EP0595383B1 - Flüssige Reinigungszusammensetzungen für harte Oberflächen mit einem kurzkettigen Amphocarboxylat-Waschmittel-Tensid - Google Patents

Flüssige Reinigungszusammensetzungen für harte Oberflächen mit einem kurzkettigen Amphocarboxylat-Waschmittel-Tensid Download PDF

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EP0595383B1
EP0595383B1 EP93202758A EP93202758A EP0595383B1 EP 0595383 B1 EP0595383 B1 EP 0595383B1 EP 93202758 A EP93202758 A EP 93202758A EP 93202758 A EP93202758 A EP 93202758A EP 0595383 B1 EP0595383 B1 EP 0595383B1
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group
detergent
composition
carbon atoms
alkyl
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French (fr)
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EP0595383A1 (de
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Ronald Anthony Masters
Michael Stephen Maile
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Procter and Gamble Co
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Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/92—Sulfobetaines ; Sulfitobetaines
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents

Definitions

  • This invention pertains to liquid detergent compositions for use in cleaning hard surfaces.
  • Such compositions typically contain detergent surfactants, solvents, builders, etc.
  • liquid detergent compositions for hard surfaces such as metal, glass, ceramic, plastic and linoleum surfaces, are commercially available in both powdered and liquid form.
  • Liquid detergent compositions are disclosed in Australian Pat. Application 82/88168, filed Sept. 9, 1982, by The Procter & Gamble Company; U.K. Pat. Application GB 2,166,153A, filed Oct. 24, 1985, by The Procter & Gamble Company; and U.K. Pat. Application GB 2,160,887A, filed June 19, 1985, by Bristol-Myers Company, all of said published applications being incorporated herein by reference.
  • These liquid detergent compositions comprise certain organic solvents, surfactant, and optional builder and/or abrasive.
  • Liquid cleaning compositions have the great advantage that they can be applied to hard surfaces in neat or concentrated form so that a relatively high level of surfactant material and organic solvent is delivered directly to the soil. Therefore, liquid cleaning compositions have the potential to provide superior soap scum, grease, and oily soil removal over dilute wash solutions prepared from powdered cleaning compositions.
  • liquid cleaning compositions and especially compositions prepared for cleaning glass, need good filming/streaking properties.
  • they can suffer problems of product form, in particular, inhomogeneity, lack of clarity, or excessive "solvent" odor for consumer use.
  • An object of the present invention is to provide detergent compositions which provide good general, including glass, cleaning without excessive filming and/or streaking.
  • the present invention relates to an aqueous, liquid, hard surface detergent composition having good filming/streaking characteristics
  • an aqueous, liquid, hard surface detergent composition having good filming/streaking characteristics
  • compositions preferably does not contain amounts of materials, like conventional detergent builders, etc., that deposit on the surface being cleaned and cause unacceptable filming/streaking.
  • the compositions can be formulated at usage concentrations, or as concentrates, and can be packaged in a container having means for creating a spray to make application to hard surfaces more convenient.
  • superior aqueous liquid detergent compositions for cleaning shiny surfaces such as glass contain C 7-10 "amphocarboxylate" detergent surfactant, typically at a pH of at least 9.5, preferably at least about 10; a hydrophobic, volatile, cleaning solvent; and, optionally, other detergent surfactant with good filming/streaking characteristics like zwitterionic detergent surfactant, and, also optionally, monoethanolamine and/or certain beta-aminoalkanol compounds, and/or volatile hydrophobic solvent.
  • C 7-10 "amphocarboxylate" detergent surfactant typically at a pH of at least 9.5, preferably at least about 10
  • a hydrophobic, volatile, cleaning solvent and, optionally, other detergent surfactant with good filming/streaking characteristics like zwitterionic detergent surfactant, and, also optionally, monoethanolamine and/or certain beta-aminoalkanol compounds, and/or volatile hydrophobic solvent.
  • aqueous, liquid hard surface detergent compositions herein contain from 0.001% to 1%, preferably from about 0.01% to about 0.5%, more preferably from about 0.02% to about 0.2%, and even more preferably from about 0.03% to about 0.08%, of C 7-10 short chain amphocarboxylate detergent surfactant. It has been found that these amphocarboxylate, and, especially glycinate, detergent surfactants provide good cleaning with superior filming/streaking for detergent compositions that are used to clean both glass and/or relatively hard-to-remove soils.
  • the detergency is good and the short chains provide improved filming/streaking, even as compared to the optional, but preferred, zwitterionic detergent cosurfactants described hereinafter.
  • the short chains provide improved filming/streaking, even as compared to the optional, but preferred, zwitterionic detergent cosurfactants described hereinafter.
  • amphocarboxylate detergent surfactants herein preferably have the generic formula: RN(R 1 )(CH 2 ) n N(R 2 )(CH 2 ) p C(O)OM wherein R is a C 7-10 hydrophobic moiety, typically a fatty acyl moiety containing from 8 to 10 carbon atoms which, in combination with the nitrogen atom forms an amido group, R 1 is hydrogen (preferably) or a C 1-2 alkyl group, R 2 is a C 1-2 alkyl or, preferably, hydroxy ethyl, each n is an integer from 1 to 3, each p is an integer from 1 to 2, preferably 1, and each M is a water-soluble cation, typically an alkali metal, ammonium, and/or alkanolammonium cation.
  • Such detergent surfactants are available, for example, from Sherex under the trade name Rewoteric AM-V, having the formula: C 7 C(O)NH(CH 2 ) 2 N(CH 2 CH 2 OH)CH 2 C(O)O (-) Na (+) and Mona Industries, under the trade name Monateric 1000, having the formula: C 7 C(O)NH(CH 2 ) 2 N(CH 2 CH 2 OH)CH 2 CH 2 C(O)O (-) Na (+)
  • Suitable optional zwitterionic detergent surfactants contain a cationic group, preferably a quaternary ammonium group, and an anionic group, preferably carboxylate, sulfate and/or sulfonate group, more preferably sulfonate.
  • Successively more preferred ratios of amphocarboxylate detergent surfactant to zwitterionic detergent cosurfactant are from 10:1 to 1:10; preferably from 3:1 to 1:3, more preferably about 1:1.
  • Zwitterionic detergent surfactants as mentioned hereinbefore, contain both a cationic group and an anionic group and are in substantial electrical neutrality where the number of anionic charges and cationic charges on the detergent surfactant molecule are substantially the same.
  • Zwitterionic detergents which typically contain both a quaternary ammonium group and an anionic group selected from sulfonate and carboxylate groups are desirable since they maintain their amphoteric character over most of the pH range of interest for cleaning hard surfaces.
  • the sulfonate group is the preferred anionic group.
  • Preferred zwitterionic detergent surfactants have the generic formula: R 3 -[C(O)-N(R 4 )-(CR 5 2 ) n ] m N(R 6 ) 2 (+) -(CR 5 2 ) p -Y (-) wherein each y is preferably a carboxylate (COO - ) or sulfonate (SO 3 - ) group, preferably sulfonate; wherein each R 3 is a hydrocarbon, e.g., an alkyl, or alkylene, group containing from 8 to 20, preferably from 10 to 18, more preferably from about 12 to about 16 carbon atoms; wherein each (R 4 ) is either hydrogen, or a short chain alkyl, or substituted (e.g., hydroxy) alkyl, containing from one to about four carbon atoms, preferably groups selected from the group consisting of methyl, ethyl, propyl, hydroxy substituted ethyl or propyl
  • the R 3 groups can be branched and/or unsaturated, and such structures can provide filming/streaking benefits, even when used as part of a mixture with straight chain alkyl R 3 groups.
  • the R 4 groups can also be connected to form ring structures.
  • hydrocarbylamidoalkylene betaines and, especially, hydrocarbylamidoalkylene sulfobetaines are excellent for use in hard surface cleaning detergent compositions, especially those formulated for use on both glass and hard-to-remove soils. They are even better when used with monoethanolamine and/or specific beta-aminoalkanol as disclosed herein.
  • a more preferred specific detergent surfactant is a C 10-14 fatty acylamidopropylene(hydroxypropylene)sulfobetaine, e.g., the detergent surfactant available from the Sherex Company as a 40% active product under the trade name "Rewoteric CAS Sulfobetaine.”
  • the level of optional zwitterionic detergent cosurfactant, e.g., HASB, in the composition is typically from 0.001% to 0.5%, preferably from about 0.02% to about 0.2%, more preferably from about 0.02% to about 0.15%, and even more preferably from about 0.03% to about 0.08%.
  • the level in the composition is dependent on the level of amphocarboxylate detergent surfactant; the eventual level of dilution to make the wash solution, etc.
  • zwitterionic detergent surfactants are set forth at Col. 4 of U.S. Pat. No. 4,287,080, Siklosi, incorporated herein by reference. Another detailed listing of suitable zwitterionic detergent surfactants for the detergent compositions herein can be found in U.S. Pat. No. 4,557,853, Collins, issued Dec. 10, 1985, incorporated by reference herein. Commercial sources of such surfactants can be found in McCutcheon's EMULSIFIERS AND DETERGENTS, North American Edition, 1984, McCutcheon Division, MC Publishing Company, also incorporated herein by reference.
  • detergent surfactants e.g., anionic, and nonionic detergent surfactants
  • anionic, and nonionic detergent surfactants that can also be used in small amounts in the composition of this invention as cosurfactants.
  • these are the alkyl- and alkylethoxylate- (polyethoxylate) sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, alpha-sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known from the detergency art.
  • detergent surfactants like the amphocarboxylate, that are amphoteric at a lower pH are desirable detergent cosurfactants.
  • detergent surfactants which are C 12 -C 18 acylamido alkylene amino alkylene sulfonates, e.g., compounds having the formula: R-C(O)-NH-(C 2 H 4 )-N(C 2 H 4 OH)CH 2 CH(OH)CH 2 SO 3 M wherein R is an alkyl group containing from about 9 to about 18 carbon atoms and M is a compatible cation are desirable cosurfactants.
  • These detergent surfactants are available as Miranol CS, OS, JS, etc.
  • the CTFA adopted name for such surfactants is cocoamphohydroxypropyl sulfonate. It is preferred that the compositions be substantially free of alkyl naphthalene sulfonates.
  • optional detergent surfactants useful herein contain a hydrophobic group, typically containing an alkyl group in the C 8 -C 18 range, and, optionally, one or more linking groups such as ether or amido, preferably amido groups.
  • the anionic detergent surfactants can be used in the form of their sodium, potassium or alkanolammonium, e.g., triethanolammonium salts; the nonionics generally contain from about 5 to about 17 ethylene oxide groups.
  • C 12 -C 18 paraffin-sulfonates and alkyl sulfates, and the ethoxylated alcohols and alkyl phenols are especially preferred in the compositions of the present type.
  • Suitable surfactants for use in such cleaners are one or more of the following: sodium linear C 8 -C 18 alkyl benzene sulfonate (LAS), particularly C 11 -C 12 LAS; the sodium salt of a coconut alkyl ether sulfate containing 3 moles of ethylene oxide; the adduct of a random secondary alcohol having a range of alkyl chain lengths of from 11 to 15 carbon atoms and an average of 2 to 10 ethylene oxide moieties, several commercially available examples of which are Tergitol 15-S-3, Tergitol 15-S-5, Tergitol 15-S-7, and Tergitol 15-S-9, all available from Union Carbide Corporation; the sodium and potassium salts of coconut fatty acids (coconut soaps); the condensation product of a straight-chain primary alcohol containing from about 8 carbons to about 16 carbon atoms and having an average carbon chain length of from about 10 to about 12 carbon atoms with from about 4 to about 8 moles of ethylene oxide per
  • the fluorocarbon surfactants examples of which are FC-129, a potassium fluorinated alkylcarboxylate, and FC-170-C, a mixture of fluorinated alkyl polyoxyethylene ethanols, both available from 3M Corporation, as well as the Zonyl fluorosurfactants, available from DuPont Corporation, can be used in small amounts. It is understood that mixtures of various surfactants can be used.
  • the composition when used full strength, or wash solution containing the composition, should contain from about 0.01% to about 1%, preferably from about 0.02% to about 0.5%, more preferably from about 0.05% to about 0.25%, of total detergent surfactant.
  • the level can, and should be, higher, typically from about 0.1% to about 10%, preferably from about 0.15% to about 2%.
  • Concentrated products will typically contain from about 0.2% to about 10%, preferably from about 0.3% to about 5%.
  • a hydrophobic, volatile, cleaning solvent i.e., one that has substantial cleaning activity, in addition to the detergent surfactant.
  • the solvents employed in the hard surface cleaning compositions herein are selected from the well-known "degreasing" solvents commonly used in, for example, the dry cleaning industry, in the hard surface cleaner industry and the metalworking industry.
  • a useful definition of such solvents can be derived from the solubility parameters as set forth in "The Hoy,” a publication of Union Carbide, incorporated herein by reference.
  • hydrogen bonding parameters are preferably less than about 7.7, more preferably from about 2 to about 7, and even more preferably from about 3 to about 6. Solvents with lower numbers become increasingly difficult to solubilize in the compositions and have a greater tendency to cause a haze on glass. Higher numbers require more solvent to provide good greasy/oily soil cleaning.
  • Cleaning solvents are typically used at a level of from 1% to 30%, preferably from about 2% to about 15%, more preferably from about 2% to about 8%.
  • Dilute compositions for use full strength typically have solvents at a level of from about 1% to about 5%, preferably from about 2% to about 3.5%.
  • Concentrated compositions contain from about 10% to about 30%, preferably from about 10% to about 20% of solvent.
  • solvents comprise hydrocarbon or halogenated hydrocarbon moieties of the alkyl or cycloalkyl type, and have a boiling point well above room temperature, i.e., above about 20°C.
  • Preferred volatile solvents have boiling points of less than about 205°C and/or vapor pressure at 25°C of at least about 0.1 mm Hg.
  • compositions of the present type will be guided in the selection of solvent partly by the need to provide good grease-cutting properties, and partly by aesthetic considerations and avoidance of filming/streaking.
  • the preferred glycol ethers useful herein have the formula R 6 O( ⁇ R 7 O) ⁇ m H wherein each R 6 is an alkyl group which contains from 1 to 8 carbon atoms, each R 7 is either ethylene or propylene, and m is a number from 1 to about 3.
  • the most preferred glycol ethers are selected from the group consisting of monopropyleneglycolmonopropyl ether, dipropyleneglycolether, monopropyleneglycolmonobutyl ether, diethyleneglycolmonohexyl ether, monoethyleneglycolmonohexyl ether, monoethyleneglycolmonobutyl ether, and mixtures thereof.
  • Any butoxy-propanol solvent should have no more than about 20%, preferably no more than about 10%, more preferably no more than about 7%, of the secondary isomer in which the butoxy group is attached to the secondary atom of the propanol for improved odor.
  • Monoethanolamine and/or C 3-6 beta-aminoalkanol compounds serve primarily as solvents when the pH is above 10.0, and especially above 10.7. They also provide alkaline buffering capacity during use. However, the most unique contribution they make is to improve the filming/streaking properties of hard surface cleaning compositions containing the optional zwitterionic detergent cosurfactant, whereas they do not provide any substantial improvement in filming/streaking when used with the optional conventional anionic or ethoxylated nonionic detergent cosurfactants. When perfumes that have a high percentage of terpenes are incorporated, the benefit is usually greater for the beta-alkanolamines, and they are often preferred, whereas the monoethanolamine is usually preferred.
  • Monoethanolamine and/or C 3-6 beta-alkanolamine are used at a level of from 0.05% to 10%, preferably from about 0.2% to about 5%.
  • “dilute” compositions they are typically present at a level of from about 0.05% to about 2%, preferably from about 0.1% to about 1.0%, more preferably from about 0.2% to about 0.7%, and even more preferably from 0.3% to 0.6%.
  • concentrated compositions they are typically present at a level of from about 0.5% to about 10%, preferably from about 1% to about 5%.
  • Preferred beta-aminoalkanols have a primary hydroxy group.
  • Suitable beta-aminoalkanols have the formula: wherein each R is selected from the group consisting of hydrogen and alkyl groups containing from one to four carbon atoms and the total of carbon atoms in the compound is from three to six, preferably four.
  • the amine group is preferably not attached to a primary carbon atom. More preferably the amine group is attached to a tertiary carbon atom to minimize the reactivity of the amine group.
  • Specific preferred beta-aminoalkanols are 2-amino, 1-butanol; 2-amino,2-methylpropanol; and mixtures thereof.
  • the most preferred beta-aminoalkanol is 2-amino,2-methylpropanol since it has the lowest molecular weight of any beta-aminoalkanol which has the amine group attached to a tertiary carbon atom.
  • the beta-aminoalkanols preferably have boiling points below about 175°C. Preferably, the boiling point is within about 5°C of 165°C.
  • Such beta-aminoalkanols are excellent materials for hard surface cleaning in general and, in the present application, have certain desirable characteristics.
  • the beta-aminoalkanols are surprisingly better than, e.g., monoethanolamine for hard surface detergent compositions that contain perfume ingredients like terpenes and similar materials.
  • monoethanolamine normally is preferred for its effect in improving the filming/streaking performance of compositions containing zwitterionic detergent surfactant.
  • the improvement in filming/streaking of hard surfaces that is achieved by combining the monoethanolamine and/or beta-aminoalkanol was totally unexpected.
  • Beta-aminoalkanols can provide superior cleaning of hard-to-remove greasy soils and superior product stability, especially under high temperature conditions, when used in hard surface cleaning compositions, especially those containing more of the optional zwitterionic detergent surfactants.
  • Beta-aminoalkanols and especially the preferred 2-amino-2-methylpropanol, are surprisingly volatile from cleaned surfaces considering their relatively high molecular weights.
  • compositions can contain, in addition to the alkanolamines discussed herein, an additional alkaline buffer to help give a pH in the product, at least initially, in use of from 9.5 to 13, preferably from about 9.7 to about 12, more preferably from about 9.7 to about 11.5. pH is usually measured on the product.
  • the buffers that are present comprise monoethanolamine and/or beta-aminoalkanol and/or, optionally, but preferably, other alkaline material selected from the group consisting of: ammonia; other C 2 -C 4 alkanolamines; alkali metal hydroxides; silicates; borates; carbonates; and/or bicarbonates; and mixtures thereof.
  • Ammonia is a preferred alkaline material, especially when the alkanolamines are not present.
  • the preferred optional alkalinity materials are alkali metal hydroxides.
  • the level of such alkalinity source is from 0% to about 5%, preferably from 0% to about 0.5%.
  • the balance of the formula is typically water and non-aqueous polar solvents with only minimal cleaning action like methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, and mixtures thereof, preferably isopropanol.
  • the level of non-aqueous polar solvent is greater when more concentrated formulas are prepared.
  • the level of non-aqueous polar solvent is from 0.5% to 40%, preferably from about 1% to about 10%, more preferably from about 3% to about 8% (especially for "dilute" compositions) and the level of water is from 50% to 99%, preferably from about 75% to about 95%.
  • compositions herein can also contain other various adjuncts which are known to the art for detergent compositions. Preferably they are not used at levels that cause unacceptable filming/streaking.
  • Such adjuncts are:
  • An optional ingredient for harder general cleaning purposes is from 0% to about 30%, preferably from about 1% to about 15%, more preferably from about 1% to about 12%, of detergent builder.
  • a level of builder of from about 0.02% to about 0.5%, preferably from about 0.1% to about 0.2%, can be useful.
  • some examples of builders for use herein are sodium nitrilotriacetate, potassium pyrophosphate, potassium tripolyphosphate, sodium or potassium ethane-1-hydroxy-1,1-diphosphonate, and the non-phosphorous chelating agents described in U.S. Pat. No.
  • the levels of builder present in the wash solution used for glass should be less than about 0.5%, preferably less than about 0.2%. Therefore, dilution is highly preferred for cleaning glass, while full strength use is preferred for general purpose cleaning.
  • detergent builders such as sodium citrate, sodium ethylenediaminetetraacetate, etc.
  • Inclusion of a detergent builder improves cleaning, but harms spotting and filming and has to be considered as a compromise in favor of cleaning. Inclusion of a detergent builder is optional and low levels are usually more preferred than high levels.
  • perfumes Most hard surface cleaner products contain some perfume to provide an olfactory aesthetic benefit and to cover any "chemical" odor that the product may have.
  • perfume components in these perfumes can provide a fresh and clean impression to the surfaces, and it is sometimes desirable that these ingredients be deposited and present on the dry surface.
  • Perfume ingredients are readily solubilized in the compositions by the optional zwitterionic detergent surfactant. Other similar detergent surfactants will not solubilize as much perfume, especially substantive perfume, or maintain uniformity to the same low temperature.
  • perfume ingredients and compositions of this invention 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 Mar. 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, all of said patents being incorporated herein by reference. Normally, the art-recognized perfume compositions are not very substantive to minimize their effect on hard surfaces.
  • Perfumes can be classified according to their volatility, as mentioned hereinbefore.
  • the highly volatile, low boiling, perfume ingredients typically have boiling points of about 250°C or lower. Many of the more moderately volatile perfume ingredients are also lost substantially in the cleaning process.
  • the moderately volatile perfume ingredients are those having boiling points of from about 250°C to about 300°C.
  • the less volatile, high boiling, perfume ingredients referred to hereinbefore are those having boiling points of about 300°C or higher. A significant portion of even these high boiling perfume ingredients, considered to be substantive, is lost during the cleaning process, and it may be desirable to have means to retain more of these ingredients on the dry surfaces.
  • perfume ingredients 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, incorporated herein by reference.
  • Examples of the highly volatile, low boiling, perfume ingredients are: anethole, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl formate, iso-bornyl acetate, camphene, cis-citral (neral), citronellal, citronellol, citronellyl acetate, paracymene, decanal, dihydrolinalool, dihydromyrcenol, dimethyl phenyl carbinol, eucalyptol, 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, beta-caryophyllene, cedrene, cinnamic alcohol, coumarin, dimethyl benzyl carbinyl acetate, ethyl vanillin, eugenol, iso-eugenol, 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.
  • Cedarwood terpenes are
  • 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-cyclo-penta-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.
  • any particular perfume ingredient is primarily dictated by aesthetic considerations, but more water-soluble materials are preferred, as stated hereinbefore, since such materials are less likely to adversely affect the good filming/streaking properties of the compositions. If the terpene types of perfume ingredients are used, the beta-aminoalkanols are preferred for product stability.
  • compositions have exceptionally good cleaning properties. They can also be formulated either to be diluted or to have good "shine” properties, i.e., when used to clean glossy surfaces, without rinsing.
  • compositions can be formulated either to be diluted or to be used at full strength, where the product is sprayed onto the surface to be cleaned and then wiped off with a suitable material like cloth, a paper towel, etc.
  • the level of amphocarboxylate detergent surfactant (a) is disclosed herein.
  • the other ingredients are typically adjusted to complement the amphocarboxylate detergent surfactant.
  • the ratio of amphocarboxylate detergent surfactant (a) to any zwitterionic cosurfactant (c) is typically from 3:1 to 1:3; the ratio of total surfactant (a) + (c) to hydrophobic cleaning solvent (b) being from 1:10 to 1:40; and the ratio of total surfactant (a) + (c) to the monoethanolamine and/or beta-aminoalkanol (d) being from 1:1 to 1:7.
  • Concentrated formulas are typically from 2 to 4, preferably about 3 times more concentrated by volume. They can be packaged in a package that comprises a means for creating a spray, e.g., a pump, aerosol propellant and spray valve, etc.
  • a paper towel is folded into eighths. Two milliliters of test product are applied to the upper half of the folded paper towel. The wetted towel is applied in one motion with even pressure from top to bottom of a previously cleaned window or mirror. The window or mirror with the applied product(s) is allowed to dry for ten minutes before grading under stress lighting conditions by expert judges. After the initial grading, the residues are buffed with a dry paper towel using a single downward wipe and then regraded.

Claims (11)

  1. Wäßrige flüssige Detergenzzusammensetzung für harte Oberflächen mit verbesserten Eigenschaften hinsichtlich der Filmbildung/Streifenbildung, umfassend:
    (a) ein grenzflächenaktives Detergenzmittel der allgemeinen Formel:

            RN(R1(CH2)nN(R2)(CH2)pC(O)OM,

    worin R ein hydrophober C7-10-Rest ist, einschließlich eines Fettacylrestes mit 8 bis 10 Kohlenstoffatomen, welcher in Kombination mit dem Stickstoffatom eine Amidogruppe ausbildet, R1 Wasserstoff oder eine C1-2-Alkylgruppe darstellt, R2 ein C1-2-Alkyl oder Hydroxyethyl bedeutet, jedes n eine ganze Zahl von 1 bis 3 darstellt, jedes p eine ganze Zahl von 1 bis 2 ist und M ein wasserlösliches Kation bedeutet, welches vorzugsweise unter Alkalimetallkationen, Amnoniumkationen, Alkanolammoniumkationen und Gemischen hievon ausgewählt ist;
    (b) ein flüchtiges, hydrophobes, reinigendes Lösungsmittel;
    (c) fakultativ Monoethanolamin und/oder einen beta-Aminoalkanol mit 3 bis 6 Kohlenstoffatomen, vorzugsweise Monoethanolamin; und
    (d) als Rest ein wäßriges Lösungsmittelsystem und geringfügige Bestandteile.
  2. Zusammensetzung nach Anspruch 1, worin (a) in einer Menge von 0,001% bis 1% vorliegt.
  3. Zusammensetzung nach Anspruch 1 oder Anspruch 2, welche zusätzlich als co-grenzflächenaktives Detergenzmittel 0,02% bis 0,2% von einem Hydrocarbylamidoalkylensulfobetain der Formel:

            R3-C(O)-N(R4)-(CR5 2)n-N(R6)2 (+) -(CR5 2)p-SO3 (-)

    umfaßt, worin jeder Rest R3 eine Alkyl- oder Alkylengruppe mit 10 bis 18 Kohlenstoffatomen darstellt, jeder Rest (R4) und jeder Rest (R6) von der aus Wasserstoff, Methyl, Ethyl, Propyl, Hydroxy substituiertem Ethyl oder Propyl bestehenden Gruppe und Gemischen hievon ausgewählt ist, jeder Rest (R5) von der aus Wasserstoff und Hydroxygruppen bestehenden Gruppe ausgewählt ist und jedes n und jedes p eine Zahl von 1 bis 4 darstellt; wobei in jedem beliebigen (CR5 2)-Rest nicht mehr als eine Hydroxygruppe vorliegt.
  4. Zusammensetzung nach Anspruch 1 oder Anspruch 2, welche zusätzlich ein grenzflächenaktives Detergenzmittel in Form von 0,001% bis 2% Hydrocarbylamidoalkylenbetain der Formel

            R3-C(O)-N(R4)-(CR5 2)n-N(R6)2 (+)-(CR5 2)p-COO(-)

    umfaßt, worin jeder Rest R3 eine Alkyl- oder Alkylengruppe mit 10 bis 18 Kohlenstoffatomen darstellt, jeder Rest (R4) und jeder Rest (R6) von der aus Wasserstoff, Methyl, Ethyl, Propyl, Hydroxy substituiertem Ethyl oder Propyl bestehenden Gruppe und Gemischen hievon ausgewählt ist, jeder Rest (R5) von der aus Wasserstoff und Hydroxygruppen bestehenden Gruppe ausgewählt ist und jedes n und jedes p eine Zahl von 1 bis 4 darstellt; wobei in jedem beliebigen (CR5 2)-Rest nicht mehr als eine Hydroxygruppe vorliegt.
  5. Zusammensetzung nach Anspruch 3 oder Anspruch 4, worin das Verhältnis von dem genannten grenzflächenaktiven Mittel (a) zu dem genannten co-grenzflächenaktiven Detergenzmittel von 3:1 bis 1:3, vorzugsweise von 2:1 bis 1:2, stärker bevorzugt 1:1 beträgt.
  6. Zusammensetzung nach einem der Ansprüche 1 bis 5, worin die Menge an reinigendem Lösungsmittel (b) von 1% bis 30%, vorzugsweise von 2% bis 15% beträgt
  7. Zusammensetzung nach einem der Ansprüche 1 bis 6, worin das reinigende Lösungsmittel (b) ein Glykolether der Formel R6O(̵R7O)̵mH ist, worin jeder Rest R6 eine Alkylgruppe mit 1 bis 8 Kohlenstotfatomen darstellt, jeder Rest R7 entweder Ethylen oder Propylen bedeutet und m eine Zahl von 1 bis 3 ist, welcher vorzugsweise von der aus Monopropylenglykolmonopropylether, Dipropylenglykolmonobutylether, Monopropylenglykolmonobutylether, Diethylenglykolmonohexylether, Monoethylenglykolmonohexylether, Monoethylenglykolmonobutylether bestehenden Gruppe und Gemischen hievon ausgewahlt ist, stärker bevorzugt Monopropylenglykolmonobutylether ist.
  8. Zusammensetzung nach einem der Ansprüche 1 bis 7, worin n 2 ist und p 1 beträgt.
  9. Zusammensetzung nach einem der Ansprüche 1 bis 8, welche einen pH-Wert von 9,5 bis 13, vorzugsweise von etwa 9,7 bis etwa 12 aufweist.
  10. wäßrige flüssige Detergenzzusammensetzung für harte Oberflächen mit verbesserten Eigenschaften hinsichtlich der Filmbildung/Streifenbildung, umfassend:
    (a) 0,03% bis 0,08% von einem grenzflächenaktiven Detergenzmittel der allgemeinen Formel:

            RN(R1)(CH2)nN(R2)CH2C(O)OM,

    worin R ein hydrophober C7-10-Rest ist, einschließlich eines Fettacylrestes mit 8 bis 10 Kohlenstoffatomen, welcher in Kombination mit dem Stickstoffatom eine Amidogruppe ausbildet, R1 Wasserstoff oder eine C1-2-Alkylgruppe darstellt, jedes n eine ganze Zahl von 1 bis 3 darstellt, R2 ein C1-2-Alkyl oder Hydroxyethyl bedeutet und M ein wasserlösliches Kation darstellt, welches unter Alkalimetallkationen, Anmoniumkationen, Alkanolanmoniumkationen und Gemischen hievon ausgewählt ist;
    (b) 2% bis 3,5% Monopropylenglykolmonobutylether;
    (c) als ein co-grenzflächenaktives Detergenzmittel 0,03% bis 0,08% an Hydrocarbylamidoalkylensulfobetain der Formel:

            R3-C(O)-N(R4)-(CR5 2)n-N(R6)2 (+)-(CR5 2)p-SO3 (-),

    worin jeder Rest R3 eine Alkyl- oder Alkylengruppe mit 10 bis 18 Kohlenstoffatomen darstellt, jeder Rest (R4) und jeder Rest (R6) von der aus Wasserstoff, Methyl, Ethyl, Propyl, Hydroxy substituiertem Ethyl oder Propyl bestehenden Gruppe und Gemischen hievon ausgewählt ist, jeder Rest (R5) von der aus Wasserstoff und Hydroxygruppen bestehenden Gruppe ausgewählt ist und jedes n und jedes p eine Zahl von 1 bis 4 darstellt; wobei in jedem beliebigen (CR5 2)-Rest nicht mehr als eine Hydroxygruppe vorliegt.
    (d) 0,3% bis 0,6% Monoethanolamin und/oder einen beta-Aminoalkanol mit 3 bis 6 Kohlenstoffatomen; und
    (e) als Rest ein wäßriges Lösungsmittelsystem, das vorzugsweise 3% bis 8% Isopropanol umfaßt, und geringfügige Bestandteile.
  11. Konzentrierte Zusammensetzung, welche bei Verdünnung mit Wasser die Zusammensetzung nach einem der Ansprüche 1 bis 10 liefern wird, wobei der Volumsvergrößerung mindestens 2:1, vorzugsweise mindestens 3:1 beträgt.
EP93202758A 1992-10-26 1993-09-24 Flüssige Reinigungszusammensetzungen für harte Oberflächen mit einem kurzkettigen Amphocarboxylat-Waschmittel-Tensid Expired - Lifetime EP0595383B1 (de)

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US966207 1992-10-26

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EP0595383B1 true EP0595383B1 (de) 1997-03-12

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US5523024A (en) * 1992-02-07 1996-06-04 The Clorox Company Reduced residue hard surface cleaner
US5585342A (en) * 1995-03-24 1996-12-17 The Clorox Company Reduced residue hard surface cleaner
US5817615A (en) * 1992-02-07 1998-10-06 The Clorox Company Reduced residue hard surface cleaner
US5531933A (en) * 1993-12-30 1996-07-02 The Procter & Gamble Company Liquid hard surface detergent compositions containing specific polycarboxylate detergent builders
AU675833B2 (en) * 1994-03-23 1997-02-20 Amway Corporation Concentrated all-purpose light duty liquid cleaning composition and method of use
JPH10501286A (ja) * 1994-06-09 1998-02-03 エス．シー．ジョンソン アンド サン，インコーポレーテッド 向上したくもり止め性を有するガラスクリーナー
US5534198A (en) * 1994-08-02 1996-07-09 The Procter & Gamble Company Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity
US5547476A (en) * 1995-03-30 1996-08-20 The Procter & Gamble Company Dry cleaning process
US5632780A (en) * 1995-03-30 1997-05-27 The Procter & Gamble Company Dry cleaning and spot removal proces
DK0823937T3 (da) * 1995-05-05 1999-12-27 Procter & Gamble Glasrensningssammensætninger med lineært alkylsulfatoverfladeaktive midler
DE69734427T2 (de) 1996-02-14 2006-07-20 Stepan Co., Northfield Hydrotrop enthaltende reiniger für harte oberflächen mit verminderter rückstandsbildung
US5726139A (en) * 1996-03-14 1998-03-10 The Procter & Gamble Company Glass cleaner compositions having good filming/streaking characteristics containing amine oxide polymers functionality
GB2335661A (en) * 1998-03-26 1999-09-29 Reckitt & Colman Inc Hard surface cleaners comprising amphoteric surfactant
AU5343199A (en) * 1999-08-09 2001-03-05 Rhodia Inc. Process for making salt-free amphoterics with high mono amphopropionate content
JP2003003197A (ja) 2001-01-05 2003-01-08 Procter & Gamble Co:The アミンオキシドモノマー単位含有高分子石鹸泡増進剤を使用する組成物および方法
JP4825516B2 (ja) * 2005-12-27 2011-11-30 花王株式会社 洗浄剤組成物

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DE3270670D1 (en) * 1981-11-12 1986-05-22 Procter & Gamble Liquid detergent compositions
AU659994B2 (en) * 1990-01-29 1995-06-08 Procter & Gamble Company, The Liquid hard surface detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol
US5252245A (en) * 1992-02-07 1993-10-12 The Clorox Company Reduced residue hard surface cleaner

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DE69308726T2 (de) 1997-10-30
GR3023697T3 (en) 1997-09-30
DE69308726D1 (de) 1997-04-17
CA2109188A1 (en) 1994-04-27
CA2109188C (en) 1997-12-23
ATE150077T1 (de) 1997-03-15
MX9306633A (es) 1994-06-30
DK0595383T3 (da) 1997-05-05
ES2100444T3 (es) 1997-06-16
JPH06228590A (ja) 1994-08-16

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