WO2006131689A1 - Améliorations des compositions organiques ou les concernant - Google Patents

Améliorations des compositions organiques ou les concernant Download PDF

Info

Publication number
WO2006131689A1
WO2006131689A1 PCT/GB2006/001794 GB2006001794W WO2006131689A1 WO 2006131689 A1 WO2006131689 A1 WO 2006131689A1 GB 2006001794 W GB2006001794 W GB 2006001794W WO 2006131689 A1 WO2006131689 A1 WO 2006131689A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
constituent
hard surface
surface cleaning
cleaning composition
Prior art date
Application number
PCT/GB2006/001794
Other languages
English (en)
Inventor
James Chi-Cheng Feng
Jeanne Marie Weller
Original Assignee
Reckitt Benckiser Inc
Reckitt Benckiser (Uk) Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB0601036A external-priority patent/GB2429015A/en
Application filed by Reckitt Benckiser Inc, Reckitt Benckiser (Uk) Limited filed Critical Reckitt Benckiser Inc
Publication of WO2006131689A1 publication Critical patent/WO2006131689A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D1/02—Anionic 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
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • 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
    • 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
    • C11D3/2082—Polycarboxylic 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
    • 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
    • C11D3/2086—Hydroxy 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • 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
    • C11D3/43—Solvents

Definitions

  • the present invention relates to improved cleaning compositions which find particular use in hard surface cleaning applications.
  • Hard surface cleaning compositions are commercially important products and enjoy a wide field of use, and are known in assisting in the removal of dirt and grime from surfaces, especially those characterized as useful for cleaning "hard surfaces".
  • Hard surfaces include those which are frequently encountered in lavatories, for example lavatory fixtures such as toilets, shower stalls, bathtubs, bidets, sinks, etc., as well as countertops, walls, floors, etc. hi such lavatory environments two types of commonly encountered stains in lavatories include "hard water” stains and "soap scum” stains. Such hard surfaces, and such stains, may also be found in different environments as well, including kitchens, hospitals, etc.
  • Hard water stains are mineral stains caused by the deposition of salts, such as calcium or magnesium salts which are frequently present in hard water which is commonly encountered.
  • Soap scum stains are residues of fatty acid soaps, such as soaps which are based on alkaline salts of low fatty acids. These fatty acids are known to precipitate in hard water due to the presence of metal salts therein leaving an undesirable residue upon such surfaces.
  • compositions of cleaning agents have been produced, and it is generally known to the art which cleaning agents are generally suited for one type of stain but not necessarily for both classes of stains.
  • highly acidic cleaning agents comprising strong acids, such as hydrochloric acids
  • strong acids such as hydrochloric acids
  • Other classes of cleaning compositions and formulations are known to be useful upon soap scum stains.
  • generally such compositions comprise an organic and/or inorganic acid, one or more synthetic detergents from commonly recognized classes such as those described in U.S. Pat. No. 5,061,393; U.S. Pat. No.
  • compositions described in these patents are claimed to be effective in the removal of soap scum stains from such hard surfaces and may find further limited use in other classes of stains.
  • compositions are known to the art which do provide disinfection and sanitization through the use of certain classes of anionic surfactants coupled with an acidic component, such as that described in U.S. Pat. No. 5143720. However, the compositions in this U.S. patent would not be expected nor are believed to provide any significant cleaning benefit.
  • compositions which comprise 0.1-10% by weight of an acid sequestrant constituent; 0.1-10% by weight of a mixture of hydrophobic and hydrophilic solvents; 1 -8% by weight of a surfactant and/or hydrotrope constituent; 0- 20% by weight of one or more optional constituents; the balance to 100% by weight, water wherein the aqueous hard surface cleaning composition exhibits a pH of 7.0 or less, especially a pH of 5.0 and less.
  • the improved hard surface cleaning compositions feature low irritability to the eyes and skin of consumers.
  • the compositions also provide disinfecting effects. However these compositions are silent as to their cleaning efficacy of metal and metallic surfaces.
  • compositions having an acidic pH providing good removal of soap scum stains, and further feature low levels of irritability to the user.
  • the compositions comprise about 0. 1-10 % by weight of an acid sequestrant constituent; about 0.1 -10 % by weight of a mixture of hydrophobic and hydrophilic solvents; about 0.001-1 % by weight of a single constituent which exhibits both anionic surfactant and hydrotrope properties; about 0-20 % by weight of one or more optional constituents; the balance to 100 % by weight of water, wherein the aqueous hard surface cleaning composition exhibits a pH of 7 or less, especially a pH of about 5 or less.
  • the improved hard surface cleaning compositions feature low irritability to the eyes and skin of consumers.
  • the compositions also provide disinfecting effects. However these compositions are silent as to their cleaning efficacy of metal and metallic surfaces.
  • compositions which provide an improved cleaning, and desirably also a simultaneous sanitizing or disinfecting benefit to treated hard surfaces.
  • inventive compositions which provide the benefits of good cleaning to a treated hard surface, and especially to provide improved cleaning compositions which provide good removal of stains from hard surfaces, particularly good cleaning of metal or metallic surfaces.
  • inventive compositions may also provide a useful sanitizing or disinfecting benefit to treated surfaces
  • a yet further object of the invention is to provide a readily pourable and readily pumpable cleaning composition which features the benefits described above. It is also among the objects of the invention to provide a process for the cleaning of hard surfaces, particularly metal or metallic hard surfaces, which process comprises the step of: providing an improved cleaning composition as outlined above, and applying an effective amount to a hard surface requiring such treatment in order to provide an effective cleaning bbenefit.
  • an aqueous acidic hard surface cleaning composition which comprises the following essential constituents:
  • Constituent (A) an acid sequestrant comprising citric acid together with another acid
  • Constituent (B) an organic solvent constituent consisting solely of one or more hydrophobic solvents
  • Constituent (C) a material having both surfactant and hydrotrope properties
  • the aqueous acid hard surface cleaning compositions of the invention may also include one or more further optional constituents such as known art additives.
  • said constituents may include: further surfactants, particularly surfactants which are useful for the removal of greasy soils, foaming agents and foam stabilizers, coloring agents, including dyes and pigment compositions, fragrances (whether natural or synthetically produced), fragrance adjuvants and/or fragrance solubilizers, viscosity modifying agents including thickeners or gelling agents, pH- adjusting agents, pH buffers, antioxidants, water softening agents, further solubilizing agents which might be useful in the solubilization of one or more of the constituents in water, preservative compositions, as well as other known art additives not particularly elucidated here.
  • Such constituents as described above include known art compositions, including those described in McCutcheon's Detergents and Emulsif ⁇ ers, North American Edition, 1998; Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., Vol. 23, pp. 478-541, the contents of which are herein incorporated by reference.
  • compositions according to the invention are preferably acidic in character, exhibiting a pH of less than 7.
  • the pH is in the range of about 1 to about 5, yet more desirably is a pH in the range of about 1 to about 4, and most desirably is a pH of about 1 to about 3.
  • an improved process for cleaning of surfaces, especially hard surfaces which includes the step of applying an effective amount of a the aforementioned aqueous acid hard surface cleaning composition to a hard surface in need of a cleaning treatment, particularly in the locus of stains on said surface.
  • an improved process for the cleaning of metal and metallic surfaces which process includes the step of applying a cleaning effective amount of the aforementioned aqueous acidic hard surface cleaning composition to a metal or metallic surface in need of a cleaning treatment, particularly in the locus of stains on such surfaces, including tarnished surfaces, hi a yet further aspect of the invention there is provided a process for the manufacture of an aqueous acid hard surface cleaning composition as described hererin.
  • Constituent A The constituents which comprise Constituent A is a combination of citric acid together with another acid which in combination is found to be effective in the removal of hard water stains from hard surfaces, particularly lavatory surfaces as denoted above.
  • the acids which are useful in Constituent A may include any inorganic acid, or may include any organic acid, and may also include mixtures of two or more acids which or soluble or dispersible in water.
  • Exemplary useful in inorganic acids include: sulfuric acid, hydrochloric acid, phosphoric acid, as well as other water dispersible or water soluble inorganic or mineral acids not specifically eludicated herein but which nonetheless may be found effective in the inventive compositions.
  • Exemplary useful organic acids include any known art organic acid which may be found effective in the inventive compositions.
  • Generally useful organic acids are those which include at least one carbon atom, and include at least one carboxyl group
  • water soluble organic acids which contain from 1 to about 6 carbon atoms, and at least one carboxyl group as noted.
  • exemplary useful organic acids include: citric acid, cresylic acid, dodecylbenzene sulfonic acid, phosphoric acid, salicylic acid, sorbic acid, sulfamic acid, acetic acid, benzoic acid, boric acid, capric acid, caproic acid, cyanuric acid, dihydroacetic acid, dimethylsulfamic acid, propionic acid, polyacrylic acid, 2-ethyl-hexanoic acid, formic acid, fumaric acid, I-glutamic acid, isopropyl sulfamic acid, naphthenic acid, oxalic acid, phosphorous acid, valeric acid, benzene sulfonic acid, xylene sulfonic acid, as well as any acid listed as a registered pesticide active ingredient with the United
  • Further useful acids include: sulfonic acids, maleic acid, acetic acid, adipic acid, lactic acid, butyric acid, gluconic acid, malic acid, tartaric acid, as well as glycolic acid. Desirably glycolic acid and citric acid are used, as they are effective, in plentiful supply, and may be advantageously used.
  • These acid sequestrants provide free acidity within the cleaning composition.
  • the free acid reacts with fatty acid metal salts within soap scum stains, releasing the metal ions and freeing the fatty acid, which facilitates the removal of these undesired stains from hard surfaces.
  • These acid sequestrants also sequester the resulting free metal ions which are released from the soap scum stains.
  • the acid sequestrants are selected to feature disinfecting properties, they concomitantly provide requisite anti- microbial activity necessary to disinfect the cleaned surface.
  • Constituent A necessarily comprises a first acid sequestrant which comprises citric acid and a second acid sequestrant which is at least one further acid described above, as it has been observed by the inventor that citric acid provides good disinfecting action in the compositions of the invention, but in certain formulations may be insufficiently acidic in order to effectively remove certain stains.
  • the addition of at least one further acid provides additional cleaning effect which was not observed in certain formulations with citric acid alone.
  • the further acid is selected from the group consisting of lactic acid, tartaric acid, and glycolic acid.
  • inventive compositions are necessarily acidic in nature (pH ⁇ 7.0) there should be sufficient acid present in the composition such that the pH of the composition is desirably less than 6, preferably from about 5.0 to about 1.0, more preferably from about 4.0 to about 1.0.
  • Constituent A is desirably present in the formulations in ranges of about 0.1 to about 10%wt, preferably about l%wt. to about 8%wt, and more preferably about 5%wt. to about 6% wt., based on the total weight of a composition.
  • citric acid comprises at least about l%wt. of the total weight of the acid sequestrants of Constituent A, more preferably citric acid comprises at least about 25%wt, yet more preferably at least about 40%wt., and most preferably citric acid comprises at least about 50%wt.of the total weight of Constituent A.
  • Constituent B is an organic solvent constituent consisting solely of one or more hydrophobic solvents.
  • Constituent B acts to assist in the dissolution of the fatty acids from a hard surface being treated with the inventive compositions. Certain fatty acids present in the soap scum residues are solubilized and/or rendered at least partially miscible in water due to the presence of Constituent B, which facilitates the removal of the stain from the surface.
  • Constituent B are also useful in penetrating the stain and act as a carrier for the further constituents of the invention, especially the constituents comprising Constituent A, thus bringing them through the layer of the stain to the surface upon which the stain is present, and thereby aiding in the effective dissolution of the stain and its removal.
  • the hydrophobic solvents forming Constituent B should demonstrate solubilization of the aliphatic portions of the fatty acids within the soap scum stains.
  • Exemplary useful hydrophobic solvents include mineral spirits, tripropylene glycol n- butyl ether, propylene glycol phenyl ether, dipropylene glycol n-propyl ether, ethylene glycol phenyl ether, and particularly propylene glycol n-butyl ether and dipropylene glycol n-butyl ether; Constituent B may be one such solvent or a mixture of two or more hydrophobic solvents.
  • the one or more hydrophobic solvents of Constituent B exhibit a solubility in water of about 0 ml/ 100 ml water to about 20 ml/ 100 ml water, but desirably the one or more hydrophilic solvents of Constituent B exhibit an aqueous solubility in water of not more than 30 nil/ 100 ml water.
  • Constituent B is desirably present in amounts of about 0.1 %wt. to about 10%wt. based on the total weight of the inventive composition, preferably about l%wt. to about 5%wt, and more preferably about 1.5%wt. to about 4% by weight.
  • the sole organic solvents present are hydrophobic solvents, which are present to the exclusion of hydrophilic solvents.
  • Preferred as the sole organic solvents are those which exhibit an aqueous solubility in water of not more than about 20 ml/100 ml water.
  • Constituent C The constituents comprising Constituent C provide for the reduction of the interfacial tension between the soil and the compositions of the invention which facilitates the wetting of the stain as well as providing a hydrotropic functionality. Such a hydrotropic functionality aids in the solubilization of greater amounts of fatty acids in a stain and in the removal of the stain from a surface.
  • Exemplary materials useful as Constituent C include one or more compounds such as: alkyl phenoxy benzene disulfonates (also known as alkyl diphenyl oxide disulfonates), linear alkyl benzene sulfonates and alkylnaphthalene sulfonates and salts thereof. Such compositions are known to the art, and available as anionic surfactants.
  • alkali metal salts ammonium salts, amine salts, aminoalcohol salts or the magnesium salts of one or more of the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates, olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, acyl sarcosinates, acyl isethionate
  • alkyl phenoxy benzene disulfonates include metal salts and organic salts of alkylphenoxy benzene disulfonates, such as sodium dodecyl diphenyloxide disulfonate, sodium hexyl diphenyloxide disulfonate, sodium n-decyl diphenyloxide disulfonate, as well as sodium n-hexadecyl diphenyloxide disulfonate.
  • metal counterions or organic counterions may be substituted in the place of the sodium noted in the recited alkyl phenoxy benzene disulfonates noted above, as well as mixtures of two or more alkyl phenoxy benzene disulfonates. Many of these materials are available under the Dowfax® (Dow Chemical, Midland, Mich.) or Calfax® (Pilot Chemical, Santa Fe Springs, Calif.) trademarks.
  • Exemplary linear alkyl benzene sulfonates include metal salts and organic salts of linear alkyl benzene sulfonates, such as sodium dodecylbenzene sulfonate, sodium nonylbenzene sulfonate, isopropylamine salts of linear alkyl benzene sulfonic acid, triethanolamine dodecylbenzene sulfonate, diethanolamine dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, sodium tridecylbenzene sulfonate, as well as mixtures of sodium dodecylbenzenesulfonate with sodium toluene sulfonate, sodium cuniene sulfonate and/or with sodium xylene sulfonate.
  • linear alkyl benzene sulfonates such as sodium dodecylbenzene sul
  • Exemplary alkylnaphthalene sulfonates include metal salts and organic salts of alkylnaphthalene sulfonates such as sodium diisopropylnaphthalene sulfonate, butylnaphthalene sodium sulfonate, nonylnaphthalene sodium sulfonate, sodium dibutylnaphthalene sulfonate and sodium dimethylnaphthalene sulfonate.
  • Other metal counterions or organic counterions may be substituted in the place of the counterions noted in the recited alkylnaphthalene sulfonates noted above, as well as mixtures of two or more alkylnaphthalene sulfonates.
  • Further useful as constituents used in Constituent C include sodium xylene sulfonate, sodium cumene sulfonate, and naphthalene sulfonates, as well as mixtures of two or more of the above
  • Constituent C is a single constituent which exhibits both anionic surfactant and hydrotrope properties.
  • Constituent C is present in amounts of about 0.00 l%wt. to about 10%wt. based on the total cleaning composition weight, preferably is present in amounts of about l%wt. to about 5%wt, and more preferably about 1.5%wt. to about 2.5%wt.
  • a further essential constituent of the invention is at least one inorganic chloride salt.
  • the inorganic chloride salt is desirably present in an amount effective to provide improved cleaning of metal surfaces, particularly copper surfaces which are immersed or contacted with the inventive compositions.
  • the inorganic chloride salt(s) used in the compositions of the present invention can be any water- soluble inorganic chloride salt or mixtures of such salts.
  • water-soluble means having a solubility in water of at least 10 grams per hundred grams of water at 20° C.
  • suitable salts include various alkali metal and/or alkaline earth metal chlorides including sodium chloride, calcium chloride, magnesium chloride and zinc chloride.
  • the inorganic chloride salt(s) is present hi the compositions of the present invention in an amount which will provide an improved cleaning of metal surfaces, particularly copper surfaces, compared to an identical composition which excludes the inorganic chloride salts(s).
  • the inorganic chloride salt(s) are present in amounts of from about 0.00001 to about 10% by weight, desirably from about 0.00001 to about 10% by weight, more desirably from about 0.001 to about 2.5% by weight, yet more desirably from about 0.01 to about 1.5% by weight and most desirably from about 0.2 to about 1.5%weight.
  • inorganic chloride salt(s) and weight percentages thereof are described with reference to one or more of the Examples.
  • the inventors have unexpectedly discovered that sulfate salts do not provide improved cleaning of metal surfaces this function, and the inventors do not expect that other non-chloride alkali metal and/or alkaline earth metal salts, e.g. those based on borates, bromides, fluorides, phosphates, carbonates, bicarbonates, citrates, acetates, lactates, provide such an improved metal cleaning function.
  • the sole inorganic salts present are one or more inorganic chloride salts.
  • the compositions according to the invention are aqueous in nature.
  • Water is added to Constituents A, B, C and D in order to provide 100% by weight of the composition.
  • the water may be tap water, but is preferably distilled and is most preferably deionized water. If the water is tap water, it is preferably substantially free of any undesirable impurities such as organics or inorganics, especially minerals salts which are present in hard water, which may thus interfere with the operation of Constituents A, B, C, as well as any other optional components which may be included in the inventive compositions.
  • compositions according to the invention may comprise one or more of the following optional components, the total weight of such optional constituents preferably not exceeding about 20%wt. of the total weight of the composition, more preferably not exceeding about 10%wt, and most preferably less than 10%wt. based on the total weight of the composition according to the invention.
  • Non-ionic surfactants of the conventionally known and used variety in this class of cleaning agents may be added in effective amounts, i.e., amounts which are shown to be effective in the cleaning compositions in facilitating the removal of greasy soils. Such greasy soils are to be differentiated from the hard water stains and the soap scum stains described earlier in this specification. However, it is also to be appreciated that the non- ionic surfactants of this optional constituent also may be at least partially effective in the solubilization and removal of soap scum stains.
  • nonionic surfactants include known nonionic surfactants which generally consist of a hydrophobic moiety, such as C 6 - C 20 primary or secondary, branched or straight chain monoalcohols, Cs-Ci 8 mono- or dialkyphenols, C 6 -C 20 fatty acid amides, and a hydrophilic moiety which consists of alkylene oxide units.
  • These nonionic surfactants are, for instance, alkoxylation products of the above hydrophobic moieties, containing from 2 to 30 moles of alkylene oxide.
  • alkylene oxides ethylene-, propylene- and butyl ene oxides and mixtures thereof are used.
  • any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with an atkylene oxide, especially ethylene oxide or with the polyhydration product thereof, a polyalkylene glycol, especially polyethylene glycol, to form a water soluble or water dispersible nonionic surfactant compound.
  • suitable nonionic surfactants which may be used in the present invention include the following:
  • One class of useful nonionic surfactants include polyalkylene oxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with an alkylene oxide, especially an ethylene oxide, the ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • the alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene and the like.
  • Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol.
  • a further class of useful nonionic surfactants include the condensation products of aliphatic alcohols with from about 1 to about 60 moles of an alkylene oxide, especially an ethylene oxide.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol and the condensation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from about 10 to 14 carbon atoms).
  • Other examples are those C 6 -Cn straight-chain alcohols which are ethoxylated with from about 3 to about 6 moles of ethylene oxide. Their derivation is well known in the art.
  • Examples include Alfonic® 810-4.5, which is described in product literature from Sasol as a C8-10 having an average molecular weight of 356, an ethylene oxide content of about 4.85 moles (about 60 wt.%), and an HLB of about 12; Alfonic® 810-2, which is described in product literature as a C8-C10 having an average molecular weight of 242, an ethylene oxide content of about 2.1 moles (about 40 wt.%), and an HLB of about 12; and Alfonic® 610-3.5, which is described in product literature as having an average molecular weight of 276, an ethylene oxide content of about 3.1 moles (about 50 wt.%), and an HLB of 10.
  • Alcohol ethoxylates are ClO oxo-alcohol ethoxylates available from BASF under the Lutensol® ON tradename. They are available in grades containing from about 3 to about 11 moles of ethylene oxide (available under the names Lutensol® ON 30; Lutensol® ON 50; Lutensol® ON 60; Lutensol® ON 65; Lutensol® ON 66; Lutensol® ON 70; Lutensol® ON 80; and
  • Neodol® 91 series non-ionic surfactants available from Shell Chemical Company which are described as Cp-Cn ethoxylated alcohols.
  • the Neodol® 91 series non-ionic surfactants of interest include Neodol® 91-2.5, Neodol® 91-6, and Neodol® 91-8.
  • Neodol® 91-2.5 has been described as having about 2.5 ethoxy groups per molecule
  • Neodol 91-6 has been described as having about 6 ethoxy groups per molecule
  • Neodol 91-8 has been described as having about 8 ethoxy groups per molecule.
  • ethoxylated alcohols include the Rhodasurf® DA series non-ionic surfactants available from Rhodia which are described to be branched isodecyl alcohol ethoxylates.
  • Rhodasurf® DA-530 has been described as having 4 moles of ethoxylation and an HLB of 10.5;
  • Rhodasurf® DA-630 has been described as having 6 moles of ethoxylation with an HLB of 12.5;
  • Rhodasurf® DA-639 is a 90% solution of DA-630.
  • ethoxylated alcohols include those from Tomah Products (Milton, WI) under the Tomadol® tradename with the formula RO(CH 2 CH 2 O) n H where R is the primary linear alcohol and n is the total number of moles of ethylene oxide.
  • Tomadol® tradename with the formula RO(CH 2 CH 2 O) n H where R is the primary linear alcohol and n is the total number of moles of ethylene oxide.
  • Tomah include 91-2.5; 91-6; 91-8 - where R is linear C 9 /C 10 /Cii and n is 2.5, 6, or 8; 1-3; 1-5; 1-7; 1-73B; 1-9; where R is linear C n and n is 3, 5, 7 or 9; 23-1; 23-3; 23-5; 23-6.5 - where R is linear C 12 /C 13 and n is 1, 3, 5, or 6.5; 25-3; 25-7; 25-9; 25-12 - where R is linear C12/C13/C14/ Ci 5 and n is 3, 7, 9, or 12; and 45-7; 45-13 - where R is linear Ci 4 / Ci 5 and n is 7 or 13.
  • a further class of useful nonionic surfactants include primary and secondary linear and branched alcohol ethoxylates, such as those based on C 6 -CiS alcohols which further include an average of from 2 to SO moles of ethoxylation per mol of alcohol. These examples include the Genapol® UD (ex.
  • Genapol® LID 030 Ci i-oxo-alcohol polyglycol ether with 3 EO
  • Genapol ⁇ UD 050 Cn-oxo-alcohol polyglycol ether with 5 EO
  • Genapol® UD 070 Cn- oxo-alcohol polyglycol ether with 7 EO
  • Genapol® UD 080 Cn-oxo-alcohol polyglycol ether with 8 EO
  • Genapol® UD 088 Cn-oxo-alcohol polyglycol ether with 8 EO
  • Genapol® UD 110 Ci i-oxo-alcohol polyglycol ether with 11 EO.
  • a further class of useful nonionic surfactants include those surfactants having a formula RO(CH 2 CH 2 O) n H wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from Ci 2 H 25 to Ci 6 H 33 and n represents the number of repeating units and is a number of from about 1 to about 12. Surfactants of this formula are presently marketed under the Genapol® tradename (ex.
  • surfactants include the "26-L” series of the general formula RO(CH 2 CH 2 O) n H wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from Ci 2 H 25 to Ci 6 H 33 and n represents the number of repeating units and is a number of from 1 to about 12, such as 26-L-I 5 26-L- 1.6, 26-L-2, 26-L-3, 26-L-5, 26-L-45, 26-L-50, 26-L-60, 26-L- 6ON, 26-L-75, 26-L-80, 26-L-98N, and the 24-L series, derived from synthetic sources and typically contain about 55% Ci 2 and 45% Ci 4 alcohols, such as 24-L-3, 24-L-45, 24- L-50, 24-L-60, 24-L-60N, 24-L-75, 24-L-92, and 24-L-98N, all sold under the Genapol® tradename.
  • a further class of useful nonionic surfactants include alkoxy block copolymers, and in particular, compounds based on ethoxy/propoxy block copolymers.
  • Polymeric alkylene oxide block copolymers include nonionic surfactants in which the major portion of the molecule is made up of block polymeric C 2 -C 4 alkylene oxides.
  • Such nonionic surfactants while preferably built up from an alkylene oxide chain starting group, and can have as a starting nucleus almost any active hydrogen containing group including, without limitation, amides, phenols, thiols and secondary alcohols.
  • One group of such useful nonionic surfactants containing the characteristic alkylene oxide blocks are those which may be generally represented by the formula (A): HO-(EO) ⁇ (PO)y(EO) z -H (A)
  • (EO) x +y equals 20 to 50% of the total weight of said compounds, and, the total molecular weight is preferably in the range of about 2000 to 15,000.
  • PLURONIC ex. BASF
  • Emulgen ex. Kao.
  • a further group of such useful nonionic surfactants containing the characteristic alkylene oxide blocks are those can be represented by the formula (B):
  • R is an alkyl, aryl or aralkyl group, where the R group contains 1 to 20 carbon atoms, the weight percent of EO is within the range of 0 to 45% in one of the blocks a, b, and within the range of 60 to 100% in the other of the blocks a, b, and the total number of moles of combined EO and PO is in the range of 6 to 125 moles, with 1 to 50 moles in the PO rich block and 5 to 100 moles in the EO rich block.
  • Specific nonionic surfactants which in general are encompassed by Formula B include butoxy derivatives of propylene oxide/ethylene oxide block polymers having molecular weights within the range of about 2000-5000.
  • useful nonionic surfactants include those which can be represented by formula (C) as follows:
  • BO represents butylene oxide
  • R is an alkyl group containing I to 20 carbon atoms
  • n is about 5-15
  • x is about 5-15.
  • nonionic surfactants include those which may be represented by the following formula (D):
  • BO represents butylene oxide
  • n is about 5-15, preferably about 15
  • x is about 5-15, preferably about 15, and
  • y is about 5-15, preferably about 15.
  • Still further exemplary useful nonionic block copolymer surfactants include ethoxylated derivatives of propoxylated ethylene diamine, which may be represented by the following formula:
  • (PO) represents propoxy
  • the amount of (PO) x is such as to provide a molecular weight prior to ethoxylation of about 300 to 7500
  • the amount of (E0) y is such as to provide about 20% to 90% of the total weight of said compound.
  • Further useful non-ionic surfactants which may be used in the inventive compositions include those presently marketed under the trade name Pluronics® (ex. BASF).
  • the compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the molecular weight of the hydrophobic portion of the molecule is of the order of 950 to 4,000 and preferably 200 to 2,500.
  • polyoxyethylene radicals of the hydrophobic portion tends to increase the solubility of the molecule as a whole so as to make the surfactant water-soluble.
  • the molecular weight of the block polymers varies from 1,000 to 15,000 and the polyethylene oxide content may comprise 20% to 80% by weight.
  • these surfactants are in liquid form and particularly satisfactory surfactants are available as those marketed as Pluronics® L62 and Pluronics® L64.
  • Alkylmonoglyocosides and alkylpolyglycosides which find use in the present inventive compositions include known nonionic surfactants which are alkaline and electrolyte stable.
  • Alkylmonoglycosides and alkylpolyglycosides are prepared generally by reacting a monosaccharide, or a compound hydrolyzable to a monosaccharide with an alcohol such as a fatty alcohol in an acid medium.
  • an alcohol such as a fatty alcohol in an acid medium.
  • Various glycoside and polyglycoside compounds including alkoxylated glycosides and processes for making them are disclosed in U.S. Pat. Nos.
  • One exemplary group of such useful alkylpolyglycosides include those according to the formula: R 2 O-(C n H 2n O) n -(Z) x wherein:
  • R. 2 is a hydrophobic group selected from alkyl groups, alkylphenyl groups, hydroxyalkylphenyl groups as well as mixtures thereof, wherein the alkyl groups may be straight chained or branched, and which contain from about 8 to about 18 carbon atoms, n has a value of 2 - 8, especially a value of 2 or 3; r is an integer from 0 to 10, but is preferably 0,
  • Z is derived from glucose; and, x is a value from about 1 to 8, preferably from about 1.5 to 5.
  • the alkylpolyglycosides are nonionic fatty alkylpolyglucosides which contain a straight chain or branched chain Cs -C 1 5 alkyl group, and have an average of from about 1 to 5 glucose units per fatty alkylpolyglucoside molecule. More preferably, the nonionic fatty alkylpolyglucosides which contain straight chain or branched Cg -Ci 5 alkyl group, and have an average of from about 1 to about 2 glucose units per fatty alkylpolyglucoside molecule.
  • a further exemplary group of alkyl glycoside surfactants suitable for use in the practice of this invention may be presented by the following formula (A): wherein:
  • R is a monovalent organic radical containing from about 6 to about 30, preferably from about 8 to 18 carbon atoms,
  • R 1 is a divalent hydrocarbon radical containing from about 2 to about 4 carbon atoms
  • y is a number which has an average value from about 0 to about 1 and is preferably 0.
  • G is a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms; and, x is a number having an average value from about 1 to 5 (preferably from 1.1 to 2);
  • I l Z is O 2 M 1 , °- C ⁇ R2 ⁇ 0(CH 2 ), CO 2 M 1 , OSO 3 M 1 , or 0(CH 2 )SO 3 M 1 ;
  • b is a number of from O to 3x +1 preferably an average of from 0.5 to 2 per glycosal group;
  • p is 1 to 10,
  • M 1 is H + or an organic or inorganic counterion, particularly cations such as, for example, an alkali metal cation, ammonium cation, monoethanolamine cation or calcium cation.
  • R is generally the residue of a fatty alcohol having from about 8 to 30 and preferably 8 to 18 carbon atoms.
  • alkylglycosides examples include, for example APG 325 CS Glycoside® which is described as being a 50% C 9 -C 11 alkyl polyglycoside, also commonly referred to as D- glucopyranoside, (commercially available from Henkel KGaA) and Glucopon® 625 CS which is described as being a 50% Cio -Ci 6 alkyl polyglycoside, also commonly referred to as a D-glucopyranoside, (ex. Henkel).
  • APG 325 CS Glycoside® which is described as being a 50% C 9 -C 11 alkyl polyglycoside, also commonly referred to as D- glucopyranoside, (commercially available from Henkel KGaA)
  • Glucopon® 625 CS which is described as being a 50% Cio -Ci 6 alkyl polyglycoside, also commonly referred to as a D-glucopyranoside, (ex. Henkel).
  • nonionic surfactants which may be included in the inventive compositions include alkoxylated alkanolamides, preferably C8-C24 alkyl di(C2-C3 alkanol amides), as represented by the following formula: R 5 -CO-NH-R 6 -OH wherein R 5 is a branched or straight chain C 8 -C 24 alkyl radical, preferably a Ci 0 -Ci 6 alkyl radical and more preferably a Cn-Ci 4 alkyl radical, and R 6 is a Ci-C 4 alkyl radical, preferably an ethyl radical.
  • the inventive compositions may also include a nonionic amine oxide constituent.
  • Exemplary amine oxides include:
  • Alkyl di (lower alkyl) amine oxides in which the alkyl group has about 10- 20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated.
  • the lower alkyl groups include between 1 and 7 carbon atoms. Examples include lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, and those in which the alkyl group is a mixture of different amine oxide, dimethyl cocoamine oxide, dimethyl (hydrogenated tallow) amine oxide, and myristyl/palmityl dimethyl amine oxide;
  • Alkylmorpholine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated.
  • the amine oxide constituent is an alkyl di (lower alkyl) amine oxide as denoted above and which may be represented by the following structure:
  • Ri is a straight chained Ci-C 4 alkyl group, preferably both Rj are methyl groups; and,
  • R 2 is a straight chained Cs-Ci 8 alkyl group, preferably is Ci O -Ci 4 alkyl group, most preferably is a Ci 2 alkyl group.
  • Each of the alkyl groups may be linear or branched, but most preferably are linear.
  • the amine oxide constituent is lauryl dimethyl amine oxide.
  • Technical grade mixtures of two or more amine oxides may be used, wherein amine oxides of varying chains of the R 2 group are present.
  • the amine oxides used in the present invention include R 2 groups which comprise at least 50%wt, preferably at least 60%wt. ofCi 2 alkyl groups and at least 25%wt. of C H alkyl groups, with not more than 15%wt. of C i ⁇ , Cis or higher alkyl groups as the R 2 group.
  • nonionic surfactant constituent when present, my comprise two or more nonionic surfactants.
  • nonionic surfactants are per se, known to the art, and are more particularly described in McCutcheon 's Detergents and Emulsifiers, noted above.
  • Foaming agents, and foam stabilizing agents may be provided, including alkyl sulfates, alkyl sulfonates, amine oxides, as well as alkanolamides. Such may be especially desirable where the composition is packaged in a pressurized device, i.e., an aerosol canister or in a hand-held pumpable container (such as a hand held trigger-spraying vessel).
  • a pressurized device i.e., an aerosol canister or in a hand-held pumpable container (such as a hand held trigger-spraying vessel).
  • fragrances natural or synthetically produced.
  • Such fragrances may be added in any conventional manner, admixing to a composition or blending with other constituents used to form a composition, in amounts which are found to be useful to enhance or impart the desired scent characteristic to the composition, and/or to cleaning compositions formed therefrom.
  • Fragrances refer to and to include any non-water soluble fragrance substance or mixture of such substances including those which are naturally derived (i.e., obtained by extraction of flower, herb, blossom or plant), those which are artificially derived or produced (i.e., mixture of natural oils and/or oil constituents), and those which are synthetically produced substances (odiferous substances).
  • perfumes are complex mixtures or blends various organic compounds including, but not limited to, certain alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils such as from about 0 to about 85% by weight, usually from about 10 to about 70% by weight, the essential oils themselves being volatile odiferous compounds and also functioning to aid in the dissolution of the other components of the perfume, hi the present invention, the precise composition of the perfume is of no particular consequence to cleaning performance so long as it may be effectively included as a constituent of the compositions, and have a pleasing fragrance.
  • the perfume, as well as the other ingredients used in making up compositions of the invention should be cosmetically acceptable, i.e., feature low toxicity or no toxicity, hypoallergenic character, etc.
  • compositions which include a fragrance it is frequently desirable to include a fragrance solubilizer which assists in the dispersion, solution or mixing of the fragrance constituent in an aqueous base.
  • a fragrance solubilizer which assists in the dispersion, solution or mixing of the fragrance constituent in an aqueous base.
  • These include known art compounds, including condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri-Cio-C2o alkanoic acid esters having a HLB of 8 to 17 are also known as nonionic surfactants.
  • Suitable surfactants include water soluble nonionic surfactants of which many are commercially known and, by way of non-limiting example, include the primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkylphenol ethoxylates and ethylene-oxide-propylene oxide condensates of primary alkanols, and condensates of ethylene oxide with sorbitan fatty acid esters.
  • This fragrance solubilizer component is added in minor amounts, preferably in an amount effective in aiding in the solubilization of the fragrance component, but not in any significantly greater proportion, such that it would be considered as a detergent constituent.
  • Such minor amounts recited herein are generally up to about 0.5% by weight of the total composition, but more generally present an amount of about 0. 1% by weight and less, and preferably present in amounts of about 0.05% by weight and less.
  • constituents are one or more coloring agents which find use in modifying the appearance of the compositions and enhance their appearance from the perspective of a consumer or other end user.
  • Known coloring agents may be incorporated in the compositions in any effective amount to improve or impart to compositions a desired appearance or color.
  • Such a coloring agent or coloring agents may be added in a conventional fashion, i.e., admixing to a composition or blending with other constituents used to form a composition.
  • pH buffering compositions so as to maintain the pH of the inventive compositions may also be added. While the compositions of the invention generally does not require a pH buffering composition, the use of such a pH buffering composition may provide the benefit of hard water ion sequestration.
  • useful pH buffer compounds and/or pH buffering systems or compositions are alkali metal phosphates, polyphosphates, pyrophosphates, triphosphates, tetraphosphates, silicates, metasilicates, polysilicates, carbonates, hydroxides, and mixtures of the same. Certain salts, such as the alkaline earth phosphates, carbonates, hydroxides, can also function as buffers.
  • buffers such materials as aluminosilicates (zeolites), borates, aluminates and certain organic materials such as gluconates, succinates, maleates, citrates, and their alkali metal salts.
  • zeolites aluminosilicates
  • borates aluminates
  • certain organic materials such as gluconates, succinates, maleates, citrates, and their alkali metal salts.
  • gluconates such as gluconates, succinates, maleates, citrates, and their alkali metal salts.
  • citric acid such as is available in an anhydrous salt form of an alkali metal citric acid is added as it is readily commercially available, and effective.
  • a buffering agent is desirable in certain cases wherein long term, i.e., prolonged storage, is to be anticipated for a composition, as well as insuring the safe handling of said aqueous composition.
  • Preservatives which do not include a disinfectant component may also be added in minor amounts in the formulations according to the invention. Compositions known in the art may be used. Examples of such preservatives compounds include those which are presently commercially available under the trademarks Kathono ® CG/ICP (Rohm & Haas, Philadelphia Pa.), Suttocide® A (Sutton Labs, Chatham NJ.) as well as Midtect® TFP (Tri-K Co., Emerson, N.J.).
  • Such preservatives are generally added in only minor amounts, i.e., amounts of about 0.5% by weight of the total composition, more generally an amount of about 0.1% by weight and less, and preferably present in amounts of about 0.05% by weight and less.
  • preservative constituents are not necessary in the inventive compositions.
  • Thickening and/or gelling agents may be added to the hard surface cleaning compositions according to the present invention in order to modify the viscous and/or thixatropic properties thereof. For example, in certain applications it is contemplated that it may be desirable to provide a more viscous, viz., higher viscosity than that of water, whether for aesthetic or functional reasons.
  • a suitable amount of a gelling agent may be desired not only for aesthetic reasons but also to limit the spreading of the composition as it is applied to a surface.
  • This function is desirable in providing a means to apply the composition over a limited area, such as directly onto a stain, without applying an excess onto the surrounding area of a surface.
  • This function also aids in the surface retention time on non-horizontal surfaces, ensuring that the cleaning composition is in contact with a stained surface without flowing off too rapidly.
  • thixotropic properties may also be desired under certain circumstances.
  • known thickening and gelling agents including, but not limited to, cellulose compounds, xanthan gums, polymers and/or clays may be added.
  • compositions described in this specification include particularly: disinfection, good removal of hard water stains, good removal of soap scum stains, relatively low toxicity, as well as ease in handling of the composition due to its readily pourable or pumpable characteristic. Further, when one or more of the optional constituents are added, i.e., fragrance, foaming agents, coloring agents, the aesthetic and consumer appeal of the product is favorably improved.
  • compositions provide certain technical benefits when used on hard surfaces, particularly: satisfactory removal of hard water stains, satisfactory removal of soap scum stains, and optionally but desirably in preferred embodiments also provide satisfactory disinfection or sanitization of hard surfaces.
  • the compositions are readily pourable and are desirably provided as a ready to use pourable product in a manually squeezable (manually deformable) bottle. In use, the consumer generally applies an effective amount of the composition and within a few moments thereafter, wipes off the treated area with a rag, towel, brush or sponge, usually a disposable paper towel or sponge.
  • the composition according to the invention may be left on the stained area until it has effectively loosened the stain deposits after which it may then be wiped off, rinsed off, or otherwise removed.
  • multiple applications may also be used.
  • compositions are desirably provided as a ready to use product which may be directly applied to a hard surface.
  • hard surfaces suitable for coating with the polymer include surfaces composed of refractory materials such as: glazed and unglazed tile, brick, porcelain, ceramics as well as stone including marble, granite, and other stones surfaces; glass; metals; plastics e.g. polyester, vinyl; fiberglass, Formica®, Corian® and other hard surfaces known to the industry.
  • Hard surfaces which are to be particularly denoted are lavatory fixtures such as shower stalls, bathtubs and bathing appliances (racks, curtains, shower doors, shower bars) toilets, bidets, wall and flooring surfaces especially those which include refractory materials and the like.
  • hard surfaces which are to be denoted are those associated with kitchen environments and other environments associated with food preparation, including cabinets and countertop surfaces as well as walls and floor surfaces especially those which include refractory materials, plastics, Formica®, Corian® and stone. Still further hard surfaces include those associated with medical facilities, e.g., hospitals, clinics as well as laboratories, e.g., medical testing laboratories.
  • compositions are particularly effective in the cleaning of metal and metallic surfaces. Such surfaces are commonly encountered in lavatory environments, e.g., lavatory fixtures, as well as kitchen environments, e.g, cookware, utensils, dishware and the like.
  • the compositions also find use in the cleaning of metal surfaces upon or within the interior of kitchen and lavatory appliances, e.g. in the cleaning of metal surfaces on kitchen appliances, including but not limited to polished, chromed, burnished or so called 'brushed" or matte metal surfaces such as on kitchen countertops, appliance housings, appliance surfaces including exterior surfaces such as doors, as well as interior surfaces such as the interior spaces of dishwashers, ovens, kitchen ranges and the like.
  • inventive compositions provide excellent cleaning benefits and also surprisingly provide improved cleaning and reduction of stains, tarnish or other metal discoloration, e.g., as may be caused by the buildup of dirt, grease, and the like or metal oxidation of treated metal surfaces.
  • This effect is most pronounced on copper surfaces, however it is to be understood that the inventive compositions find use in the cleaning treatment of all metal surfaces as may be encountered in such environments.
  • metals include aluminum, copper, steel, stainless steel, brass, metal alloys which may include one or more of the former metals, as well as chromed metal and non-metal substrates which have a metal or metallized surface.
  • the hard surface cleaner composition provided according to the invention can be desirably provided as a ready to use product in a manually operated spray-dispensing container.
  • a typical container is generally made of synthetic polymer plastic material, such as polyethylene, polypropylene, polyvinyl chloride or the like, and includes a spray nozzle, a dip tube and associated pump dispensing parts, and is thus ideally suited for use in a consumer "spray and wipe” application.
  • the consumer generally applies an effective amount of the cleaning composition using the pump and within a few moments thereafter, wipes off the treated area with a rag, towel, or sponge, usually a disposable paper towel or sponge.
  • the cleaning composition according to the invention may be left on the stained area until it has effectively loosened the stain deposits, after which it may then be wiped off, rinsed off, or otherwise removed.
  • the compositions according to the invention may be formulated so that they may be useful in conjunction with an "aerosol" type product wherein they are discharged from a pressurized aerosol container.
  • an aerosol type product it is preferred that corrosion resistant aerosol containers, such as coated or lined aerosol containers be used. Such are preferred as they are known to be resistant to the effects of acidic formulations.
  • propellants such as liquid propellants as well as propellants of the non-liquid form, i.e., pressurized gases, including carbon dioxide, air, nitrogen, hydrocarbons as well as others may be used.
  • cleaning compositions are most beneficial for use in undiluted form, viz., their form as described above, they may also be diluted to form a cleaning composition therefrom.
  • cleaning compositions may be easily prepared by diluting measured amounts of the compositions in further amounts of water by the consumer or other end user in certain weight ratios of composition to water, and optionally, agitating the same to ensure even distribution of the composition in the water.
  • aqueous compositions according to the invention may be used without further dilution, but may also be used with a further aqueous dilution, i.e., in composition to water concentrations of about 1:0 to extremely dilute dilutions such as about 1:10,000, but preferably would be used in a weight or volume ratio proportion of about 1 : 10 to about 1 : 100. Generally better results and faster removal are to be expected at lower relative dilutions of the composition and the water.
  • compositions according to the invention are easily produced by any of a number of known art techniques.
  • a part of the water is supplied to a suitable mixing vessel further provided with a stirrer or agitator, and while stirring, the remaining constituents are added to the mixing vessel, including any final amount of water needed to provide to 100%wt. of the inventive composition.
  • a measured amount of water was provided after which the constituents were added in the following sequence: thickening agents, surfactant, acid and then the remaining constituents. Mixing, which generally lasted from 5 minutes to 60 minutes was maintained until the particular formulation appeared to be homogeneous.
  • the exemplary compositions were readily pourable, and retained well mixed characteristics (i.e., stable mixtures) upon standing.
  • the constituents may be added in any order.
  • inventive formulations "EF' through “ES” including certain particularly preferred formulations are shown in Table 1 below.
  • the constituents were used "as supplied” from their respective supplier and unless otherwise stated, the percent actives in each of the as supplied constituents are considered to be 100% active.
  • To each of the compositions was added deionized water or tap water in "quantum sufficient” (q.s.) in order to provide 100 parts by weight of the specific composition.
  • two comparative compositions were also produced as indicated below on Table 2.
  • the constituents were used "as supplied” from their respective supplier and unless otherwise stated, the percent actives in each of the as supplied constituents are considered to be 100% active.
  • To each of the compositions was added deionized water or tap water in "quantum sufficient" (q.s.) in order to provide 100 parts by weight of the specific composition.
  • the first of these comparative compositions, Cl included no inorganic salts.
  • the second of these comparative compositions, C2 included sodium sulfate as an inorganic salt.
  • compositions of Table 1 were subjected to several tests to evaluate the ability of the compositions to clean soiled copper metal surfaces.
  • compositions according to El, E2, E3 and E4 were evaluated by partially immersing a penny into a volume of each of the aforesaid compositions and thereafter rinsing with distilled or tap water and allowing to dry. No surface agitation or stirring of the test composition was performed. Also the pennies were approximately 50% immersed so that the resultant "cleaned” and "uncleaned” sides could be visually evaluated on a side-by-side basis. A composition according to comparative Cl was similarly tested as well.
  • the degree of cleaning efficacy was judged on a scale of "0" to ⁇ 5", with no visually observed cleaning of the penny to the judged as a "0" score, and within the maximum cleaning to a shiny brightness being a established as the highest end of the scale and being rated a "5".
  • the results of the cleaning test are disclosed on the following Table 4A.
  • compositions comprising inorganic chloride salts were observed to be better performing in this cleaning of the copper surface than other inorganic salts, namely the inorganic sulfate salts, as exemplified by the results of C2.
  • Formulations of the present invention are expected to have good cleaning efficacy of hard surfaces, including surfaces other than metal or metallic surfaces.
  • certain of the preferred inventive composition will also provide an effective sanitizing or disinfecting benefit against one or more of the following: Staphylococcus aureus (gram positive type pathogenic bacteria) (ATCC 6538), Salmonella choleraesuis (gram negative type pathogenic bacteria) (ATCC 10708),
  • Escheria colt (gram negative type pathogenic bacteria) (ATCC 11229) and Pseudomonas aeruginosa (ATCC 15442).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne des compositions de nettoyage de surfaces dures ayant un pH acide qui présentent de bonnes propriétés de nettoyage et en particulier d’élimination efficace des taches de mousse de savon, tout en présentant de faibles niveaux potentiels d'irritabilité pour l'utilisateur. Lesdites compositions comprennent d’environ 0,1 à 10 % en poids d'un constituant de type agent séquestrant d’acide ; d’environ 0,1 à 10 % en poids d'un constituant de type solvant organique constitué uniquement d’un ou plusieurs solvants hydrophobes ; d’environ 0,001 à 1 % en poids d'un constituant simple qui présente à la fois les propriétés d'un agent tensioactif anionique et des propriétés hydrotropes ; une quantité efficace de nettoyage de métal d'un sel de type chlorure inorganique ; et, d’environ 0 à 20 % en poids d'un ou plusieurs constituants facultatifs ; le complément jusqu’à 100 % en poids étant constitué d’eau, lesquelles compositions sont de nature acide, et présentent de préférence un pH d’environ 5 ou moins. Lesdites compositions confèrent également de préférence des effets désinfectants. L’invention concerne également des procédés de production desdites compositions, ainsi que leurs procédés d’utilisation.
PCT/GB2006/001794 2005-06-07 2006-05-16 Améliorations des compositions organiques ou les concernant WO2006131689A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US68806605P 2005-06-07 2005-06-07
US60/688,066 2005-06-07
GB0601036,7 2006-01-19
GB0601036A GB2429015A (en) 2005-06-07 2006-01-19 An aqueous hard-surface cleaning composition

Publications (1)

Publication Number Publication Date
WO2006131689A1 true WO2006131689A1 (fr) 2006-12-14

Family

ID=36648670

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2006/001794 WO2006131689A1 (fr) 2005-06-07 2006-05-16 Améliorations des compositions organiques ou les concernant

Country Status (1)

Country Link
WO (1) WO2006131689A1 (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101210213B (zh) * 2006-12-31 2011-01-05 S.C.约翰逊父子公司 厨房清洁剂组合物
US20110245131A1 (en) * 2008-12-25 2011-10-06 Jeff Jianhai Mu Surfactant Compositions with Wide PH Stability
WO2014152189A1 (fr) * 2013-03-15 2014-09-25 Maria Beug-Deeb Inc. Dba T&M Associates Procédés et compositions pour nettoyer et désinfecter des surfaces
US20150159122A1 (en) * 2013-12-09 2015-06-11 General Electric Company Cleaning solution and methods of cleaning a turbine engine
EP3118300A1 (fr) * 2015-07-13 2017-01-18 The Procter and Gamble Company Compositions acides de nettoyage de surfaces dures comprenant un solvant
WO2017072482A1 (fr) * 2015-10-30 2017-05-04 Reckitt Benckiser Llc Compositions thérapeutiques ayant un effet antimicrobien
US9926517B2 (en) 2013-12-09 2018-03-27 General Electric Company Cleaning solution and methods of cleaning a turbine engine
US9957066B2 (en) 2015-02-13 2018-05-01 General Electric Company Detergent delivery methods and systems for turbine engines
US10610611B2 (en) * 2015-07-20 2020-04-07 S. C. Johnson & Son, Inc. Water-based fragrance composition, fragrance delivery device, and method of providing a long-lasting scent
US10676621B2 (en) 2016-03-04 2020-06-09 S. C. Johnson & Son, Inc. Multi-purpose floor finish composition
US11046913B2 (en) 2016-03-04 2021-06-29 S. C. Johnson & Son, Inc. Neutral floor cleaner compositions
US20210380906A1 (en) * 2020-06-05 2021-12-09 Fluid Energy Group Ltd. Stable Nitric Acid Blends And Uses Thereof
US11312922B2 (en) 2019-04-12 2022-04-26 Ecolab Usa Inc. Antimicrobial multi-purpose cleaner comprising a sulfonic acid-containing surfactant and methods of making and using the same
US11834632B2 (en) 2013-12-09 2023-12-05 General Electric Company Cleaning solution and methods of cleaning a turbine engine

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19918185A1 (de) * 1999-04-22 2000-10-26 Cognis Deutschland Gmbh Reinigungsmittel für harte Oberflächen
US6184195B1 (en) * 1997-11-28 2001-02-06 Reckitt Benckiser Inc. Blooming type germicidal hard surface cleaners comprising biphenyl-based solvents
US6221823B1 (en) * 1995-10-25 2001-04-24 Reckitt Benckiser Inc. Germicidal, acidic hard surface cleaning compositions
US6281182B1 (en) * 2000-04-06 2001-08-28 Colgate-Palmolive Co. Acidic cleaning composition comprising a glycol ether mixture
US20020187918A1 (en) * 2000-02-01 2002-12-12 Reckitt Benckiser Inc. Hard surface cleaning compositions and method of removing stains
US20030083219A1 (en) * 2000-06-05 2003-05-01 Rees Wayne M. Biocidal cleaner composition containing acid-anionic surfactant-alcohol combinations and method of using the composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6221823B1 (en) * 1995-10-25 2001-04-24 Reckitt Benckiser Inc. Germicidal, acidic hard surface cleaning compositions
US6184195B1 (en) * 1997-11-28 2001-02-06 Reckitt Benckiser Inc. Blooming type germicidal hard surface cleaners comprising biphenyl-based solvents
DE19918185A1 (de) * 1999-04-22 2000-10-26 Cognis Deutschland Gmbh Reinigungsmittel für harte Oberflächen
US20020187918A1 (en) * 2000-02-01 2002-12-12 Reckitt Benckiser Inc. Hard surface cleaning compositions and method of removing stains
US6281182B1 (en) * 2000-04-06 2001-08-28 Colgate-Palmolive Co. Acidic cleaning composition comprising a glycol ether mixture
US20030083219A1 (en) * 2000-06-05 2003-05-01 Rees Wayne M. Biocidal cleaner composition containing acid-anionic surfactant-alcohol combinations and method of using the composition

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101210213B (zh) * 2006-12-31 2011-01-05 S.C.约翰逊父子公司 厨房清洁剂组合物
US20110245131A1 (en) * 2008-12-25 2011-10-06 Jeff Jianhai Mu Surfactant Compositions with Wide PH Stability
US8338356B2 (en) * 2008-12-25 2012-12-25 Dow Global Technologies Llc Surfactant compositions with wide pH stability
WO2014152189A1 (fr) * 2013-03-15 2014-09-25 Maria Beug-Deeb Inc. Dba T&M Associates Procédés et compositions pour nettoyer et désinfecter des surfaces
US20150159122A1 (en) * 2013-12-09 2015-06-11 General Electric Company Cleaning solution and methods of cleaning a turbine engine
US11834632B2 (en) 2013-12-09 2023-12-05 General Electric Company Cleaning solution and methods of cleaning a turbine engine
US9926517B2 (en) 2013-12-09 2018-03-27 General Electric Company Cleaning solution and methods of cleaning a turbine engine
US9957066B2 (en) 2015-02-13 2018-05-01 General Electric Company Detergent delivery methods and systems for turbine engines
EP3118300A1 (fr) * 2015-07-13 2017-01-18 The Procter and Gamble Company Compositions acides de nettoyage de surfaces dures comprenant un solvant
US10610611B2 (en) * 2015-07-20 2020-04-07 S. C. Johnson & Son, Inc. Water-based fragrance composition, fragrance delivery device, and method of providing a long-lasting scent
CN108471742A (zh) * 2015-10-30 2018-08-31 雷克特本克斯尔有限责任公司 提供抗微生物益处的处理组合物
WO2017072482A1 (fr) * 2015-10-30 2017-05-04 Reckitt Benckiser Llc Compositions thérapeutiques ayant un effet antimicrobien
US10676621B2 (en) 2016-03-04 2020-06-09 S. C. Johnson & Son, Inc. Multi-purpose floor finish composition
US11046913B2 (en) 2016-03-04 2021-06-29 S. C. Johnson & Son, Inc. Neutral floor cleaner compositions
US11214697B2 (en) 2016-03-04 2022-01-04 S. C. Johnson & Son, Inc. Multi-purpose floor finish composition
US11866674B2 (en) 2016-03-04 2024-01-09 S.C. Johnson & Son, Inc. Neutral floor cleaner compositions
US11312922B2 (en) 2019-04-12 2022-04-26 Ecolab Usa Inc. Antimicrobial multi-purpose cleaner comprising a sulfonic acid-containing surfactant and methods of making and using the same
US11891586B2 (en) 2019-04-12 2024-02-06 Ecolab Usa Inc. Highly acidic antimicrobial multi-purpose cleaner and methods of making and using the same
US20210380906A1 (en) * 2020-06-05 2021-12-09 Fluid Energy Group Ltd. Stable Nitric Acid Blends And Uses Thereof
US12065628B2 (en) * 2020-06-05 2024-08-20 Dorf Ketal Chemicals Fze Stable nitric acid blends and uses thereof

Similar Documents

Publication Publication Date Title
WO2006131689A1 (fr) Améliorations des compositions organiques ou les concernant
US7196046B2 (en) Hard surface cleaner comprising a suspension of alginate beads
US7186676B2 (en) Hard surface cleaning compositions comprising alginate materials and xanthan gum
US7256167B2 (en) Hard surface cleaner comprising suspended particles and oxidizing agent
CA2396742C (fr) Composition de nettoyage de surfaces dures
AU2007330593B2 (en) Aqueous highly acidic hard surface cleaning compositions
EP1899449B1 (fr) Compositions acides de nettoyage de surfaces dures
US7119055B2 (en) Hard surface cleaners comprising a thickening gum mixture
AU2007226419B2 (en) Aqueous highly acidic hard surface cleaning compositions
US7288512B2 (en) Hard surface cleaning compositions comprising suspended alginate inclusions
AU2004213642B2 (en) Hard surface cleaning compositions
GB2429015A (en) An aqueous hard-surface cleaning composition
AU2004213627B2 (en) Hard surface cleaning compositions
WO2009112794A1 (fr) Compositions épaissies de nettoyage de surfaces dures comprenant un alcoolate d'amine grasse
GB2429016A (en) Acidic hard surface cleaning compositions

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06743904

Country of ref document: EP

Kind code of ref document: A1