EP0875556A2 - Agent de rinçage pour vaisselle en plastique - Google Patents

Agent de rinçage pour vaisselle en plastique Download PDF

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Publication number
EP0875556A2
EP0875556A2 EP98301705A EP98301705A EP0875556A2 EP 0875556 A2 EP0875556 A2 EP 0875556A2 EP 98301705 A EP98301705 A EP 98301705A EP 98301705 A EP98301705 A EP 98301705A EP 0875556 A2 EP0875556 A2 EP 0875556A2
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EP
European Patent Office
Prior art keywords
composition
rinse
plasticware
oxide
aqueous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP98301705A
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German (de)
English (en)
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EP0875556A3 (fr
Inventor
Steven E. Lentsch
Matthew J. Sopha
Victor F. Man
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Ecolab Inc
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Ecolab Inc
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Priority claimed from US08/841,110 external-priority patent/US5880088A/en
Application filed by Ecolab Inc filed Critical Ecolab Inc
Publication of EP0875556A2 publication Critical patent/EP0875556A2/fr
Publication of EP0875556A3 publication Critical patent/EP0875556A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3738—Alkoxylated silicones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • 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
    • C11D1/004—Surface-active compounds containing F
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • the invention relates to warewashing processes and chemicals used in washing plastic cookware, dishware and flatware. More particularly, the invention relates to primarily organic materials that can be added to water to promote a sheeting action in an aqueous rinse used after an alkaline detergent cycle. Such aqueous rinse aids promote effective sheeting to result in removal of aqueous rinse materials and solids contained therein from plastic cookware, dishware and flatware in acceptable drying time without cracking the plasticware.
  • Such automatic warewashing machines clean dishes using two or more cycles which can include initially a wash cycle followed by a rinse cycle.
  • Such dishwashers can also utilize soak cycle, prewash cycle, scrape cycle, second wash cycle, a rinse cycle, a sanitizing cycle and a drying cycle, if required.
  • Such cycles can be repeated if needed and additional cycles can be used.
  • After passing through a wash, rinse and dry cycle, dishware, cups, glasses, etc. can exhibit spotting that arises from the uneven draining of the water from the surface of the ware after the rinse step. Spotting is aesthetically unacceptable in most consumer and institutional environments.
  • Rinse agents available in the consumer and institutional markets comprise liquid or solid forms which are typically added to, dispersed or dissolved in water to form an aqueous rinse. Such dissolution can occur from a rinse agent installed onto the 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.
  • Commonly available commercial rinse agents typically comprise a low foaming surface active agent made from homopolymers or copolymers of an alkylene oxide such as ethylene oxide or propylene oxide or mixtures thereof.
  • the surfactants are formed by reacting an alcohol, a glycol, a carboxylic acid, an amine or a substituted phenol with various proportions and combinations of ethylene oxide and propylene oxide to form both random and block copolymer substituents.
  • the commonly available rinse agents have primarily focused on reducing spotting and filming on surfaces such as glass, ceramics, china and metal.
  • plastic dishware is more commonly used now, especially in the institutional market.
  • a special problem for rinse aid surfactants used for plasticware is the attack and crazing of the ware.
  • Block copolymer surfactants do not seem to attack plastics as strongly as fatty alcohol or alkyl phenol-based nonionic surfactants.
  • Linear alkoxylates show they do not attack plexiglass, polystyrene, or Tupperware®, common utensil plastics. Nevertheless, current surfactants have not provided the desired sheeting in an acceptable drying time following the rinse cycle.
  • U.S. Patent 5,298,289 describes the treatment and after-treatment of surfaces, especially metals, with derivatives of polyphenol compounds. These compositions are also said to be useful in treating plastic and painted surfaces to improve rinsability without water breaks.
  • the surfactants employed are a combination of previously known anionic and nonionic surfactants.
  • Liquid dishwashing detergent compositions are described in U.S. Patent 4,492,646 containing highly ethoxylated nonionic surfactants to reduce spotting and filming on surfaces such as glass, ceramics and metal.
  • European Patent Publication 0,432,836 describes the use of alkyl polyglycoside surfactants in rinse aid compositions on polycarbonate.
  • Fluorinated surfactants are described in U.S. Patent 4,089,804 where a non-ethoxylated fluoroaliphatic sulfonamide alcohol is added to typical fluorinated hydrocarbon surfactants as a synergist.
  • the compositions are described as useful in a wide variety of industries, e.g., household cosmetic and personal products. Rinse aid for dishwashing is mentioned.
  • organosilanes have been described in rinse aid compositions where the organosilane contains either a nitrogen, phosphorous or sulfur cationic group in combination with an anion, e.g. a monofunctional organic acid.
  • U.S. Patent 4,005,024 describes such compounds in a rinse aid composition to attract specific soil particles.
  • Aminosilanes have been described with a low foaming ethoxylated nonionic surfactant in rinse aid compositions in automatic dishwashing machines.
  • the present invention is a rinse aid composition for plasticware, formulated as a dilutable liquid, gel or solid concentrate and, when diluted, forming an aqueous rinse, and including in addition to conventional rinse aid surfactants, e.g. hydrocarbon surfactants, about 0.1 to 10 wt-% of a polyalkylene oxide-modified polydimethylsiloxane or a polybetaine-modified polysiloxane, alone or in combination with about 0.1 to 10 wt-% of a fluorinated hydrocarbon nonionic surfactant.
  • conventional rinse aid surfactants e.g. hydrocarbon surfactants, about 0.1 to 10 wt-% of a polyalkylene oxide-modified polydimethylsiloxane or a polybetaine-modified polysiloxane, alone or in combination with about 0.1 to 10 wt-% of a fluorinated hydrocarbon nonionic surfactant.
  • a second aspect of the present invention is a method of cleaning plasticware by: (a) first contacting the ware with an alkaline aqueous cleaning agent in a warewashing machine at 100-180°F to produce cleaned plasticware, and (b) contacting the cleaned plasticware with an aqueous rinse containing a major proportion of an aqueous diluent having about 2 to 100 parts per million of hydrocarbon surfactants, and about 0.01 to 10 parts per million of a polyalkylene oxide-modified polydimethylsiloxane or polybetaine-modified polysiloxane, optionally in combination with about 0.01 to 10 parts per million of a fluorinated hydrocarbon surfactant, e.g. an ethoxylated fluoroaliphatic sulfonamide alcohol.
  • a fluorinated hydrocarbon surfactant e.g. an ethoxylated fluoroaliphatic sulfonamide alcohol.
  • an aqueous rinse agent includes concentrate materials that are diluted with an aqueous stream to produce an aqueous rinse.
  • an aqueous rinse agent is an aqueous material that is contacted with ware in a rinse cycle.
  • a sheeting agent is the polymeric material used to promote the even draining of the aqueous rinse. Sheeting is defined as forming a continuous, evenly draining film, leaving virtually no spots or film upon the evaporation of water.
  • the term “dish” or the term “ware” is used in the broadest sense of the term to refer to various types of articles used in the preparation, serving, consumption, and disposal of food stuffs including pots, pans, trays, pitchers, bowls, plates, saucers, cups, glasses, forks, knives, spoons, spatulas, and other glass, metal, ceramic, plastic composite articles commonly available in the institutional or household kitchen or dining room.
  • plasticware includes the above articles made from, e.g., polycarbonate, melamine, polypropylene, polyester resin, polysulfone, and the like.
  • the siloxane surfactant employed as an additive in the present invention alone or in combination with a fluorochemical surfactant described below is a polyalkylene oxide-modified polydimethylsiloxane, nonionic surfactant or a polybetaine-modified polysiloxane amphoteric surfactant.
  • Both, preferably, are linear polysiloxane copolymers to which polyethers or polybetaines have been grafted through a hydrosilation reaction. This process results in an alkyl-pendant (AP type) copolymer, in which the polyalkylene oxide groups, for example, are attached along the siloxane backbone through a series of hydrolytically stable Si-C bonds.
  • R is -(CH 2 ) 3 -O-(EO) x -(PO) y -Z or EO is ethyleneoxy
  • PO is 1,2-propyleneoxy
  • Z is hydrogen or alkyl of 1-6 carbon atoms
  • the weight ratio in % of EO:PO may vary from 100:0 to 0:100.
  • a broad range of surfactants have been developed varying x and y above and coefficients n and m.
  • n is 0 or ⁇ 1 and m is at least 1.
  • siloxanes where Z is hydrogen, methyl or butyl and the weight ratio of EO:PO is 100:0 to 40:60, or in the polybetaines where n is 0 to 200 and m is 1 to 50.
  • siloxane surfactants herein described and 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. Patent No. 4,654,161.
  • the particular siloxanes used in the present invention are described as having, e.g., low surface tension, high wetting ability and excellent lubricity. For example, these surfactants are said to be among the few capable of wetting polytetrafluoroethylene surfaces.
  • the fluorochemical surfactant employed as an additive in the present invention in combination with a silane, defined above, is a nonionic fluorohydrocarbon, such as, for example, fluorinated alkyl polyoxyethylene ethanols, fluorinated alkyl alkoxylate and fluorinated alkyl esters. These FluoradTM surfactants are available from 3M.
  • a fluorinated alkyl polyoxyethylene ethanol included as a preferred surfactant is a polyoxyethylene adduct of a fluoroaliphatic sulfonamide alcohol which has excellent wetting, spreading and leveling properties.
  • surfactants may be described as having the formula: R f SO 2 N(C 2 H 5 ) (CH 2 CH 2 O) x H wherein R f is C n F 2n+1 in which n is 6-10 and x may vary from 10 to 20. Particularly valuable is the surfactant where n is 8 and x is 14. This particular surfactant identified as FC-170C is available from 3M.
  • fluorocarbon surfactants and silicone surfactants have been known to be good wetting agents and used individually in rinse aid formulations, there is no description of their being used effectively in plasticware as rinse aids.
  • fluorocarbon surfactants and silicone surfactants have been known to be good wetting agents and used individually in rinse aid formulations, there is no description of their being used effectively in plasticware as rinse aids.
  • we have found in the present invention that the use of certain polysiloxane copolymers in a mixture with hydrocarbon surfactants provide excellent rinse aids on plasticware.
  • silicone polysiloxane copolymers and fluorocarbon surfactants with conventional hydrocarbon surfactants also provide excellent rinse aids on plasticware. This combination has been found to be better than the individual components except with certain polyalkylene oxide-modified polydimethylsiloxanes and polybetaine polysiloxane copolymers of the present invention where the effectiveness is about equivalent.
  • the preferred embodiments of the present invention encompass the polysiloxane copolymers alone and the combination with the fluorocarbon surfactant preferably involves polyether polysiloxanes, the nonionic siloxane surfactants.
  • the amphoteric siloxane surfactants, the polybetaine polysiloxane copolymers may be employed alone as the additive in the conventional rinse aids to provide the same results.
  • hydrocarbon surfactants in conventional rinse aid formulations are nonionic surfactants, typically a polyether compound prepared from ethylene oxide, propylene oxide, in a homopolymer or a block or heteric copolymer.
  • polyether compounds are known as polyalkylene oxide polymers, polyoxyalkylene polymers, or polyalkylene glycol polymers.
  • sheeting or rinse agents have a molecular weight in the range of about 500 to about 15,000.
  • Certain types of polyoxypropylene-polyoxyethylene glycol polymer rinse aids have been found to be particularly useful.
  • Those surfactants comprising at least one block of a polyoxypropylene and having at least one other block of polyoxyethylene attached to the polyoxypropylene block.
  • Additional blocks of polyoxyethylene or polyoxypropylene can be present in a molecule. These materials having an average molecular weight in the range of about 500 to about 15,000 are commonly available as PLURONIC® manufactured by the BASF Corporation and available under a variety of other trademarks of their chemical suppliers.
  • rinse aid compositions called PLURONIC® R reverse pluronic structure
  • rinse aids made by reacting ethylene oxide or propylene oxide with an alcohol anion and an alkyl phenol anion, a fatty acid anion or other such anionic material can be useful.
  • One particularly useful rinse aid composition can comprise a capped polyalkoxylated C 6-24 linear alcohol.
  • the rinse aids can be made with polyoxyethylene or polyoxypropylene units and can be capped with common agents forming an ether end group.
  • One particularly useful species of this rinse aid is a benzyl ether of a polyethoxylated C 12-14 linear alcohol; see U.S. Patent No. 3,444,247.
  • Alcohol ethoxylates having EO and PO blocks can be particularly useful since the stereochemistry of these compounds can permit occlusion by urea, a feature useful in preparing solid rinse aids.
  • Particularly useful polyoxypropylene polyoxyethylene block polymers are those comprising a center block of polyoxypropylene units and blocks of polyoxyethylene units to each side of the center block. These copolymers have the formula shown below: (EO) n - (PO) m - (EO) n wherein m is an integer of 21 to 54; n is an integer of 7 to 128. Additional useful block copolymers are block polymers having a center block of polyoxyethylene units and blocks of polyoxypropylene units to each side of the center block. The copolymers have the formula as shown below: (PO) n - (EO) m - (PO) n wherein m is an integer of 14 to 164 and n is an integer of 9 to 22.
  • hydrotropic agent In the preparation of conventional rinse aid compositions, a hydrotropic agent is often employed in the formulation. Such an agent may also be used in the present invention.
  • Hydrotropy is a property that relates to the ability of materials to improve the solubility or miscibility of a substance in liquid phases in which the substance tends to be insoluble. Substances that provide hydrotropy are called hydrotropes and are used in relatively lower concentrations than the materials to be solubilized.
  • a hydrotrope modifies the solvent to increase the solubility of an insoluble substance or creates micellar or mixed micellar structures resulting in a stable suspension of the insoluble substance in the solvent.
  • the hydrotropic mechanism is not thoroughly understood. Hence either hydrogen bonding between primary solvent, in this case water, and the insoluble substance are improved by the hydrotrope or the hydrotrope creates a micellar structure around the insoluble composition to maintain the material in a suspension/solution.
  • the hydrotropes are most useful in maintaining a uniform solution of the cast rinse composition both during manufacture and when dispersed at the use location.
  • the combination of the polyalkylene oxide materials and the casting aids tends to be partially incompatible with aqueous solution and can undergo a phase change or phase separation during storage of the solution.
  • the hydrotrope solubilizer maintains the rinse composition in a single phase solution having the nonionic rinsing agent uniformly distributed throughout the composition.
  • hydrotrope solubilizers are used at about 0.1 to 20 wt-% and include, for example, small molecule anionic surfactants and semi-polar nonionic surfactants.
  • the most preferred range of hydrotrope solubilizers is about 1 to 10 wt-%.
  • the small molecule anionic surfactants include aromatic sulfonic acid or sulfonated hydrotropes such as C 1-5 substituted benzene sulfonic acid or naphthalene sulfonic acid.
  • aromatic sulfonic acid or sulfonated hydrotropes such as C 1-5 substituted benzene sulfonic acid or naphthalene sulfonic acid.
  • hydrotrope are xylene sulfonic acid or naphthalene sulfonic acid or salts thereof.
  • the semi-polar type of nonionic surface active agents include amine oxide hydrotropes such as tertiary amine oxides corresponding to the general formula: wherein the arrow is a conventional representation of a semi-polar bond; and, R 1 , R 2 , and R 3 may be aliphatic, aromatic, heterocyclic, alicyclic, or combinations thereof.
  • R 1 is an alkyl radical of from about 8 to about 24 carbon atoms
  • R 2 and R 3 are selected from the group consisting of alkyl or hydroxyalkyl of 1-3 carbon atoms and mixtures thereof
  • R 4 is an alkylene or a hydroxyalkylene group containing 2 to 3 carbon atoms
  • n ranges from 0 to about 20.
  • Useful water soluble amine oxide hydrotropes are selected from alkyl di-(lower alkyl) amine oxides, specific examples of which are n-decyldimethylamine oxide, 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-hydroxy
  • Such materials do not provide any pronounced surfactant or sheeting activity but significantly improve the solubility of the organic materials of the rinse aid in the aqueous rinse compositions.
  • a preferred embodiment of a rinse aid composition for plasticware which is suitable for dilution to form an aqueous rinse includes: (a) about 2 to 90 wt-% of one or more nonionic surfactants; (b) about 1 to 20 wt-% of a hydrotrope; (c) about 0.1 to 10 wt-% of a polysiloxane copolymer of the formula wherein R is -(CH 2 ) 3 -O-(EO) x -(PO) y -Z or n is 0 or ⁇ 1; m is at least 1, Z is hydrogen or alkyl of 1-6 carbon atoms, and the weight ratio in % of EO:PO may vary from 100:0 to 0:100, and, optionally, (d) about 0.1 to 10 wt-% of an ethoxylated fluoroaliphatic sulfonamide alcohol.
  • Another embodiment of the rinse aid composition of the present invention is the above-described siloxane surfactant with a rinse aid composition containing a nonionic block copolymer and a defoamer composition, and, optionally, in combination with the above-described fluorocarbon surfactant.
  • the nonionic ethylene oxide propylene oxide block copolymer in this case would not have been expected to provide effective sheeting action and low foam in an aqueous rinse due to its high cloud point and poor wetting properties.
  • rinse agents diluted into an aqueous rinse providing effective sheeting and low foaming properties have been prepared from high cloud point, high foaming surfactants with an appropriate defoamer as described in U.S. Patent No. 5,589,099.
  • Illustrative but non-limiting examples of various suitable high cloud point nonionic surface active agents for these rinse agents include polyoxyethylene-polyoxypropylene block copolymers having the formula: (EO) x (PO) y (EO) z wherein x, y and z reflect the average molecular proportion of each alkylene oxide monomer in the overall block copolymer composition.
  • x typically ranges from about 30 to 130
  • y typically ranges from about 30 to 70
  • z typically ranges from about 30 to 130
  • x plus y is typically greater than about 60.
  • the total polyoxyethylene component of the block copolymer constitutes typically at least about 10 wt-% of the block copolymer and commonly 20 wt-% or more of the block copolymer.
  • the material preferably has a molecular weight greater than about 1,000 and more preferably greater than about 2,000.
  • Defoaming agents include a variety of different materials adapted for defoaming a variety of compositions.
  • Defoamers can comprise an anionic or nonionic material such as polyethylene glycol, polypropylene glycol, fatty acids and fatty acid derivatives, fatty acid sulfates, phosphate esters, sulfonated materials, silicone based compositions, and others.
  • Defoamers may include food additive defoamers including silicones and other types of active anti-foam agents.
  • Silicone foam suppressers include polydialkylsiloxane preferably polydimethylsiloxane. Such silicone based foam suppressers can be combined with silica. Such silica materials can include silica, fumed silica, derivatized silica, silanated silica, etc. Commonly available anti-foaming agents combine a polydimethylsiloxane and silica gel. Another food additive defoaming agent comprises a fatty acid defoamer. Such defoamer compositions can comprise simple alkali metal or alkaline earth metal salts of a fatty acid or fatty acid derivatives.
  • Such derivatives include mono, di- and tri- fatty acid esters of polyhydroxy compounds such as ethylene glycol, glycerine, propylene glycol, hexylene glycol, etc.
  • defoaming agents comprise a fatty acid monoester of glycerol.
  • Fatty acids useful in such defoaming compositions can include any C 8-24 saturated or unsaturated, branched or unbranched mono or polymeric fatty acid and salts thereof, including for example myristic acid, palmitic acid, stearic acid, behenic acid, lignoceric acid, palmitoleic acid, oleic acid, linoleic acid, arachidonic acid, and others commonly available.
  • Other food additive anti-foam agents available include water insoluble waxes, preferably microcrystalline wax, petroleum wax, synthetic petroleum wax, rice base wax, beeswax having a melting point in the range from about 35° to 125°C with a low saponification value, white oils, etc. Such materials are used in the rinse agents at a sufficient concentration to prevent the accumulation of any measurable stable foam within the dish machine during a rinse cycle.
  • the defoaming composition may be present in the composition of the present invention from about 0.1-30 wt-%, preferably 0.2-25 wt-%.
  • a rinse aid composition for plasticware suitable for dilution to form an aqueous rinse also includes: (a) about 5 to 40 wt-% of a nonionic block copolymer composition of ethylene oxide and propylene oxide, having a molecular weight of ⁇ 2000 and a cloud point, measured with a 1 wt-% aqueous solution, greater than 30°C; (b) about 0.2 to 25 wt-% of a food additive defoamer composition; (c) about 0.1 to 10 wt-% of a polysiloxane copolymer of the formula wherein R is -(CH 2 ) 3 -O-(EO) x -(PO) y -Z or n is 0 or ⁇ 1; m is at least 1, Z is hydrogen or alkyl of 1-6 carbon atoms, and the weight ratio in % of EO:PO may vary from 100:0 to 0:100, and, optionally, (d) about
  • Still another embodiment of the present invention is a rinse aid composition containing the above-described siloxane surfactant with a rinse aid composition containing solely food additive ingredients and, optionally, in combination with the above-described fluorocarbon surfactant.
  • the compositions include a class of nonionic surfactants, namely, the polyalkylene oxide derivatives of sorbitan fatty acid esters, which exhibit surprising levels of sheeting action, with a careful selection of defoamer compositions.
  • the effective defoamer compositions are selected from the group consisting of a silicone defoamer, an alkali metal (e.g.
  • silicone based materials are used to defoam the sorbitan material.
  • Sorbitol and sorbitan can be derivatized with an alkylene oxide such as ethylene oxide or propylene oxide or derivatized with fatty acids or with both using conventional technology to produce nonionic surfactant sheeting agent materials.
  • alkylene oxide such as ethylene oxide or propylene oxide
  • fatty acids or with both using conventional technology to produce nonionic surfactant sheeting agent materials.
  • These sheeting agents are typically characterized by the presence of from 1 to 3 moles of a fatty acid, in ester form, per mole of surfactant and greater than 15 moles of alkylene oxide, preferably 15 to 40 moles of alkylene oxide and most preferably 15 to 25 moles of ethylene oxide per mole of surfactant.
  • the composition of the surfactant is a mixture of a large number of compounds characterized by the molar proportion of alkylene oxide and the molar proportion of fatty acid residues on the sorbitol or sorbitan molecules.
  • the compositions are typically characterized by average concentrations of the alkylene oxide (typically ethylene oxide) and the fatty acid on the overall compositions.
  • alkylene oxide typically ethylene oxide
  • fatty acid typically ethylene oxide
  • Examples of preferred nonionic surfactants are Polysorbate 20®, also known as Tween 20® (ICI), typically considered to be a mixture of laureate esters of sorbitol and sorbitan consisting predominantly of the mono fatty acid ester condensed with approximately 20 moles of ethylene oxide.
  • Polysorbate 60® is a mixture of stearate esters of sorbitol and sorbitan consisting predominantly of the mono fatty acid ester condensed with approximately 20 moles of ethylene oxide. Selected polysorbate nonionic surfactant materials are approved for direct use in food intended for human consumption under specified conditions and levels of use.
  • Alkoxylated sorbitan or sorbitol aliphatic esters suitable for use in the rinse aid composition include any sorbitan or sorbitol aliphatic ester derivatized with an alkylene oxide capable of providing effective sheeting action or rinsing performance in cooperation with the other components of the rinse agent composition.
  • the preferred compositions are the ethylene oxide condensates with sorbitan or sorbitol fatty acid esters.
  • these materials are approved food additives, in the form of a liquid or waxy solid, that can be easily formulated into concentrated liquid or solid rinse agents.
  • Alkoxylated sorbitan or sorbitol fatty acid esters suitable for use in the rinse agent include mono, di- and tri-esters and mixtures thereof.
  • Sorbitan fatty acid esters may be derivatized by esterification of sorbitol or sorbitan with such fatty acids as lauric, myristic, palmitic, stearic, oleic, linoleic, and other well known similar saturated, unsaturated (cis or trans), branched and unbranched fatty acid.
  • Preferred food additive or GRAS fatty acids are the sorbitan esters approved as direct food additives (e.g.
  • sorbitan monostearate POE 20 Sorbitan monolaurate, POE 20 Sorbitan monostearate, P0E 20 Sorbitan tristearate, POE 20 Sorbitan monooleate and mixtures thereof.
  • the preferred useful ethoxylated sorbitan or sorbitol fatty acid ester include monoesters derivatized with ethylene oxide.
  • a preferred rinse aid composition for plasticware suitable for dilution to form an aqueous rinse, further includes: (a) about 5 to 50 wt-% of a sorbitan fatty acid ester containing greater than about 15 moles of alkylene oxide per mole of sorbitan; (b) about 0.2 to 25 wt-% of a defoamer composition selected from the group consisting of an alkali metal or alkaline earth metal salt of a fatty acid, a silicone, a fatty acid ester of glycerol, and mixtures thereof; (c) about 0.1 to 10 wt-% of a polysiloxane copolymer of the formula wherein R is -(CH 2 ) 3 -O-(EO) x -(PO) y -Z or n is 0 or ⁇ 1; m is at least 1, Z is hydrogen or alkyl of 1-6 carbon atoms, and the weight ratio in % of EO:PO may vary from 100
  • the rinse agents of the invention can, if desired, contain a polyvalent metal complexing or chelating agent that aids in reducing the harmful effects of hardness components in service water.
  • a polyvalent metal complexing or chelating agent that aids in reducing the harmful effects of hardness components in service water.
  • calcium, magnesium, iron, manganese, etc., ions present in service water can interfere with the action of either washing compositions or rinsing compositions.
  • a chelating agent can effectively complex and remove such ions from inappropriate interaction with active ingredients increasing rinse agent performance.
  • Both organic and inorganic chelating agents are common. Inorganic chelating agents include such compounds as sodium tripolyphosphate and higher linear and cyclic polyphosphate species.
  • Organic chelating agents include both polymeric and small molecule chelating agents. Polymeric chelating agents commonly comprise polyanionic compositions such as polyacrylic acid compounds.
  • Small molecule organic chelating agents include salts of ethylenediaminetetraacetic acid and hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid, ethylenediaminetetrapropionates, triethylenetetraminehexacetates, and the respective alkali metal ammonium and substituted ammonium salts thereof.
  • Amino phosphates are also suitable for use as chelating agents in the composition of the invention and include ethylenediamine(tetramethylene phosphates), nitrilotrismethylenephosphonates, diethylenetriamine (pentamethylenephosphonates). These amino phosphonates commonly contain alkyl or alkyl groups with less than 8 carbon atoms.
  • Preferred chelating agents include approved food additive chelating agents such as disodium salt of ethylenediaminetetraacetic acid.
  • the liquid rinse agent compositions of the invention have a liquid base component which can function as a carrier with various aqueous diluents to form the aqueous rinse.
  • Liquid bases are preferably water or a solvent compatible with water to obtain compatible mixtures thereof.
  • Exemplary nonlimiting solvents in addition to water include low molecular weight C 1-6 primary and secondary mono, di-, and trihydrate alcohol such as ethanol, isopropanol, and polyols containing from two to six carbon atoms and from two to six hydroxyl groups such as propylene glycol, glycerine, 1,3-propane diol, propylene glycol, etc.
  • compositions of the invention can be formulated using conventional formulating equipment and techniques.
  • the compositions of the invention typically can comprise proportions as set forth in Table I.
  • the materials are manufactured in commonly available mixing equipment by charging to a mixing chamber the liquid diluent or a substantial proportion of a liquid diluent.
  • a liquid diluent is added preservatives or other stabilizers. Care must be taken in agitating the rinse agent as the formulation is completed to avoid degradation of polymer molecular weight or exposure of the composition to elevated temperatures.
  • the materials are typically agitated until uniform and then packaged in commonly available packaging and sent to storage before distribution.
  • the liquid materials of the invention can be adapted to a solid block rinse by incorporating into the composition a casting agent.
  • organic and inorganic solidifying materials can be used to render the composition solid.
  • organic materials are used because inorganic compositions tend to promote spotting in a rinse cycle.
  • the most preferred casting agents are polyethylene glycol and an inclusion complex comprising urea and a nonionic polyethylene or polypropylene oxide polymer.
  • Polyethylene glycols (PEG) are used in melt type solidification processing by uniformly blending the sheeting agent and other components with PEG at a temperature above the melting point of the PEG and cooling the uniform mixture.
  • An inclusion complex solidifying scheme is set forth in Morganson et al., U.S. Patent No. 4,647,258.
  • the organic nature of the rinse agents of the invention can be subject to decomposition and microbial attack.
  • Preferred stabilizers that can limit oxidative decomposition or microbial attack include food grade stabilizers, food grade antioxidants, etc.
  • Most preferred materials for use in stabilizing the compositions of the invention include C 1-10 mono, di- and tricarboxylic acid compounds. Preferred examples of such acids include acetic acid, citric acid, lactic, tartaric, malic, fumaric, sorbic, benzoic, etc.
  • Optional ingredients which can be included in the rinse agents of the invention in conventional levels for use include solvents, processing aids, corrosion inhibitors, dyes, fillers, optical brighteners, germicides, pH adjusting agents (monoethanol amine, sodium carbonate, sodium hydroxide, hydrochloride acid, phosphoric acid, etc.), bleaches, bleach activators, perfumes and the like.
  • the range of actives in the solid and liquid concentrate compositions of the invention are set forth in Table I and the ranges in the aqueous rinse in Table II. Although the actives in the Tables include fluorocarbon surfactants, the Tables may also be read in the absence of such surfactant. Actives Useful (wt-%) Preferred (wt-%) Liquid Solid Hydrocarbon surfactant 2-90 8-60 5-75 Fluorocarbon surfactant 0.1-10 0.5-5 0.5-5 Siloxane surfactant 0.1-10 0.5-5 0.5-5 Actives Useful (ppm) Preferred (ppm) Hydrocarbon surfactant 2-200 20-150 Fluorocarbon surfactant 0.01-10 0.1-1.0 Siloxane surfactant 0.01-10 0.1-3.0
  • Liquid rinse agents of the invention are typically dispensed by incorporating compatible packaging containing the liquid material into a dispenser adapted to diluting the liquid with water to a final use concentration wherein the active material is present in the aqueous rinse as shown in Table II above in parts per million parts of the aqueous rinse.
  • dispensers for the liquid rinse agent of the invention areDRYMASTER-P sold by Ecolab Inc., St. Paul, Minnesota.
  • Solid block products may be conveniently dispensed by inserting a solid block 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, Minnesota.
  • a spray-type dispenser such as the volume SOL-ET controlled ECOTEMP Rinse Injection Cylinder system manufactured by Ecolab Inc., St. Paul, Minnesota.
  • a dispenser cooperates with a warewashing machine in the rinse cycle.
  • the dispenser directs a spray of 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 dishes to affect a complete rinse.
  • This dispenser and other similar dispensers are capable of controlling the effective concentration of the active block copolymer and the additives 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 solid block.
  • test procedure is first to select appropriate test substrates to evaluate the test formulations. These substrates are typical pieces of plasticware commonly used in institutional accounts. In preparation for the sheeting test, the test substrates are conditioned with 0.2% Hotpoint soil in softened water at 160°F for three minutes in the modified Champion 1 KAB dishmachine. The test procedure is to add test rinse aid in increments of 10 ppm actives, to the machine pump, circulate the test solution at 160°F for 30 seconds, turn off the machine and observe the type of water break on each test substrate. There are three types of water break. These are:
  • test rinse aid per 10 ppm active increment
  • results are recorded for each test substrate. The test continues until a good performance profile is obtained that allows a judgment to be made regarding the relative performance of the test formulations.
  • Table 1 contains results for a commercially available rinse aid. Note that none of the plastic substrates exhibit complete sheeting until 70 ppm actives are used.
  • Table 2 contains results for the same set of actives containing FluoradTM FC-170C. It performs marginally better at 60 ppm to complete sheet on some of the plastic substrates.
  • Table 3 contains results for the same set of actives containing Silwet® L-77. It also performs marginally better at 60 ppm to complete sheet on some of the plastic substrates.
  • Table 4 contains results for the invention. This contains both Silwet® L-77 and FluoradTM FC-170C. It performs much better at 40 ppm to complete sheet on several of the plastic substrates.
  • the invention represented as Formulation 4 was also evaluated in four institutional test accounts relative to the commercially available rinse aid represented as Formulation 1. In each account at either the same or even at a lower concentration, there has been a significant improvement in drying results on plasticware. With the commercially available product large residual droplets of rinse water remained on the plasticware so that the dry time was much too long, i.e., the plasticware was stacked wet. With the invention, the dry time was greatly reduced and the plasticware was stacked dry.
  • Formula 5 contained the same active ingredients as Formula 4 of Example I.
  • Tables 5, 6 and 7 show similar effectiveness as with the Formula 4 compositions.
  • silicone additive can radically affect results. Some additives provide much better results when added to the basic set of rinse aid ingredients, some do not affect results much, and some detract from results.
  • the invention represented as Formulation 9 was also evaluated in eight institutional test accounts relative to the commercially available rinse aid represented as Formulation 1. In each account at either the same or even at a lower concentration, there has been a significant improvement in drying results on plasticware. With the commercially available product large residual droplets of rinse water remained on the plasticware so that the dry time was much too long. With the invention either there were very small residual droplets of rinse water or the rinse water sheeted from the plasticware. The dry time was greatly reduced and results were judged as acceptable.
  • Formulations 25-29 are to the concentrate, and refer to the components by wt-%.
  • Formulations 30-34 are illustrative of the use concentrations at which the products were tested as plasticware rinse aids.
  • Formulations 30-34 are recommended use concentrations which depend on the type of machine being used and thus do not illustrate the minimum dose concentration. All of these formulations were tested as previously described and all performed satisfactorily in accordance with the objects of the present invention.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Paints Or Removers (AREA)
EP98301705A 1997-04-29 1998-03-09 Agent de rinçage pour vaisselle en plastique Withdrawn EP0875556A3 (fr)

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US841198 1997-04-29
US841110 1997-04-29
US08/841,110 US5880088A (en) 1994-09-12 1997-04-29 Rinse aid for plasticware
US08/841,198 US5880089A (en) 1994-09-12 1997-04-29 Rinse aid for plasticware

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WO2001000760A1 (fr) * 1999-06-24 2001-01-04 Ecolab Inc. Compositions detergentes permettant d'eliminer des salissures organiques ou graisseuses complexes
WO2001019948A1 (fr) * 1999-09-16 2001-03-22 Henkel Kommanditgesellschaft Auf Aktien Agent de rinçage
WO2002012422A1 (fr) * 2000-08-03 2002-02-14 Ecolab Inc. Composition detergente compatible avec les matieres plastiques et methode de nettoyage de matieres plastiques
EP1550710A1 (fr) * 2003-12-29 2005-07-06 The Procter & Gamble Company Compositions de rinçage
EP1553160A1 (fr) * 2003-12-29 2005-07-13 The Procter & Gamble Company Compositions de rinçage
WO2010131217A2 (fr) 2009-05-12 2010-11-18 Ecolab Usa Inc. Agent de rinçage permettant un séchage rapide et un égouttage rapide
WO2017076802A1 (fr) * 2015-11-02 2017-05-11 Henkel Ag & Co. Kgaa Mélange de tensioactifs contenant de l'oxyde d'amine destiné à améliorer l'efficacité de rinçage
US10000725B2 (en) 2012-06-22 2018-06-19 Ecolab Usa Inc. Solid fast draining/drying rinse aid for high total dissolved solid water conditions
US10421933B2 (en) 2012-06-22 2019-09-24 Ecolab Usa Inc. Solid rinse aid composition and method of making same

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USD483998S1 (en) 2001-05-01 2003-12-23 Pactiv Corporation Plate having condiment wells
USD481592S1 (en) 2001-05-01 2003-11-04 Pactiv Corporation Plate having condiment wells
USD480922S1 (en) 2001-05-01 2003-10-21 Pactiv Corporation Plate having condiment wells
US7172072B2 (en) 2001-05-01 2007-02-06 Pactiv Corporation Compartment plates having themes and method for manufacturing and packaging the same
USD489941S1 (en) 2001-05-01 2004-05-18 Pactiv Corporation Plate having condiment wells
JP5008805B2 (ja) * 2001-08-03 2012-08-22 株式会社Ａｄｅｋａ Ｃｉｐ洗浄用脱臭剤組成物
USD485731S1 (en) 2003-02-19 2004-01-27 Pactiv Corporation Plate having two compartments
JP4769412B2 (ja) 2003-09-02 2011-09-07 積水メディカル株式会社 電子メディエーター、電子メディエーター固定化電極およびこれを用いた生物燃料電池
JP5924835B2 (ja) * 2012-04-09 2016-05-25 株式会社Adeka 硬質表面用洗浄剤組成物

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WO2001000760A1 (fr) * 1999-06-24 2001-01-04 Ecolab Inc. Compositions detergentes permettant d'eliminer des salissures organiques ou graisseuses complexes
US6425959B1 (en) 1999-06-24 2002-07-30 Ecolab Inc. Detergent compositions for the removal of complex organic or greasy soils
US6506261B1 (en) 1999-06-24 2003-01-14 Ecolab Inc. Detergent compositions for the removal of complex organic or greasy soils
WO2001019948A1 (fr) * 1999-09-16 2001-03-22 Henkel Kommanditgesellschaft Auf Aktien Agent de rinçage
WO2002012422A1 (fr) * 2000-08-03 2002-02-14 Ecolab Inc. Composition detergente compatible avec les matieres plastiques et methode de nettoyage de matieres plastiques
US6838422B2 (en) 2000-08-03 2005-01-04 Ecolab Inc. Plastics compatible detergent composition and method of cleaning plastics
EP1550710A1 (fr) * 2003-12-29 2005-07-06 The Procter & Gamble Company Compositions de rinçage
EP1553160A1 (fr) * 2003-12-29 2005-07-13 The Procter & Gamble Company Compositions de rinçage
WO2005066322A1 (fr) * 2003-12-29 2005-07-21 The Procter & Gamble Company Composition d'aide au rincage
EP2430141A2 (fr) * 2009-05-12 2012-03-21 Ecolab Usa Inc. Agent de rinçage permettant un séchage rapide et un égouttage rapide
WO2010131217A2 (fr) 2009-05-12 2010-11-18 Ecolab Usa Inc. Agent de rinçage permettant un séchage rapide et un égouttage rapide
EP2430141A4 (fr) * 2009-05-12 2013-06-12 Ecolab Usa Inc Agent de rinçage permettant un séchage rapide et un égouttage rapide
EP3184617A1 (fr) * 2009-05-12 2017-06-28 Ecolab USA Inc. Adjuvant de rinçage pour un drainage et un séchage rapide
EP3425035A1 (fr) * 2009-05-12 2019-01-09 Ecolab USA Inc. Adjuvant de rinçage pour un drainage et un séchage rapide
US10689597B2 (en) 2009-05-12 2020-06-23 Ecolab Usa Inc. Fast drying and fast draining rinse aid comprising an ethoxylated alcohol/EO-PO block copolymer mixture
EP3936594A1 (fr) * 2009-05-12 2022-01-12 Ecolab USA Inc. Adjuvant de rinçage pour un drainage et un séchage rapide
US11479742B2 (en) 2009-05-12 2022-10-25 Ecolab Usa Inc. Fast drying and fast draining rinse aid with a ternary mixture of nonionic surfactants
US10000725B2 (en) 2012-06-22 2018-06-19 Ecolab Usa Inc. Solid fast draining/drying rinse aid for high total dissolved solid water conditions
US10421933B2 (en) 2012-06-22 2019-09-24 Ecolab Usa Inc. Solid rinse aid composition and method of making same
US11421185B2 (en) 2012-06-22 2022-08-23 Ecolab Usa Inc. Solid fast draining/drying rinse aid for high total dissolved solid water conditions
US11827865B2 (en) 2012-06-22 2023-11-28 Ecolab Usa Inc. Solid fast draining/drying rinse aid for high total dissolved solid water conditions
WO2017076802A1 (fr) * 2015-11-02 2017-05-11 Henkel Ag & Co. Kgaa Mélange de tensioactifs contenant de l'oxyde d'amine destiné à améliorer l'efficacité de rinçage

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AU746975B2 (en) 2002-05-09
CA2232341A1 (fr) 1998-10-29
AU5641698A (en) 1998-11-05
JPH10310799A (ja) 1998-11-24
EP0875556A3 (fr) 2001-01-24
CA2232341C (fr) 2008-04-08

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