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EP0876458B2 - Reinigungsmittel für harte oberflächen - Google Patents

Reinigungsmittel für harte oberflächen Download PDF

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Publication number
EP0876458B2
EP0876458B2 EP95944437A EP95944437A EP0876458B2 EP 0876458 B2 EP0876458 B2 EP 0876458B2 EP 95944437 A EP95944437 A EP 95944437A EP 95944437 A EP95944437 A EP 95944437A EP 0876458 B2 EP0876458 B2 EP 0876458B2
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EP
European Patent Office
Prior art keywords
composition
carboxylate
polymer
containing polymer
process according
Prior art date
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EP95944437A
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English (en)
French (fr)
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EP0876458A1 (de
EP0876458B1 (de
Inventor
Neil James Gordon
Vincent Reniers
Alan David Willey
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Procter and Gamble Co
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Procter and Gamble Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • the present invention relates to compositions for cleaning hard-surfaces, especially in-house hard-surfaces.
  • compositions for cleaning hard-surfaces have been disclosed in the art. Much of the focus for such compositions has been on providing outstanding cleaning on a variety of surfaces and soils. For some specialised cleaners, such as glass cleaners, much effort has additionally been devoted to the formulation of so-called "streak-free" products, i.e. products which leave no or little visible residues after use.
  • the object of the present invention is to formulate hard-surface cleaning compositions which clean and provide gloss to the cleaned surface. That is different from a "streak-free" composition, in that gloss additionally requires improved reflectance of light from the cleaned surface.
  • a variety of products are commercially available for delivering gloss to surfaces, and they are disclosed for instance in US 3,960,575 and US 4,218,250. Both references recommend the use of various silicones for delivering gloss.
  • Such compositions are not fully formulated hard-surface cleaners, so that they do not clean efficiently, and indeed the formulation of silicone in hard-surface cleaners has not shown any gloss benefits. See for instance EP 374 471 which discloses a hard-surface cleaning composition with, amongst other essentials, a silicone for improved resistance to soil redeposition.
  • compositions may be used to clean in-house hard-surfaces made of a variety of material like glazed and non-glazed ceramic tiles, vinyl, linoleum, melamine, both in diluted and neat conditions.
  • US 4784 786 discloses a composition for cleaning glass which can be readily applied to and removed from a soiled glass surface to leave the surface clean and free of streaking and cloudiness.
  • Said compositions comprise amongst other ingredients, surfactants, glycol ether, an anionic polysulfonic acid and an anhydride compound comprising an olefin-maleic anhydride copolymer. No divalent counterions are disclosed.
  • WO 94/26858 discloses a liquid hard-surface composition (pH 2-8) with nonionic surfactants (1-30%) and anionic polymers having an average molecular weight of less than 1 000 000. Said compositions bring a surprising initial cleaning benefit in addition to the anti-soiling benefit. Indeed, WO 94/26858 discloses that acrylic, methacrylic and maleic anhydride derivatives such as copolymers of styrene with maleic produce a streak-free finish after drying. No divalent counterions are disclosed.
  • EP-A-658 184 discloses liquid or gel dishwashing detergent compositions containing alkyl amphocarboxylic acid (5%-95%) and magnesium or calcium salts (0.1%-4%), said compositions having a pH in a 10% solution in water at 20°C of 7 to 10.
  • said compositions comprise co-surfactants, like nonionic surfactants (5%-95%).
  • No carboxylate-containing polymers are disclosed. Also no hard-surfaces application is disclosed.
  • EP-A-162 033 discloses heavy-duty liquid detergents comprising proteolytic or amylolytic enzymes, an anionic surfactant (10%-50%), optionally other surfactants like nonionic ethoxylated surfactants (2%-25%), from 1 to 30 millimoles of calcium ions per liter of composition and detergent builders (2%-15%) like polycarboxylates including water-soluble salts of specific polymeric aliphatic polycarboxylic acids (e.g., polymers and copolymers of maleic acid).
  • EP-A-162 033 further discloses that the level of calcium ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with fatty acids and the like in the composition.
  • Sources of calcium ions are for example calcium chloride and/or calcium acetate. No hard-surface application is disclosed.
  • EP-A-602 179 discloses that the addition of calcium salts to compositions containing a polyhydroxy fatty acid amide, and an anionic surfactant improves the removal of greasy soils while delivering good hand mildness.
  • EP-A-602 179 discloses dishwashing compositions comprising an anionic surfactant (3%-95%), a polyhydroxy fatty acid amide (3%-40%) and calcium ions (0.1% to 3%).
  • the compositions have a pH of from 5.5 to 10 in a 10% solution in water at 20°C.
  • said compositions comprise polycarboxylate polymers having a molecular weight of 750 000 to 4 000 000 (0.1%-10%). No hard-surface cleaning application is disclosed.
  • EP-A-670 884 discloses fully formulated liquid detergent compositions (pH 7.5-9.5) comprising a polyhydroxy fatty acid amide surfactant (5%-50%), a nonionic (5%-50%), a source of calcium (0.5%-2%) and soap.
  • Optional ingredients are polycarboxylate builders such as copolymers of maleic anhydride with ethylene or vinyl methyl ether and polymeric polycarboxylic dispersing agents (0.1%-7%) that can be prepared by polymerizing or copolymerizing suitable unsaturated monomers including acrylic acid, maleic acid.
  • Acrylic/maleic-based copolymers with a molecular weight of 2 000 to 100 000 are disclosed. No hard-surface application is disclosed.
  • GB 1430 204 discloses compositions suitable to clean various soiled subtracts including hard-surfaces.
  • Said compositions comprise a polymer (3%-35%) such as acrylic polymers and polycarbonates, optionally metal ions such as calcium or magnesium (0.1%-5%), and builders (0.1%-5%) such as copolymers of vinyl methyl ether and maleic anhydride, and carboxymethyl cellulose.
  • a surfactant may be used as optional but no levels thereof are disclosed, let alone particular classes of surfactants.
  • GB 1430 204 also discloses a process of cleaning a soiled surface, said process comprising the steps of applying to said surface said composition, allowing said composition to form a tacky film to which soils adhere, allowing said composition to dry, whereby as a result of said drying, said film fractures to form a removable residue and then removing said residue.
  • the presence of the metal ions increases the brittleness of the film.
  • the present invention encompasses a process of cleaning hard-surfaces wherein a liquid composition having a pH of from 6 to 13 and comprising a carboxylate-containing polymer and a divalent counterion, added in the form of a non-complex salt or as one ingredient with said carboxylate-containing polymer, in a molar ratio of said polymer to said divalent counterion of from 12:1 to 1:32 and from 0.1% to 50% by weight of the total composition of a surfactant, is applied onto said surface, wherein said carboxylate-containing polymer is a cellulose derivative, a polyacrylate an acrylic/maleic-based copolymer or a mixture thereof.
  • the present invention also encompasses a liquid hard-surface cleaning composition having a pH of from 6 to 13 and comprising a carboxylate-containing polymer and a divalent counterion, added in the form of a non-complex salt or as one ingredient with said carboxylate-containing polymer, in a molar ratio of said polymer to said divalent counterion of from 12:1 to 1:32 and from 0.1% to 50% by weight of the total composition of a surfactant, wherein said carboxylate-containing polymer is a cellulose derivative, a polyacrylate an acrylic/maleic-based copolymer or a mixture thereof. said composition being free of a proteolytic or amylolytic enzyme and of polyhydroxy fatty acid amide.
  • the present invention relates to a process of cleaning hard-surfaces wherein a liquid composition comprising a carboxylate-containing polymer and a divalent counterion, added in the form of a non-complex salt or as one ingredient with said carboxylate-containing polymer, in a molar ratio of said polymer to said divalent counterion of from 12:1 to 1:32 and a surfactant, is applied onto said surfaces, wherein said carboxylate-containing polymer is a cellulose derivative, a polyacrylate, an acrylic/maleic-based copolymer or a mixture thereof.
  • hard-surfaces it is meant herein any kind of in-house hard-surfaces with the exception of dishes and any utensiles used for the cooking and for eating/drinking.
  • Preferred herein “hard-surfaces” has to be understood as any fixed household hard-surface including floors, walls, windows, fixtures and fittings and the like.
  • Said liquid composition may be applied to the surface to be cleaned in its neat form or in its diluted form.
  • diluted form it is meant herein that said liquid composition is diluted by the user typically with water.
  • the composition is diluted prior use to a typical dilution level of 10 to 200 times its weight of water.
  • Usual recommended dilution level is a 1.2% dilution of the composition in water which corresponds to an active level of from 0.01% to 0.5% by weight of the resulting washing solution.
  • the present invention is a liquid hard-surface cleaning composition
  • a carboxylate-containing polymer and a divalent counterion added in the form of a non-complex salt or as one ingredient with said carboxylate-containing polymer, in molar ratio of said polymer to said divalent counterion of from 12:1 to 1:32 and from 0.1% to 50% by weight of the total composition of a surfactant, wherein said carboxylate-containing polymer is a cellulose derivative, a polyacrylate, an acrylic maleic-based copolymer or a mixture thereof, said composition being free of a proteolytic or amylolytic enzyme and of polyhydroxy fatty acid amide.
  • the compositions according to the present invention comprise a carboxylate-containing polymer, or mixtures thereof.
  • carboxylate-containing polymer it is meant herein a polymer or copolymer comprising at least a monomeric unit which contains at least a carboxylate functionality.
  • carboxylate-containing polymers can be employed according to the present invention homo- or co-polymeric polyacrylates or mixtures thereof. Indeed, such carboxylate-containing polymers can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 1,000,000, more preferably from about 10,000 to 150,000 and most preferably from about 20,000 to 100,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferred carboxylate-containing polymer.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982. Particularly preferred is a copolymer of maleic / acrylic acid with an average molecular weight of about 70,000. Such copolymers are commercially available from BASF under the trade name SOKALAN CP5.
  • carboxylate-containing polymers to be used herein include cellulose derivatives such as carboxymethylcellulose.
  • carboxymethylcellulose may be used as a salt with conventional cation such as sodium, potassium, amines or substituted amines.
  • the compositions according to the present invention comprise a divalent counterion, or mixtures thereof.
  • All divalent ions known to those skilled in the art may be used herein.
  • Preferred divalent ions to be used herein are calcium, zinc, cadmium, nickel, copper, cobalt, zirconium, chromium and/or magnesium and more preferred are calcium, zinc and/or magnesium.
  • Said divalent ions are added in the form of salts for example as chloride, acetate, sulphate, formate and/or nitrate.
  • calcium may be added in the form of calcium chloride, magnesium as magnesium acetate or magnesium sulphate and zinc as zinc chloride.
  • said carboxylate-containing polymer and said divalent counterion may be added as one ingredient provided that the molar ratio of said carboxylate-containing polymer to said divalent counterion/salt is from 12:1 to 1:32.
  • said polymer and said divalent counterion are present in the compositions for cleaning hard-surfaces herein in a molar ratio of said polymer to said divalent counterion of from 12:1 to 1:32, preferably of from 8:1 to 1:16, more preferably of from 6:1 to 1:12 and most preferably of from 4:1 to 1:6.
  • Preferred molar ratios of said polymer to said divalent counterion are those where improved gloss is obtained in the most economic way.
  • molar ratio of said polymer to said divalent counterion it is meant herein the number of moles of carboxylate-containing monomer to the number of moles of divalent ion.
  • carboxylate-containing polymer is an acrylic acid/maleic acid copolymer the molar ratio is stated as a range based on the theoretical molar ratio of a pure acrylic acid polymer to divalent ions and a pure maleic acid polymer to divalent ions.
  • compositions for the cleaning of hard-surfaces comprise from 0.01% to 20% by weight of the total composition of said carboxylate-containing polymer, or mixtures thereof, preferably from 0.1% to 10%, more preferably from 0.1% to 5% and from 0.01 % to 4% by weight of the total composition of said divalent counterion, or mixtures thereof, preferably from 0.02% to 2%, and more preferably from 0.02% to 1%.
  • improved gloss it is meant herein that the gloss observed, when cleaning a hard-surface according to the present invention with a composition comprising a surfactant, a carboxylate-containing polymer and a divalent counterion in a molar ratio of said polymer to said divalent counterion of from 12:1 to 1:32, is improved as compared to the gloss observed when cleaning said surface with the same composition without said surfactant, or with the same composition without said divalent counterion and said carboxylate-containing polymer in a molar ratio of said polymer to said divalent counterion of from 12:1 to 1:32.
  • This gloss improvement is observed in both neat or diluted usage conditions, and especially in the embodiment where the diluted usage is performed with soft water, i.e. a water with a water hardness of less than 171.5 ppm CaCO 3 (10 grains/gallons).
  • This gloss benefit may be evaluated by reflectance as judged by a gloss meter and/or by a visual grading as judged by a panel of graders.
  • the compositions according to the present invention comprise a surfactant, or mixtures thereof.
  • Said surfactant is present in the compositions according to the present invention in amounts of from 0.1% to 50% by weight of the total composition, preferably from 0.1% to 20% and more preferably of from 1% to 10%. It is said surfactant which in combination with said polymer and divalent counterion, is deposited on the surface cleaned and contributes to the gloss benefit.
  • Surfactants to be used herein include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.
  • nonionic surfactants are the nonionic surfactants.
  • Suitable nonionic surfactants for use herein include a class of compounds which may be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be branched or linear aliphatic (e.g. Guerbet or secondary alcohols) or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • a well-known class of nonionic synthetic detergents is made available on the market under the trade name "Pluronic".
  • These compounds are formed by condensing ethylene oxide with an hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the hydrophobic portion of the molecule which, of course, exhibits water-insolubility has a molecular weight of from about 1500 to 1800.
  • the addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water-solubility of the molecule as a whole and the liquid character of the products is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.
  • nonionic synthetic detergents include :
  • Particularly preferred surfactants include also the anionic surfactants.
  • Suitable anionic surfactants for use herein include alkali metal (e.g., sodium or potassium) fatty acids, or soaps thereof, containing from about 8 to about 24, preferably from about 10 to about 20 carbon atoms.
  • the fatty acids including those used in making the soaps can be obtained from natural sources such as, for instance, plant or animal-derived glycerides (e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale oil, fish oil, tallow, grease, lard and mixtures thereof).
  • the fatty acids can also be synthetically prepared (e.g., by oxidation of petroleum stocks or by the Fischer-Tropsch process).
  • Alkali metal soaps can be made by direct saponification of fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and coconut soaps.
  • tallow is used herein in connection with fatty acid mixtures which typically have an approximate carbon chain length distribution of 2.5% C14, 29% C16, 23% C18, 2% palmitoleic, 41.5% oleic and 3% linoleic (the first three fatty acids listed are saturated). Other mixtures with similar distribution, such as the fatty acids derived from various animal tallows and lard, are also included within the term tallow.
  • the tallow can also be hardened (i.e., hydrogenated) to convert part or all of the unsaturated fatty acid moieties to saturated fatty acid moieties.
  • coconut refers to fatty acid mixtures which typically have an approximate carbon chain length distribution of about 8% C8, 7% C10, 48% C12, 17% C14, 9% C16, 2% C18, 7% oleic, and 2% linoleic (the first six fatty acids listed being saturated).
  • Other sources having similar carbon chain length distribution such as palm kernel oil and babassu oil are included with the term coconut oil.
  • Suitable anionic surfactants for use herein include water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in the molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
  • these synthetic detergents are the sodium, ammonium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, especially those of the types described in U.S. Pat. Nos.
  • sodium alkyl glyceryl ether sulfonates especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about three moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates with about four units of ethylene oxide per molecule and in which the alkyl radicals contain about 9 carbon atoms; the reaction product of fatty acids esterified with isothionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of a methyl taurine in which the fatty acids, for example, are derived from coconut oil; and others known in the
  • Suitable zwitterionic detergents to be used herein comprise the betaine and betaine-like detergents wherein the molecule contains both basic and acidic groups which form an inner salt giving the molecule both cationic and anionic hydrophilic groups over a broad range of pH values.
  • Some common examples of these detergents are described in U.S. Pat. Nos. 2,082,275, 2,702,279 and 2,255,082.
  • Preferred zwitterionic detergent compounds have the formula wherein R1 is an alkyl radical containing from about 8 to about 22 carbon atoms, R2 and R3 contain from 1 to 3 carbon atoms, R4 is an alkylene chain containing from 1 to about 3 carbon atoms, X is selected from the group consisting of hydrogen and a hydroxyl radical, Y is selected from the group consisting of carboxyl and sulfonyl radicals and wherein the sum of R1, R2 and R3 radicals is from 14 to 24 carbon atoms.
  • Amphoteric and ampholytic detergents which can be either cationic or anionic depending upon the pH of the system are represented by detergents such as dodecylbeta-alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 2,658,072, N-higher alkylaspartic acids such as those produced according to the teaching of U.S. Pat. No. 2,438,091, and the products sold under the trade name "Miranol", and described in U.S. Pat. No. 2,528,378. Additional synthetic detergents and listings of their commercial sources can be found in McCutcheon's Detergents and Emulsifiers, North American Ed. 1980.
  • compositions according to the present invention are liquid hard-surface cleaning compositions.
  • the liquid compositions of the present invention are preferably but not necessarily formulated as aqueous compositions.
  • Aqueous compositions typically comprise from 50% to 98% by weight of the total composition of water, preferably from 60% to 95%, and more preferably from 80% to 95%.
  • compositions according to the present invention have a pH of from 6 to 13, preferably of from 6.5 to 12, and more preferably of from 7 to 11.
  • the pH of the compositions herein can be adjusted by any of the means well-known to the man skilled in the art such as addition of NaOH, KOH, K2CO3, Na2CO3 and the like.
  • compositions herein can further comprise a variety of optional ingredients.
  • Suitable optional ingredients for use herein include builders, chelants, solvents, buffers, bactericides, hydrotropes, colorants, stabilizers and/or perfumes.
  • Suitable perfumes to be used herein include materials which provide an olfactory aesthetic benefit and/or cover any "chemical" odor that the product may have.
  • the main function of a small fraction of the highly volatile, low boiling (having low boiling points), perfume components in these perfumes is to improve the fragrance odor of the product itself, rather than impacting on the subsequent odor of the surface being cleaned.
  • perfume components in these perfumes provide a fresh and clean impression to the surfaces, and it is desirable that these ingredients be deposited and present on the dry surface.
  • Perfume ingredients can be readily solubilized in the compositions, for instance by the nonionic detergent surfactants.
  • the perfume ingredients and compositions suitable to be used herein are the conventional ones known in the art. Selection of any perfume component, or amount of perfume, is based solely on aesthetic considerations.
  • Suitable perfume compounds and compositions can be found in the art including U.S. Pat. Nos. : 4,145,184, Brain and Cummins, issued March 20, 1979; 4,209,417, Whyte, issued June 24, 1980; 4,515,705, Moeddel, issued May 7, 1985; and 4,152,272, Young, issued May 1, 1979.
  • the degree of substantivity of a perfume is roughly proportional to the percentages of substantive perfume material used.
  • Relatively substantive perfumes contain at least 1%, preferably at least 10%, substantive perfume materials.
  • Substantive perfume materials are those odorous compounds that deposit on surfaces via the cleaning process and are detectable by people with normal olfactory acuity. Such materials typically have vapor pressures lower than that of the average perfume material.
  • Perfume ingredients useful herein, along with their odor character, and their physical and chemical properties, such as boiling point and molecular weight, are given in "Perfume and Flavor Chemicals (Aroma Chemicals),” Steffen Arctander, published by the author, 1969.
  • Examples of the highly volatile, low boiling, perfume ingredients are : anethole, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl formate, isobornyl acetate, camphene, ciscitral (neral), citronellal, citronellol, citronellyl acetate, para-cymene, decanal, dihydrolinalool, dihydromyrcenol, dimethyl phenyl carbinol, eucaliptol, geranial, geraniol, geranyl acetate, geranyl nitrile, cis-3-hexenyl acetate, hydroxycitronellal, d-limonene, linalool, linalool oxide, linalyl acetate, linalyl propionate, methyl anthranilate, alpha-methyl ionone, methyl nonyl acetaldehyde,
  • lavandin contains as major components : linalool; linalyl acetate; geraniol; and citronellol. Lemon oil and orange terpenes both contain about 95% of d-limonene.
  • moderately volatile perfume ingredients are : amyl cinnamic aldehyde, iso-amyl salicylate, betacaryophyllene, cedrene, cinnamic alcohol, coumarin, dimethyl benzyl carbinyl acetate, ethyl vanillin, eugenol, iso-eug-enol, flor acetate, heliotropine, 3-cis-hexenyl salicylate, hexyl salicylate, lilial (para-tertiarybutyl-alpha-methyl hydrocinnamic aldehyde), gamma-methyl ionone, nerolidol, patchouli alcohol, phenyl hexanol, beta-selinene, trichloromethyl phenyl carbinyl acetate, triethyl citrate, vanillin, and veratraldehyde.
  • Examples of the less volatile, high boiling, perfume ingredients are : benzophenone, benzyl salicylate, ethylene brassylate, galaxolide (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gama-2-benzopyran), hexyl cinnamic aldehyde, lyral (4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-10-carboxaldehyde), methyl cedrylone, methyl dihydro jasmonate, methyl-beta-naphthyl ketone, musk indanone, musk ketone, musk tibetene, and phenylethyl phenyl acetate.
  • compositions herein may comprise a perfume ingredient, or mixtures thereof, in amounts up to 5.0% by weight of the total composition, preferably in amounts of 0.1 % to 1.5%.
  • Suitable amino phosphonate compounds for use herein include amino alkylene poly (alkylene phosphonate), alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates.
  • the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities.
  • Preferred amino phosphonate chelant to be used herein is diethylene triamine penta methylene phosphonate. Such phosphonate chelant is commercially available from Monsanto under the trade name DEQUEST®.
  • Chelants can be incorporated in the compositions herein in amounts ranging from 0.0% to 10.0% by weight of the total composition, preferably 0.1 % to 5.0%.
  • compositions were made by mixing the listed ingredients in the listed proportions. All proportions are % by weight of the total composition. These compositions were used neat and diluted to clean hard-surfaces like floors. Excellent cleaning performance and excellent gloss were delivered to the surfaces cleaned.
  • Compositions (weight%) 1 2 3 C7/C9/C11 EO6.5 3.0 3.0 3.0 C12/C13 EO3 1.0 1.0 1.0 C13/C15 EO3O 2.0 2.0 2.0 Palm Kernal Fatty Acid 0.4 0.4 0.4 Perfume 0.45 0.45 0.45 Sokolan® CP5 1.0 0 0 Carboxymethyl cellulose 0 1.0 0 Primal® B 924 0 0 1.0 CaCl2.2H2O 1.0 1.0 1.0 Water and minors --------up to 100%-------- pH 10.5 10.5 10.5 10.5
  • the molar ratio of said carboxylate-containing polymer to calcium ions in examples 1 to 3 is from 2.1:1 to 1.2:1.
  • the molar ratio of said carboxylate-containing polymer to said divalent ions in examples 5 and 8 is from 4.2: 1 to 2.4:1, in examples 6 and 7 is from 2.1:1 to 1.2:1, in example 9 is from 6.3:1 to 3.6:1, in example 10 is from 1.1:1 to 1:1.7, and from 3.5:1 to 2.1:1 in example 11.

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Claims (11)

  1. Verfahren zum Reinigen einer harten Oberfläche, bei dem eine flüssige Zusammensetzung mit einem pH von 6 bis 13 umfassend ein carboxylathaltiges Polymer und ein zweiwertiges Gegenion, welches in Form eines Nichtkomplex-SaIzes oder als ein Bestandteil mit dem carboxylathaltigen Polymer zugesetzt ist, in einem Molverhältnis von Polymer zu zweiwertigem Gegenion von 12 : 1 bis 1 : 32, und 0,1 bis 50 Gew.-% der gesamten Zusammensetzung eines Tensids, auf die Oberfläche aufgebracht wird. wobei das carboxylathaltige Polymer ein Cellulosederivat, ein Polyacrylat, ein Acrylsäure-/Maleinsäure-basiertes Copolymer oder eine Mischung hiervon ist.
  2. Verfahren zum Reinigen einer harten Oberfläche nach Anspruch 1, wobei die Zusammensetzung auf die Oberfläche aufgebracht wird, nachdem sie mit Wasser verdünnt worden ist.
  3. Verfahren nach Anspruch 2, wobei die Oberfläche nicht gespült wird, nachdem die Zusammensetzung aufgebracht worden ist.
  4. Flüssige Reinigungsmittelzusammensetzung für harte Oberflächen mit einem pH von 6 bis 13 umfassend ein carboxylathaltiges Polymer und ein zweiwertiges Gegenion, das in Form eines Nichtkomplex-Salzes oder als ein Bestandteil mit dem carboxylathaltigen Polymer zugesetzt ist, in einem Molverhältnis von Polymer zu zweiwertigem Gegenion von 12 : 1 bis 1 : 32. und 0.1 bis 50 Gew.-% der gesamten Zusammensetzung eines Tensids, wobei das carboxylathaltige Polymer ein Cellulosederivat, ein Polyacrylat, ein Acrylsäure-/Maleinsäure-basiertes Copolymer oder eine Mischung hiervon ist, wobei die Zusammensetzung frei ist an einem proteolytischen oder amylolytischen Enzym und an Polyhydroxyfettsäureamid.
  5. Zusammensetzung oder Verfahren nach mindestens einem der vorangehenden Ansprüche, wobei die Zusammensetzung eine wäßrige flüssige Zusammensetzung mit einem pH von 6,5 bis 12, und vorzugsweise 7 bis 11, ist.
  6. Zusammensetzung oder Verfahren nach mindestens einem der vorangehenden Ansprüche, wobei das carboxylathaltige Polymer Carboxymethylcellulose oder ein Polymer auf Acrylsäurebasis mit einem Durchschnittsmolekulargewicht in seiner Säureform von vorzugsweise 2000 bis 1000000. oder ein Copolymer auf Acryl-/Maleinsäurebasis. worin das Verhältnis von Acrylat- zu Maleat-Monomeren im Bereich von 30 : 1 bis 1 : 1 liegt, mit einem Durchschnittsmolekulargewicht von vorzugsweise 2000 bis 100000, oder Mischungen hiervon sind.
  7. Zusammensetzung oder Verfahren nach mindestens einem der vorangehenden Ansprüche, wobei das zweiwertige Gegenion ein Salz von Calcium, Zink, Cadmium, Nickel, Kupfer, Cobalt, Zirkon, Chrom, Magnesium oder Mischungen hiervon, und vorzugsweise Calciumchlorid und/oder Magnesiumsulfat und/oder Zinkchlorid ist.
  8. Zusammensetzung oder Verfahren nach mindestens einem der vorangehenden Ansprüche, wobei das Polymer und das zweiwertige Gegenion in einem Molverhältnis von Polymer zu zweiwertigem Gegenion von 8 : 1 bis 1 : 16, vorzugsweise 6 : 1 bis 1 : 12 und weiter vorzugsweise 4 : 1 bis 1 : 6, vorliegen.
  9. Zusammensetzung oder Verfahren nach mindestens einem der vorangehenden Ansprüche. wobei die Zusammensetzung weiterhin einen wahlweisen Bestandteil umfaßt, gewählt aus der Gruppe der Parfüme, Komplexbildner. Bullder, Lösungsmittel, Puffer, Bakterizide, Hydrotrope, Färbemittel oder Mischungen hiervon.
  10. Zusammensetzung oder Verfahren nach mindestens einem der vorangehenden Ansprüche, wobei das Tensid gewählt ist aus der Gruppe der nichtionischen Tenside, anionischen Tenside, zwitterionischen Tenside, amphoteren Tenside, kationischen Tenside und Mischungen hiervon, und vorzugsweise ein nichtionisches Tensid oder Mischungen hiervon sind.
  11. Zusammensetzung oder Verfahren nach mindestens einem der vorangehenden Ansprüche, wobei die Zusammensetzung 0.1% bis 20% der gesamten Zusammensetzung des Tensids oder Mischungen hiervon, und vorzugsweise 1% bis 10%, umfaßt.
EP95944437A 1995-12-29 1995-12-29 Reinigungsmittel für harte oberflächen Expired - Lifetime EP0876458B2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN95198022.XA CN1209831A (zh) 1995-12-29 1995-12-29 硬表面清洗组合物
PCT/US1995/017044 WO1997024425A1 (en) 1995-12-29 1995-12-29 Hard-surface cleaning compositions
CA002241815A CA2241815C (en) 1995-12-29 1995-12-29 Hard-surface cleaning compositions

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EP0876458A1 EP0876458A1 (de) 1998-11-11
EP0876458B1 EP0876458B1 (de) 2000-08-09
EP0876458B2 true EP0876458B2 (de) 2004-12-08

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EP95944437A Expired - Lifetime EP0876458B2 (de) 1995-12-29 1995-12-29 Reinigungsmittel für harte oberflächen

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EP (1) EP0876458B2 (de)
JP (1) JPH11501978A (de)
CN (1) CN1209831A (de)
AU (1) AU4648696A (de)
CA (1) CA2241815C (de)
CZ (1) CZ9802014A3 (de)
DE (1) DE69518339T3 (de)
ES (1) ES2148594T5 (de)
GR (1) GR3034496T3 (de)
HU (1) HUT78046A (de)
IL (1) IL119847A (de)
PT (1) PT876458E (de)
WO (1) WO1997024425A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002036725A1 (en) * 2000-11-02 2002-05-10 Unilever N.V. Composition for cleaning hard surfaces
JP5260210B2 (ja) * 2008-09-24 2013-08-14 花王株式会社 床用つや出し洗浄剤組成物
TWI616175B (zh) * 2012-06-11 2018-03-01 花王股份有限公司 硬質表面用濕潤薄片
CN109504550B (zh) * 2018-11-26 2020-12-01 湖北华工图像技术开发有限公司 一种激光全息模压版清洗剂
CN114940775B (zh) * 2022-06-30 2023-05-26 广州工程技术职业学院 丙烯酸盐聚合物材料的修复方法

Citations (4)

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Publication number Priority date Publication date Assignee Title
NL7404969A (de) † 1973-04-13 1974-10-15
NL7505881A (nl) † 1974-05-21 1975-11-25 Procter & Gamble Europ Werkwijze voor het bereiden van een uitpoetsbaar glans- en reinigingspreparaat.
EP0125711A1 (de) † 1983-04-19 1984-11-21 Unilever N.V. Allzweckreiniger-Zusammensetzung
JPH04332798A (ja) † 1991-05-07 1992-11-19 Kao Corp 酸性硬表面用洗浄剤組成物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU71478A1 (de) * 1974-12-13 1976-11-11
CA2143328A1 (en) * 1992-09-01 1994-03-17 Kofi Ofosu-Asante Liquid or gel dishwashing detergent containing alkyl ethoxy carboxylate, divalent ions and alkylpolyethoxypolycarboxylate
US5486307A (en) * 1993-11-22 1996-01-23 Colgate-Palmolive Co. Liquid cleaning compositions with grease release agent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7404969A (de) † 1973-04-13 1974-10-15
NL7505881A (nl) † 1974-05-21 1975-11-25 Procter & Gamble Europ Werkwijze voor het bereiden van een uitpoetsbaar glans- en reinigingspreparaat.
EP0125711A1 (de) † 1983-04-19 1984-11-21 Unilever N.V. Allzweckreiniger-Zusammensetzung
JPH04332798A (ja) † 1991-05-07 1992-11-19 Kao Corp 酸性硬表面用洗浄剤組成物

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IL119847A0 (en) 1997-03-18
DE69518339T3 (de) 2005-08-11
IL119847A (en) 2000-02-29
DE69518339T2 (de) 2001-03-29
EP0876458A1 (de) 1998-11-11
WO1997024425A1 (en) 1997-07-10
JPH11501978A (ja) 1999-02-16
ES2148594T5 (es) 2005-07-01
DE69518339D1 (de) 2000-09-14
PT876458E (pt) 2000-12-29
EP0876458B1 (de) 2000-08-09
AU4648696A (en) 1997-07-28
CA2241815C (en) 2003-05-27
HUT78046A (hu) 1999-07-28
GR3034496T3 (en) 2000-12-29
CA2241815A1 (en) 1997-07-10
CN1209831A (zh) 1999-03-03
ES2148594T3 (es) 2000-10-16
CZ9802014A3 (cs) 1998-11-11

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