate esters, styrene maleic anhydride copolymers, and cellulosic derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and the like.
  • a rinse aid composition may include up to 10 wt. %, and in some embodiments, in the range of 1 to 5 wt. %, of an anti-redeposition agent.
  • Dyes may be included to alter the appearance of the composition, as for example, FD&C Blue 1 (Sigma Chemical), FD&C Yellow 5 (Sigma Chemical), Direct Blue 86 (Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange 7 (American Cyanamid), Basic Violet 10 (Sandoz), Acid Yellow 23 (GAF), Acid Yellow 17 (Sigma Chemical), Sap Green (Keyston Analine and Chemical), Metanil Yellow (Keystone Analine and Chemical), Acid Blue 9 (Hilton Davis), Sandolan Blue/Acid Blue 182 (Sandoz), Hisol Fast Red (Capitol Color and Chemical), Fluorescein (Capitol Color and Chemical), Acid Green 25 (Ciba-Geigy), and the like.
  • Dyes may be included to alter the appearance of the composition, as for example, FD&C Blue 1 (Sigma Chemical), FD&C Yellow 5 (Sigma Chemical), Direct Blue 86 (Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange 7 (American Cyanamid
  • Fragrances or perfumes that may be included in the compositions include, for example, terpenoids such as citronellol, aldehydes such as amyl cinnamaldehyde, a jasmine such as CIS-jasmine or jasmal, vanillin, and the like.
  • the composition can also optionally include one or more functional polydimethylsiloxones.
  • a polyalkylene oxide-modified polydimethylsiloxane, nonionic surfactant or a polybetaine-modified polysiloxane amphoteric surfactant can be employed as an additive.
  • Both, in some embodiments, are linear polysiloxane copolymers to which polyethers or polybetaines have been grafted through a hydrosilation reaction.
  • siloxane surfactants are known as SILWET® surfactants available from Union Carbide or ABIL® polyether or polybetaine polysiloxane copolymers available from Goldschmidt Chemical Corp., and described in U.S. Pat. No. 4,654,161 .
  • the particular siloxanes used can be described as having, e.g., low surface tension, high wetting ability and excellent lubricity.
  • these surfactants are said to be among the few capable of wetting polytetrafluoroethylene surfaces.
  • the siloxane surfactant employed as an additive can be used alone or in combination with a fluorochemical surfactant.
  • the fluorochemical surfactant employed as an additive optionally in combination with a silane can be, for example, a nonionic fluorohydrocarbon, for example, fluorinated alkyl polyoxyethylene ethanols, fluorinated alkyl alkoxylate and fluorinated alkyl esters.
  • a nonionic fluorohydrocarbon for example, fluorinated alkyl polyoxyethylene ethanols, fluorinated alkyl alkoxylate and fluorinated alkyl esters.
  • the composition may include functional polydimethylsiloxones in an amount in the range of up to 10 wt-%.
  • functional polydimethylsiloxones in an amount in the range of up to 10 wt-%.
  • some embodiments may include in the range of 0.1 to 10 wt-% of a polyalkylene oxide-modified polydimethylsiloxane or a polybetaine-modified polysiloxane, optionally in combination with 0.1 to 10 wt-% of a fluorinated hydrocarbon nonionic surfactant.
  • the composition can also optionally include one or more humectants.
  • a humectant is a substance having an affinity for water.
  • the humectant can be provided in an amount sufficient to aid in reducing the visibility of a film on the substrate surface.
  • the visibility of a film on substrate surface is a particular concern when the rinse water contains in excess of 200 ppm total dissolved solids.
  • the humectant is provided in an amount sufficient to reduce the visibility of a film on a substrate surface when the rinse water contains in excess of 200 ppm total dissolved solids compared to a rinse agent composition not containing the humectant.
  • water solids filming or “filming” refer to the presence of a visible, continuous layer of matter on a substrate surface that gives the appearance that the substrate surface is not clean.
  • humectants that can be used include those materials that contain greater than 5 wt. % water (based on dry humectant) equilibrated at 50% relative humidity and room temperature.
  • Exemplary humectants that can be used include glycerin, propylene glycol, sorbitol, alkyl polyglycosides, polybetaine polysiloxanes, and mixtures thereof.
  • the rinse agent composition can include humectant in an amount in the range of up to 75% based on the total composition, and in some embodiments, in the range of 5 wt. % to 75 wt. % based on the weight of the composition.
  • the rinse aid may include other active ingredients, such as pH modifiers, buffering agents, cleaning enzyme, carriers, processing aids, or others, and the like.
  • the rinse aid can be formulated such that during use in aqueous operations, for example in aqueous cleaning operations, the rinse water will have a desired pH.
  • compositions designed for use in rinsing may be formulated such that during use in aqueous rinsing operation the rinse water will have a pH in the range of 3 to 5, or in the range of 5 to 9.
  • Liquid product formulations in some embodiments have a (10% dilution) pH in the range of 2 to 4.
  • Techniques for controlling pH at recommended usage levels include the use of buffers, alkali, acids, etc., and are well known to those skilled in the art.
  • the present solid composition can be made by an advantageous method of pressing the solid composition. Specifically, in a forming process, the liquid and solid components are introduced into the 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. In an exemplary embodiment, the components are mixed in the mixing system for at least approximately 5 seconds. The mixture is then discharged from the mixing system into, or through, a die, press or other shaping means. The product is then packaged. In an exemplary embodiment, the solid formed composition begins to harden between approximately 1 minute and approximately 3 hours. Particularly, the formed composition begins to harden in between approximately 1 minute and approximately 2 hours. More particularly, the formed composition begins to harden in between approximately 1 minute and approximately 20 minutes.
  • a method of making a solid rinse aid composition comprises admixing a solid acid, nonionic surfactant and short chain alkyl benzene and/or alkyl naphthalene sulfonates, allowing said mixture to set thereafter, mixing in any liquid components of said rinse aid, such as preservative, additional surfactant, water, dyes and the like, and forming a solid with the rinse aid mixture by pressing or extrusion.
  • the method of the present invention can produce a stable solid without employing a melt and solidification of the melt as in conventional casting.
  • Forming a melt requires heating a composition to melt it.
  • the heat can be applied externally or can be produced by a chemical exotherm (e.g., from mixing caustic (sodium hydroxide) and water). Heating a composition consumes energy.
  • Handling a hot melt requires safety precautions and equipment.
  • solidification of a melt requires cooling the melt in a container to solidify the melt and form the cast solid. Cooling requires time and/or energy.
  • the present method can employ ambient temperature and humidity during solidification or curing of the present compositions.
  • the solids of the present invention are held together not by solidification from a melt but by a binding agent produced in the admixed particles and that is effective for producing a stable solid.
  • the invention is formed to solid by pressing or extrusion.
  • a single- or twin-screw extruder may be used to combine and mix one or more components agents at high shear to form a homogeneous mixture.
  • the processing temperature is at or below the melting temperature of the components.
  • the processed mixture may be dispensed from the mixer by pressing, forming, extruding or other suitable means, whereupon the 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 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 resulting solid composition may take forms including, but not limited to: an extruded, molded or formed solid pellet, block, tablet, powder, granule, flake; or the formed solid can thereafter be ground or formed into a powder, granule, or flake.
  • extruded pellet materials formed have a weight of between approximately 50 grams and approximately 250 grams
  • extruded solids have a weight of approximately 100 grams or greater
  • solid blocks formed 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.
  • the solid rinse aid composition is provided in the form of a unit dose.
  • a unit dose refers to a solid rinse aid composition unit sized so that the entire unit is used during a single washing cycle.
  • the solid cleaning composition can have a mass of 1 g to 50 g.
  • the composition can be a solid, a pellet, or a tablet having a size of 50 g to 250 g, of 100 g or greater, or 40 g to 11,000 g.
  • the solid rinse aid composition is provided in the form of a multiple-use solid, such as, a block or a plurality of pellets, and can be repeatedly used to generate aqueous rinse compositions for multiple washing cycles.
  • the solid rinse aid composition is provided as a solid having a mass of 5 g to 10 kg.
  • a multiple-use form of the solid rinse aid composition has a mass of 1 to 10 kg.
  • a multiple-use form of the solid rinse aid composition has a mass of 5 kg to 8 kg.
  • a multiple-use form of the solid rinse aid composition has a mass of 5 g to 1 kg, or 5 g and to 500 g.
  • the solid rinse aid composition can be, but is not necessarily, incorporated into a packaging system or receptacle.
  • the packaging receptacle or container may be rigid or flexible, and include any material suitable for containing the compositions produced, as for example glass, metal, plastic film or sheet, cardboard, cardboard composites, paper, or the like.
  • Rinse aid compositions may be allowed to solidify in the packaging or may be packaged after formation of the solids in commonly available packaging and sent to distribution center before shipment to the consumer.
  • the temperature of the processed mixture is low enough so that the mixture may be cast or extruded directly into the container or other packaging system without structurally damaging the material.
  • the packaging used to contain the rinse aid is manufactured from a flexible, easy opening film material.
  • the rinse aid can be dispensed as a concentrate or as a use solution.
  • the rinse aid concentrate can be provided in a solid form or in a liquid form.
  • the concentrate will be diluted with water to provide the use solution that is then supplied to the surface of a substrate.
  • the aqueous use solution may contain about 2,000 parts per million (ppm) or less active materials, or about 1,000 ppm or less active material, or in the range of about 10 ppm to about 500 ppm of active materials, or in the range of about 10 to about 300 ppm, or in the range of about 10 to 200 ppm.
  • the use solution can be applied to the substrate during a rinse application, for example, during a rinse cycle, for example, in a warewashing machine, a car wash application, institutional healthcare surface cleaning or the like.
  • formation of a use solution can occur from a rinse agent installed in a cleaning machine, for example onto a dish rack.
  • the rinse agent can be diluted and dispensed from a dispenser mounted on or in the machine or from a separate dispenser that is mounted separately but cooperatively with the dish machine.
  • liquid rinse agents can be dispensed by incorporating compatible packaging containing the liquid material into a dispenser adapted to diluting the liquid with water to a final use concentration.
  • dispensers for the liquid rinse agent of the invention are DRYMASTER-P sold by Ecolab Inc., St. Paul, Minn.
  • solid products may be conveniently dispensed by inserting a solid material in a container or with no enclosure into a spray-type dispenser such as the volume SOL-ET controlled ECOTEMP Rinse Injection Cylinder system manufactured by Ecolab Inc., St. Paul, Minn.
  • a spray-type dispenser such as the volume SOL-ET controlled ECOTEMP Rinse Injection Cylinder system manufactured by Ecolab Inc., St. Paul, Minn.
  • a spray-type dispenser such as the volume SOL-ET controlled ECOTEMP Rinse Injection Cylinder system manufactured by Ecolab Inc., St. Paul, Minn.
  • the dispenser directs water onto the solid block of rinse agent which effectively dissolves a portion of the block creating a concentrated aqueous rinse solution which is then fed directly into the rinse water forming the aqueous rinse.
  • the aqueous rinse is then contacted with the surfaces to affect a complete rinse.
  • This dispenser and other similar dispensers are capable of controlling the effective concentration of the active portion in the aqueous rinse by measuring the volume of material dispensed, the actual concentration of the material in the rinse water (an electrolyte measured with an electrode) or by measuring the time of the spray on the cast block.
  • concentration of active portion in the aqueous rinse is preferably the same as identified above for liquid rinse agents.
  • composition of the invention is particularly beneficial for use with hard water.
  • the composition can provide good rinsing and levels up to 342.75 ppm (20gpg) water hardness.
  • the rinse aid composition of the invention can be used in a high solids containing water environment in order to reduce the appearance of a visible film caused by the level of dissolved solids provided in the water.
  • high solids containing water is considered to be water having a total dissolved solids (TDS) content in excess of 200 ppm.
  • TDS total dissolved solids
  • the service water contains total dissolved solids content in excess of 400 ppm, and even in excess of 800 ppm.
  • the applications where the presence of a visible film after washing a substrate is a particular problem includes the restaurant or warewashing industry, the car wash industry, the healthcare instrument reprocessing and cart washing sections, and the general cleaning of hard surfaces.
  • the rinse aid When used in these automated washing applications such as ware washers and healthcare instrument and cart washers, the rinse aid should provide effective sheeting action and low foaming properties. It is believed that the rinse aid composition of this invention is adventurously formulated to control the issues mentioned above
  • the present methods and solid rinse aid compositions may be used for cleaning a medical cart, cage, instrument, or device in a medical or health care environment.
  • cleaning a medical cart, cage, instrument, or device includes contacting the medical cart, cage, instrument, or device with an aqueous cleaning composition and then according to the invention, rinsing or contacting the same with a rinse solution comprising a dissolved rinse aid of the invention.
  • the method can also involve antimicrobial treatment of the medical cart, cage, instrument, or device by contacting with an aqueous antimicrobial composition formed by dissolving or suspending a solid antimicrobial composition, preferably a solid quaternary ammonium or solid halogen antimicrobial composition.
  • a cleaning composition can take place through manual application in a wash area or bay or through application by cart, cage, instrument, or device washing apparatus.
  • rinsing and/or antimicrobial treatment can also take place in the wash area or bay, or in a separate area or bay.
  • a typical cart, cage, instrument, or device washing apparatus includes a wash station which applies the cleaning composition.
  • a washing apparatus also includes a rinse station that can rinse the cart, cage, instrument, or device with water or another suitable rinse composition, such as a solid neutral or neutralizing rinse composition.
  • Such a washing apparatus can also, optionally, include an antimicrobial treatment station that can contact the cart, cage, instrument, or device with a dissolved solid antimicrobial composition, such as a solid quaternary ammonium or solid halogen antimicrobial composition.
  • a washing apparatus can conduct one or more of washing, rinsing, and/or antimicrobial treatment of steps at one, two, three, or more stations.
  • rinsing a medical cart, cage, instrument, or device can be employed for rinsing a medical cart, cage, instrument, or device made of a variety of materials in a medical or health care environment.
  • rinsing a medical cart, cage, instrument, or device includes rinsing the medical cart, cage, instrument, or device using an aqueous rinse composition formed by dissolving or suspending the solid rinse composition of the invention.
  • a typical cart, cage, instrument, or device washing apparatus includes a rinse station that can rinse the cart, cage, instrument, or device with a liquid rinse composition formed from a solid neutral or neutralizing rinse composition.
  • a washing apparatus can also, optionally, include a washing and/or antimicrobial treatment station.
  • the antimicrobial composition employed either for manual or machine medical cart, cage, instrument, or device antimicrobial treatment can be a solid antimicrobial composition, preferably a solid quaternary ammonium or solid halogen antimicrobial composition, which is described in greater detail herein below.
  • Medical cart cleaning can be accomplished either manually or with a machine.
  • Manual medical cart cleaning can include preparing a use composition of a solid cleaning composition and applying it to the medical cart. Applying typically includes wiping or scrubbing the medical cart with a brush, a towel, or a sponge soaked with the cleaning composition. Applying can also include spraying the cart with the use composition.
  • Manual medical cart cleaning can also include preparing a use composition of a rinse composition, preferably a neutral rinse composition, and applying it to the medical cart. Applying a rinse composition can include spraying, pouring, or wiping the use composition onto the cart.
  • Manual medical cart cleaning can also include preparing a use composition of a solid antimicrobial composition, preferably a solid quaternary ammonium or solid halogen antimicrobial composition, and applying it to the medical cart. Applying an antimicrobial composition can include spraying, pouring, or wiping the use composition onto the cart. Drying the medical cart, either manually or air drying, typically follows rinsing.
  • a solid antimicrobial composition preferably a solid quaternary ammonium or solid halogen antimicrobial composition
  • Machine cleaning of a medical cart can employ any of a variety of configurations of medical cart cleaning apparatus. Such apparatus can be adapted to dispense the solid detergent, rinse aid composition of the invention and/or antimicrobial composition.
  • a medical cart cleaning apparatus typically includes at least one chamber that houses the medical cart during washing, rinsing, and/or antimicrobial treatment.
  • Smaller medical cart cleaning apparatus typically include a single chamber sized to house, for example, 1-3 medical carts.
  • Medical carts can be introduced into the smaller apparatus by an operator through a door or other coverable opening in the chamber.
  • the apparatus then subjects the carts in the chamber to one or more of washing, rinsing, antimicrobial treatment, and/or drying cycles. Washing typically occurs by spraying the medical cart with a use wash composition. Rinsing typically occurs by spraying the medical cart with a use rinse composition.
  • antimicrobial treatment can occur by spraying the medical cart with a use antimicrobial composition. Drying can occur by blowing ambient or heated air, or by treating with steam.
  • Medical carts can be removed from the chamber by an operator through the same door or other coverable opening or through an exit door or other coverable opening on an opposite side of the apparatus.
  • Larger medical cart cleaning apparatus typically includes a transport apparatus that transports one or several carts through one or more chambers including washing, rinsing, optionally antimicrobial treatment, and/or drying stations.
  • a medical cart cleaning apparatus can resemble a touchless car wash sized and configured for cleaning medical carts instead of cars.
  • the cart is transported through the washing, rinsing, optional antimicrobial treatment, and/or drying stations by a track or rail apparatus while tipped at an acute angle from the horizontal, with its doors (if any) open. This tipping can keep the doors open and allow liquid to drain off any normally horizontal surfaces of the medical cart.
  • the entry to a larger medical cart cleaning apparatus can be covered, for example, by a door or with hanging plastic strips that allow entry of carts but that retain use compositions in the apparatus.
  • the wash station typically sprays the medical cart with use wash composition.
  • a rinse station typically sprays the medical cart with use rinse composition.
  • An optional antimicrobial treatment station typically sprays the medical cart with use antimicrobial composition.
  • blowers blow ambient or heated air on the cart, or the cart is steam treated.
  • the cart can be removed from the apparatus and towel dried.
  • One or more stations can be at different, overlapping, or the same locations.
  • the exit from the apparatus can be covered in the same manner as the entrance.
  • Mechanical cart washers can employ up to 113.56 (30) to 151.41 liter (40 gallons) of use composition of cleaning composition per wash cycle, up to 113.56 (30) to 151.41 liter (40 gallons) of use composition rinse composition per rinse cycle, and, optionally, up to 113.56 (30) to 151.41 liter (40 gallons) of use antimicrobial composition per antimicrobial treatment cycle.
  • the actual amount of cleaning, rinsing, or antimicrobial composition used will be based on the judgment of the user, and will depend upon factors such as the particular product formulation of the composition, the concentration of the composition, the number of soiled carts to be cleaned and the degree of soiling of the carts.
  • a machine that washes medical carts can also be employed to wash other wheeled medical equipment or supplies such as wheel chairs, wheeled stands, such as those that hold intravenous bags, tubes and pumps, wheeled (metro) shelves, and the like.
  • Control is Water (0 or 291.33 ppm (17gpg) depending on experimental purpose).
  • Rinse aid A is a commercially available rinse aid from Steris.
  • Rinse aid B is a commercially available rinse aid from Getinge that includes phosphoric acid.
  • Rinse aid C is a commercially available liquid rinse aid from Ecolab.
  • Commercial rinse aid D is a commercially available solid rinse aid from Ecolab that does not include any hardness or TDS components.
  • compositions of the invention were formulated per below and tested.
  • Composition of the Invention A Composition of the Invention B Name Wt % Wt % Water Deionized 0.5 0.5 dye 0.15 0.15 Kathon GC-ICP Preservative 1.4 1.4 Plurafac SLF-180 13.1 7.1 Sodium Xylene Sulfonate 96% 69.85 69.85 Citric Acid, USP, Anhydrous Grade 15 15 Dehypon GRA 6
  • Results are shown in Figure 1 . As can be seen, From the Image analysis means, one can see that the Compositions of the invention outperform the other rinse aid products.
  • Figure 3 shows the results for the Al coupon and one can see that the compositions of the invention demonstrated very little corrosion. Other metal coupons tested showed that the formulations of the invention are compatible with all metals.
  • the Inversion foam test is used to simulate Sump solution agitation. Rinse additive is added to the graduated cylinder, and the foam generated is measured after 10 180° inversions.

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Claims (12)

  1. Une composition solide d'adjuvant de rinçage comprenant :
    un acide qui est sous forme solide à température ambiante soit naturellement, soit suite à un traitement ;
    de 50 % en poids à 80 % en poids d'un ou plusieurs alkylbenzènes et/ou alkyles naphtalènes sulfonates à chaîne courte choisis dans le groupe constitué :
    du xylène sulfonate de sodium, du toluènesulfonate de sodium, du cumènesulfonate de sodium, du toluènesulfonate de potassium, du xylène sulfonate d'ammonium, du xylène sulfonate de calcium, de l'alkyle naphtalène sulfonate de sodium et du butylenaphtalène sulfonate de sodium ; et
    d'un ou plusieurs tensioactifs non ioniques.
  2. Adjuvant de rinçage selon la revendication 1, dans lequel ledit alkylbenzènesulfonate à chaîne courte est le xylène sulfonate de sodium ou le cumènesulfonate de sodium.
  3. Composition selon la revendication 1 comprenant en outre un agent chélatant, ledit agent chélatant étant du GLDA.
  4. Composition selon la revendication 1, dans laquelle ledit acide est de l'acide citrique.
  5. Composition selon la revendication 1, dans lequel ledit acide solide est présent en une quantité de 5 % en poids à 40 % en poids.
  6. Procédé de préparation de la composition d'adjuvant de rinçage solide selon l'une quelconque des revendications 1 à 5, consistant à :
    a. Mélanger un acide solide, un tensioactif non ionique et un alkylbenzènesulfonate et/ou un alkyle naphtalène sulfonate à chaîne courte ;
    b. Laisser durcir ledit mélange et ensuite
    c. Mélanger tous les composants liquides dudit adjuvant de rinçage, tels qu'un conservateur, un tensioactif supplémentaire, de l'eau et des colorants ;
    d. Former un solide avec le mélange d'adjuvant de rinçage par pressage ou extrusion.
  7. Procédé selon la revendication 6, dans lequel à l'étape b. ledit mélange est laissé durcir pour au moins 1 jour.
  8. Procédé de rinçage d'une surface dure dans une application de nettoyage comprenant les étapes consistant à :
    a. fournir une composition solide d'adjuvant de rinçage selon la revendication 1 ;
    b. mettre en contact la composition d'adjuvant de rinçage avec de l'eau pour former une solution d'utilisation ; et
    c. appliquer la solution d'utilisation sur la surface dure.
  9. Procédé selon la revendication 8, dans lequel ladite solution d'utilisation comprend 2 000 ppm ou moins de matières actives.
  10. Procédé selon la revendication 8, dans lequel ladite mise en contact est effectuée en dirigeant de l'eau sur un bloc solide d'adjuvant de rinçage.
  11. Procédé selon la revendication 8, dans lequel ledit adjuvant de rinçage solide est dissous dans une solution d'utilisation par ladite mise en contact.
  12. Procédé selon la revendication 8, dans lequel ladite surface dure comprend du métal, du verre, du plastique, de la céramique ou des carreaux.
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US9011610B2 (en) 2012-06-22 2015-04-21 Ecolab Usa Inc. Solid fast draining/drying rinse aid for high total dissolved solid water conditions
US9567551B2 (en) 2012-06-22 2017-02-14 Ecolab Usa Inc. Solid rinse aid composition and method of making same
EP3039107B1 (fr) * 2013-08-27 2019-10-23 Ecolab USA Inc. Composition d'aide au rinçage solide et son procédé de fabrication
AU2016313500B2 (en) * 2015-08-21 2018-12-06 Ecolab Usa Inc. Pyrithione preservative system in solid rinse aid products
US10221376B2 (en) * 2016-04-18 2019-03-05 Ecolab Usa Inc. Solidification process using low levels of coupler/hydrotrope
WO2020004191A1 (fr) * 2018-06-28 2020-01-02 小林製薬株式会社 Matériau de revêtement pour cuvette de toilettes
JP7329976B2 (ja) * 2018-06-28 2023-08-21 小林製薬株式会社 トイレ便器用コーティング剤

Family Cites Families (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2903486A (en) 1959-09-08 Karl h
NL272723A (fr) 1951-05-31
US2674619A (en) 1953-10-19 1954-04-06 Wyandotte Chemicals Corp Polyoxyalkylene compounds
US3048548A (en) 1959-05-26 1962-08-07 Economics Lab Defoaming detergent composition
US3382178A (en) 1965-02-01 1968-05-07 Petrolite Corp Stable alkaline detergents
US3929678A (en) 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
USRE32818E (en) 1978-02-07 1989-01-03 Ecolab Inc. Cast detergent-containing article and method of using
USRE32763E (en) 1978-02-07 1988-10-11 Ecolab Inc. Cast detergent-containing article and method of making and using
US4426362A (en) 1978-12-05 1984-01-17 Economics Laboratory, Inc. Solid block detergent dispenser
US4565647B1 (en) 1982-04-26 1994-04-05 Procter & Gamble Foaming surfactant compositions
JPS60189108A (ja) 1984-03-08 1985-09-26 日本石油化学株式会社 電気絶縁油
DE3417912C1 (de) 1984-05-15 1985-07-25 Goldschmidt Ag Th Betaingruppen enthaltende Siloxane,deren Herstellung und Verwendung in kosmetischen Zubereitungen
US4690305A (en) 1985-11-06 1987-09-01 Ecolab Inc. Solid block chemical dispenser for cleaning systems
US4687121A (en) 1986-01-09 1987-08-18 Ecolab Inc. Solid block chemical dispenser for cleaning systems
US4826661A (en) 1986-05-01 1989-05-02 Ecolab, Inc. Solid block chemical dispenser for cleaning systems
US4830773A (en) 1987-07-10 1989-05-16 Ecolab Inc. Encapsulated bleaches
US5358653A (en) * 1990-06-25 1994-10-25 Ecolab, Inc. Chlorinated solid rinse aid
CN1083483C (zh) 1994-09-12 2002-04-24 生态实验室股份有限公司 用于塑料器皿的漂清助剂
US5603776A (en) 1994-09-12 1997-02-18 Ecolab Inc. Method for cleaning plasticware
CA2167971C (fr) * 1995-02-01 2008-08-26 Paula J. Carlson Bloc de nettoyage a l'acide et methode de fabrication correspondante
ATE307868T1 (de) * 1996-02-14 2005-11-15 Stepan Co Hydrotrop enthaltende reiniger für harte oberflächen mit verminderter rückstandsbildung
US5876514A (en) * 1997-01-23 1999-03-02 Ecolab Inc. Warewashing system containing nonionic surfactant that performs both a cleaning and sheeting function and a method of warewashing
ES2226417T3 (es) * 1998-08-03 2005-03-16 THE PROCTER & GAMBLE COMPANY Formulacion de ayuda en el aclarado.
JP2002522592A (ja) * 1998-08-03 2002-07-23 ザ、プロクター、エンド、ギャンブル、カンパニー 安定非相分離すすぎ助剤分散液の製造方法
EP1352951A1 (fr) * 2002-04-11 2003-10-15 The Procter & Gamble Company Granulé détergent comprenant un tensioactif nonionique et une hydrotrope
US7279455B2 (en) * 2003-11-06 2007-10-09 Ecolab, Inc. Rinse aid composition and method of rising a substrate
JP2007077290A (ja) * 2005-09-14 2007-03-29 Daisan Kogyo Kk Ｃｉｐ用脱臭剤組成物
US8383570B2 (en) * 2007-05-25 2013-02-26 Ecolab Usa Inc. Enhanced melting point rinse aid solid compositions with synergistic preservative
US7521412B2 (en) * 2007-05-25 2009-04-21 Ecolab Inc. Dimensionally stable solid rinse aid
KR101621115B1 (ko) * 2008-12-02 2016-05-13 디버세이, 인크 빌트-인 헹굼 보조제를 포함하는 조성물의 사용에 의한 조리 장치 또는 기기의 세정
AU2010247013B2 (en) * 2009-05-12 2015-02-26 Ecolab Usa Inc. Fast drying and fast draining rinse aid
US20110126858A1 (en) * 2009-11-30 2011-06-02 Xinbei Song Method for rinsing cleaned dishware
US8685911B2 (en) * 2009-11-30 2014-04-01 The Procter & Gamble Company Rinse aid compositions
EP3039107B1 (fr) * 2013-08-27 2019-10-23 Ecolab USA Inc. Composition d'aide au rinçage solide et son procédé de fabrication

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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AU2013399081A1 (en) 2015-11-26
BR112016004119B1 (pt) 2021-06-29
JP2017210627A (ja) 2017-11-30
AU2017201539A1 (en) 2017-03-23
MX2016002237A (es) 2016-06-06
CN114164058A (zh) 2022-03-11
WO2015030836A1 (fr) 2015-03-05
EP3039107A1 (fr) 2016-07-06
JP2016534204A (ja) 2016-11-04
JP6599944B2 (ja) 2019-10-30
AU2019201156A1 (en) 2019-03-07
AU2017201539B2 (en) 2018-11-22
CN105324473A (zh) 2016-02-10
EP3039107A4 (fr) 2017-04-05
BR112016004119A2 (pt) 2017-08-01
AU2013399081B2 (en) 2016-12-22
ES2759203T3 (es) 2020-05-07
AU2019201156B2 (en) 2019-10-31
JP6208873B2 (ja) 2017-10-04

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