EP0823937B1 - Compositions de nettoyage du verre comportant des agents tensioactifs lineaires sulfates d'alkyle - Google Patents

Compositions de nettoyage du verre comportant des agents tensioactifs lineaires sulfates d'alkyle Download PDF

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EP0823937B1
EP0823937B1 EP96913006A EP96913006A EP0823937B1 EP 0823937 B1 EP0823937 B1 EP 0823937B1 EP 96913006 A EP96913006 A EP 96913006A EP 96913006 A EP96913006 A EP 96913006A EP 0823937 B1 EP0823937 B1 EP 0823937B1
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composition
weight
surfactant
detergent
surfactants
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EP0823937A1 (fr
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Ronald Anthony Masters
Charles Albert Hensley
Lori Boden Mitchell
Michael Stephen Maile
Nicola John Policicchio
Todd Christian Severson
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds

Definitions

  • This invention pertains to glass cleaning compositions, preferably clear liquid detergent compositions, for use in cleaning glass and, preferably, other hard surfaces.
  • liquid cleaning compositions especially compositions prepared for cleaning glass, that impart a smooth "gliding" feel, based on good surface lubricity, as the cleaning implement wipes and dries.
  • water-sheeting and anti-spotting benefits are preferred in glass cleaning compositions. These water-sheeting and anti-spotting benefits are typically achieved by providing a composition which leaves behind a hydrophilic residue. Waxes and silicones are extremely hydrophobic and therefore are entirely incompatible with this requirement.
  • long chain, i.e., C 14 or longer, alkyl sulfate detergent surfactants provide the desired amount of surface lubricity as the composition is wiped dry on glass as well as contributing detergency and providing acceptable filming/streaking results and product clarity. Furthermore, the long-chain alkyl sulfate surfactants are soluble in water and help to reinforce the surface hydrophilicity that is required in order to obtain water-sheeting and anti-spotting benefits.
  • WO93/16162 relates to a hard surface cleaning composition
  • a hard surface cleaning composition comprising a solvent selected from C1-6 alkanol , C3-24 alkylene glycol ether, and mixtures thereof, surfactan and a buffering system.
  • the composition is described to reduce filming and streaking.
  • the present invention relates to detergent compositions, preferably glass cleaning compositions, that impart good surface lubricity and clearing without leaving objectionable levels of filming and/or streaking.
  • said compositions contain an effective amount of substantive matenal which provides the glass with long lasting higher hydrophilicity and are in the form of an aqueous, liquid, hard surface detergent composition having improved cleaning and good spotting characteristics after rewetting, compnsing:
  • the present invention relates to detergent compositions, preferably aqueous, liquid hard surface detergent compositions having excellent surface lubricity and filming/streaking characteristics, comprising:
  • the aqueous, liquid hard surface detergent compositions herein contain less than about 1%, by weight of the composition, preferably from 0.01% to 1%, more preferably from 0.02% to 0.3%, by weight of the composition, of one or more chainlengths of a linear alcohol sulfate detergent surfactant having the general formula: R-O-SO 3 M wherein M is any suitable counterion, preferably sodium, potassium, and wherein R is an alkyl group with a chainlength of from C 8 to C 18 and mixtures thereof, preferably from C 12 to C 18 and mixtures thereof, more preferably from C 14 to C 18 and mixtures thereof, and wherein R is C 14 in more than 30%, preferably more than 35%, more preferably more than 40%, by weight of the alkyl sulfate.
  • M is any suitable counterion, preferably sodium, potassium
  • R is an alkyl group with a chainlength of from C 8 to C 18 and mixtures thereof, preferably from C 12 to C 18 and mixtures thereof, more preferably from
  • the entire alkyl sulfate surfactant can contain R of C 14 and longer chainlength(s), but more than 30%, by weight of the alkyl surfactant must be a C 14 chainlength.
  • Compositions containing only alkyl sulfate surfactants with higher chainlengths, i.e., C 16-18 provide good surface lubricity benefits. However, these chain lengths, without the required amount of C 14 chainlengths, exhibit poor filming/streaking properties.
  • compositions which are solely made up of lower-chain alkyl sulfate surfactants, i.e., C 8-12 alkyl sulfate surfactants provide acceptable filming/streaking properties but show poor surface lubricity properties.
  • compositions contain from 0.05% to 0.25%, by weight of the composition, of a C 12/14 blend in which the C 12 to C 14 weight ratio is from 1:10 to 2:1, preferably from 1:5 to 1.5:1, and more preferably from 1:3 to 1:1. This combination has been found to provide sufficient surface lubricity while avoiding objectionable filming/streaking.
  • the alcohol sulfate detergent raw materials selected are essentially free from unreacted fatty alcohol wherein the term "essentially free” is defined as having less than 2%, by weight of the composition, preferably less than 1.8%, and more preferably less than 1.5%, by weight of the composition of unreacted fatty alcohol in a nominally 30% active raw material.
  • a more preferred alkyl sulfate surfactant is a mixture of Stepanol WA-Extra®, available from the Stepan Company, with extra C 14 alkyl sulfate added such that the C 12/14 ratio is nearly 1:1.
  • Concentrated compositions can also be used in order to provide a less expensive product.
  • a higher concentration i.e., when the level of alkyl sulfate surfactant used is from about 0.10% to about 2.5%, by weight of the composition, it is preferable to dilute the composition before using it to clean a hard surface, especially glass.
  • Dilution ratios of the alkyl sulfate concentrate(s) to water can range, preferably, from 1:1 to 1:10, more preferably from 1:1.5 to 1:5, and most preferably from 1:2 to 1:5.
  • aqueous, liquid hard surface detergent compositions of the present invention can contain optional co-surfactants.
  • Suitable co-surfactants which can be used are as follows:
  • the aqueous, liquid hard surface detergent compositions (cleaners) herein can contain from 0% to 0.5%, by weight of the composition, preferably from 0.01% to 0.5%, more preferably from 0.02% to 0.2%, and even more preferably from 0.03% to 0.08%, by weight of the composition, of C 6-10 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 most of the zwitterionic detergent surfactants described hereinafter.
  • the short chains provide improved filming/streaking, even as compared to most of the zwitterionic detergent surfactants described hereinafter.
  • amphocarboxylate detergent surfactants herein preferably have the generic formula: R'N(R 1 )(CH 2 ) n N(R 2 )(CH 2 ) p C(O)OM wherein R' is a C 6-10 hydrophobic moiety, typically a fatty acyl moiety containing from 6 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 1-3 alkyl or, substituted C 1-3 alkyl, e.g., hydroxy substituted or carboxy methoxy substituted, 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 Witco under the trade name Rewoteric AM-V®, having the formula C 7 H 15 C(O)NH(CH 2 ) 2 N(CH 2 CH 2 OH)CH 2 C(O)O (-) Na (+) ; Mona Industries, under the trade name Monateric 1000®, having the formula C 7 H 15 C(O)NH(CH 2 ) 2 N(CH 2 CH 2 OH)CH 2 CH 2 C(O)O (-) Na (+) ; and Lonza under the trade name Amphoterge KJ-2®, having the formula C 7,9 H 15,19 C(O)NH(CH 2 ) 2 N(CH 2 CH 2 OCH 2 C(O)O (-) Na (+) )CH 2 C(O)O (-) Na (+) .
  • the aqueous, liquid hard surface detergent compositions (cleaners) herein can contain from 0% to 1%, by weight of the composition, of suitable zwitterionic detergent surfactant containing a cationic group, preferably a quaternary ammonium group, and an anionic group, preferably carboxylate, sulfate and/or sulfonate group, more preferably sulfonate.
  • suitable zwitterionic detergent surfactant inclusion is from 0.005% to 0.3% of surfactant, a most preferred range is from 0.01% to 0.2%, by weight of the composition.
  • Zwitterionic detergent surfactants 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 1 ] m N(R 6 ) 2 (+) -(CR 5 2 ) p 1-Y (-) wherein each Y is preferably a carboxylate (COO - ) or sulfonate (SO 3 - ) group, more 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 12 to 16 carbon atoms; wherein each (R 4 ) is either hydrogen, or a short chain alkyl, or substituted 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 and mixtures thereof, preferably methyl;
  • the R 3 groups can be branched, unsaturated, or both 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 such as imidazoline, pyridine, etc.
  • hydrocarbylamidoalkylene sulfobetaines and, to a lesser extent hydrocarbylamidoalkylene betaines 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-amino alkanol 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 Witco Company as a 40% active product under the trade name "REWOTERIC AM CAS Sulfobetaine®.”
  • the level in the composition is dependent on the eventual level of dilution to make the wash solution.
  • the composition when used full strength, or wash solution containing the composition, should contain from 0.0% to 1%, preferably from 0.005% to 0.5%, more preferably from 0.01% to 0.25%, by weight of the composition, of detergent surfactant.
  • the level can, and should be, higher, typically from 0% to 10%, preferably from about 0.005% to 2%, by weight of the composition.
  • Concentrated products will typically contain from 0% to 10%, preferably from 0.005% to 5%, by weight of the composition.
  • zwitterionic detergent e.g., HASB
  • compositions containing it can be more readily diluted by consumers since it does not interact with hardness cations as readily as conventional anionic detergent surfactants.
  • Zwitterionic detergents are also extremely effective at very low levels, e.g., below 1%.
  • zwitterionic detergent surfactants are set forth at Col. 4 of U.S. Pat. No. 4,287,080, Siklosi. 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. Commercial sources of such surfactants can be found in McCutcheon's EMULSIFIERS AND DETERGENTS, North American Edition, 1984, McCutcheon Division, MC Publishing Company.
  • the detergent compositions preferably aqueous, liquid hard surface detergent compositions, herein can contain as the cosurfactant, preferably, from 0.0% to 2.0%, more preferably from 0.005% to 0.99% of suitable anionic detergent surfactant other than the essential alkyl sulfate detergent surfactant. While it is understood that the longer chain alkyl sulfate surfactants disclosed herein are considered the primary surfactant system, additional co-surfactants can be added including alkyl sulfate surfactants of even lower chain lengths.
  • the optional anionic surfactants are suitably water-soluble alkyl or alkylaryl compounds, the alkyl having from 6 to 20 carbons, and including a sulfate or sulfonate substituent group, but excluding the essential alkyl sulfate detergent surfactant.
  • the anionic detergent surfactant can be combined with a cosurfactant, preferably an amphoteric cosurfactant.
  • Nonionic surfactants e.g., ethoxylated alcohols and/or alkyl phenols, can also be used as cosurfactants but are not preferred.
  • the anionic detergent surfactants herein preferably have the generic formula: R 9 -(R 10 ) 0-1 -SO 3 (-) M (+) wherein R 9 is a C 6 -C 20 alkyl chain, preferably a C 8 -C 16 alkyl chain; R 10 , when present, is a C 6 -C 20 alkylene chain, preferably a C 8 -C 16 alkylene chain, a C 6 H 4 phenylene group, or O; and M is the same as before.
  • detergent surfactants e.g., anionic, and, less preferably, nonionic detergent surfactants, that can be used in small amounts, preferably as cosurfactants for the essential alkyl sulfate detergent surfactant and preferred amphoteric/zwitterionic detergent cosurfactant.
  • the cosurfactant level can be small in relation to the primary surfactant.
  • alkyl- and alkylethoxylate- (polyethoxylate) sulfates Typical of these are the alkyl- and alkylethoxylate- (polyethoxylate) sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, alkyl phenol sulfonates, alpha-sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known from the detergency art.
  • detergent surfactants that are amphoteric at a lower pH are desirable anionic 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.
  • detergent surfactants useful herein contain a hydrophobic group, typically containing an alkyl group in the C 9 -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, not preferred, generally contain from 5 to 17 ethylene oxide groups.
  • Suitable surfactants for use herein in small amounts 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 8 carbons to 16 carbon atoms and having an average carbon chain length of from 10 to 12 carbon atoms with from 4 to 8 moles of ethylene oxide per mo
  • 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. It is understood that mixtures of various surfactants can be used.
  • amphocarboxylate zwitterionic detergent surfactants, and/or anionic detergent surfactants as discussed hereinbefore, can be present in the present invention.
  • the total surfactant level can be from 0.01% to 5%, by weight of the total composition however, the alkyl surfactant should be present at a level less than 1%, by weight of the composition.
  • the ratio of zwitterionic detergent surfactant to amphocarboxylate detergent surfactant is typically from 3:1 to 1:3, preferably from 2:1 to 1:2, more preferably 1:1.
  • the ratio of the primary C 14 alkyl sulfate detergent surfactant to cosurfactant, or cosurfactants, is typically from 3:1 to 1:1.
  • solvents employed in the hard surface cleaning compositions herein can be any of the well-known "degreasing" solvents commonly used in, for example, the dry cleaning industry, in the hard surface cleaner industry and the metalworking industry.
  • ⁇ H is the hydrogen bonding parameter
  • a is the aggregation number
  • (Log ⁇ 3.39066 T b /T c - 0.15848 - Log M d )
  • ⁇ T is the solubility parameter which is obtained from the formula: where ⁇ H 25 is the heat of vaporization at 25°C, R is the gas constant (1.987 cal/mole/deg), T is the absolute temperature in °K, T b is the boiling point in °K, T c is the critical temperature in °K, d is the density in g/ml, and M is the molecular weight.
  • hydrogen bonding parameters are from 2 to 7,7 preferably from 2 to 7, and more preferably from 3 to 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.
  • Hydrophobic solvents are used at a level of from 0.5% to 30%, preferably from 2% to 15%, more preferably from 3% to 8%.
  • Dilute compositions typically have solvents at a level of from 1% to about 10%, preferably from 3% to 6%.
  • Concentrated compositions contain from 10% to 30%, preferably from 10% to 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 20°C.
  • compositions of the present type will be guided in the selection of cosolvent partly by the need to provide good grease-cutting properties, and partly by aesthetic considerations.
  • kerosene hydrocarbons function quite well for grease cutting in the present compositions, but can be malodorous. Kerosene must be exceptionally clean before it can be used, even in commercial situations. For home use, where malodors would not be tolerated, the formulator would be more likely to select solvents which have a relatively pleasant odor, or odors which can be reasonably modified by perfuming.
  • the C 6 -C 9 alkyl aromatic solvents especially the C 6 -C 9 alkyl benzenes, preferably octyl benzene, exhibit excellent grease removal properties and have a low, pleasant odor.
  • glycol ethers useful herein have the formula R 11 O-(R 12 O-) m 1H wherein each R 11 is an alkyl group which contains from 3 to 8 carbon atoms, each R 12 is either ethylene or propylene, and m 1 is a number from 1 to 3.
  • glycol ethers are selected from the group consisting of monopropyleneglycolmonopropyl ether, dipropyleneglycolmonobutyl ether, monopropyleneglycolmonobutyl ether, ethyleneglycolmonohexyl ether, ethyleneglycolmonobutyl ether, diethyleneglycolmonohexyl ether, monoethyleneglycolmonohexyl ether, monoethyleneglycolmonobutyl ether, and mixtures thereof.
  • a particularly preferred type of solvent for these hard surface cleaner compositions comprises diols having from 6 to 16 carbon atoms in their molecular structure.
  • Preferred diol solvents have a solubility in water of from about 0.1 to about 20 g/100 g of water at 20°C.
  • Solvents such as pine oil, orange terpene, benzyl alcohol, n-hexanol, phthalic acid esters of C 1-4 alcohols, butoxy propanol, Butyl Carbitol® and 1(2-n-butoxy-1-methylethoxy)propane-2-ol (also called butoxy propoxy propanol or dipropylene glycol monobutyl ether), hexyl diglycol (Hexyl Carbitol®), butyl triglycol, diols such as 2,2,4-trimethyl-1,3-pentanediol, and mixtures thereof, can be used.
  • Solvents such as pine oil, orange terpene, benzyl alcohol, n-hexanol, phthalic acid esters of C 1-4 alcohols, butoxy propanol, Butyl Carbitol® and 1(2-n-butoxy-1-methylethoxy)propane-2-ol (also called butoxy propoxy
  • the butoxypropanol solvent should preferably have no more than 20%, preferably no more than 10%, more preferably no more than 7%, of the secondary isomer in which the butoxy group is attached to the secondary atom of the propanol where improved odor is preferred.
  • compositions of this invention can contain an optional alkalinity source.
  • Suitable compounds which can be used include but are not limited to alkali metal hydroxides, i.e., sodium, potassium and carbonates or sodium bicarbonates.
  • the alkalinity source can be present at a level of 0% to 0.2%, by weight of the composition. Typically said alkalinity source is present at a level of from 0.001% to 0.1%, preferably from 0.005% to 0.05%, by weight of the composition.
  • Water-soluble alkali metal carbonate and/or bicarbonate salts such as sodium bicarbonate, potassium bicarbonate, potassium carbonate, cesium carbonate, sodium carbonate, and mixtures thereof, are added to the composition of the present invention in order to improve the filming/streaking when the product is wiped dry on the surface, as is typically done in glass cleaning.
  • Preferred salts are sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, their respective hydrates, and mixtures thereof.
  • Solubilized, water-soluble alkali metal carbonate and bicarbonate salts are typically present at a level of from 0% to 0.5%, preferably from 0.001% to 0.1%, more preferably from 0.005% to 0.05%, by weight of the composition.
  • the pH in the composition at least initially, in use is preferably from 7 to 11, preferably from 7.5 to 10.5, more preferably from 8 to 10. pH is typically measured on the product.
  • An optional but preferred ingredient of this invention is the substantive material that improves the hydrophilicity of the surface being treated, especially glass. This increase in hydrophilicity provides improved appearance when the surface is rewetted and then dried. The water “sheets" off the surface and thereby minimizes the formation of, e.g., "rainspots” that form upon drying. Many malterials can provide this benefit, but the preferred materials are polymers that contain hydrophilic groups, especially carboxylate or sulfonate groups. Other materials that can provide substantivity and hydrophilicity include cationic materials that also contain hydrophilic groups and polymers that contain multiple ether linkages. Cationic materials include cationic sugar and/or starch derivatives and the typical block copolymer detergent surfactants based on mixtures of polypropylene oxide and ethylene oxide are representative of the polyether materials. The polyether materials are less substantive, however.
  • the preferred polycarboxylate polymers are those formed by polymerization of monomers, at least some of which contain carboxylic functionality. Common monomers include acrylic acid, maleic acid, ethylene, vinyl pyrrollidone, methacrylic acid, methacryloylethylbetaine, etc.
  • the preferred polysulfonate polymers are those based upon a polystyrene backbone. Preferred polymers for substantivity are those having higher molecular weights.
  • polyacrylic acid having molecular weights below 10,000 are not particularly substantive and therefore do not normally provide hydrophilicity for three rewettings with all compositions, although with higher levels and/or certain surfactants like amphoteric and/or zwitterionic detergent surfactants, molecular weights down to 1000 can provide some results.
  • the polymers should have molecular weights of more than 10,000, preferably more than 20,000, more preferably more than about 300,000, and even more preferably more than 400,000. It has also been found that higher molecular weight polymers, e.g., those having molecular weights of more than 3,000,000, are extremely difficult to formulate and are less effective in providing anti-spotting benefits than lower molecular weight polymers. Accordingly, the molecular weight should normally be, especially for polyacrylates, from 20,000 to 3,000,000; preferably from 20,000 to 2,500,000; more preferably from 300,000 to 2,000,000; and even more preferably from 400,000 to 1,500,000.
  • polycarboxylate polymers An advantage for some polycarboxylate polymers is the detergent builder effectiveness of such polymers. Surprisingly, such polymers do not hurt filming/streaking and like other detergent builders, they provide increased cleaning effectiveness on typical, common "hard-to-remove" soils that contain particulate matter.
  • compositions thicken the compositions that are aqueous liquids. This can be desirable. However, when the compositions are placed in containers with trigger spray devices, the compositions are desirably not so thick as to require excessive trigger pressure. Typically, the viscosity under shear should be less than 200 cp, preferably less than 100 cp, more preferably less than 50 cp. It can be desirable, however, to have thick compositions to inhibit the flow of the composition offthe surface, especially vertical surfaces.
  • suitable materials for use herein include poly(vinyl pyrrolidone/acrylic acid) sold under the name "Acrylidone”® by ISP, polystyrene sulfonic acid and polystyrene sulfonate salts sold under the name “Versaflex”® by National Starch, and poly(acrylic acid) sold under the name “Accumer”® by Rohm & Haas.
  • the level of substantive material should normally be from 0% to 1.0%, preferably from 0.01% to 0.5%, more preferably from 0.02% to 0.2%, by weight of the composition.
  • lower molecular weight materials such as lower molecular weight poly(acrylic acid), e.g., those having molecular weights below 10,000, and especially 2,000, do not provide good anti-spotting benefits upon rewetting, especially at the lower levels, e.g., about 0.02%.
  • substantivity should be increased, e.g., by adding groups that provide improved attachment to the surface, such as cationic groups, or the materials should be used at higher levels, e.g., more than 0.05%.
  • the balance of the formula is typically water and non-aqueous polar solvents with only minimal cleaning action like methanol, ethanol, isopropanol, ethylene glycol, glycol ethers having a hydrogen bonding parameter of greater than 7.7, propylene glycol, and mixtures thereof, preferably ethanol.
  • the level of non-aqueous polar solvent is usually greater when more concentrated formulas are prepared.
  • the level of non-aqueous polar solvent is from 0.5% to 40%, preferably from 1% to 10%, more preferably from 2% to 8% (especially for "dilute" compositions) and the level of water is from 50% to 99%, preferably from 75% to 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:
  • Suitable additional optional detergent builders include salts of ethylenediaminetetraacetic acid (hereinafter EDTA), citric acid, nitrilotriacetic acid (hereinafter NTA), sodium carboxymethylsuccinic acid, sodium N-(2-hydroxypropyl)-iminodiacetic acid, and N-diethyleneglycol-N,N-diacetic acid (hereinafter DIDA).
  • the salts are preferably compatible and include ammonium, sodium, potassium and/or alkanolammonium salts.
  • the alkanolarrmonium salt is preferred as descnbed hereinafter.
  • a preferred detergent builder is NTA (e.g., sodium), a more preferred builder is citrate (e.g., sodium or monoethanolamine), and a most preferred builder is EDTA (e.g., sodium).
  • additional optional detergent builders when present, are typically at levels of from 0.01% to 0.5%. more preferably from 0.02% to 0.3%, most preferably from 0.02% to 0.15%.
  • the levels of these additional builders present in the wash solution used for glass should be less than 0.2%. Therefore, typically, dilution is highly preferred for cleaning glass, while full strength is preferred for general purpose cleaning, depending on the concentration of the product.
  • a 30.5 cm x 30.5 cm (12" x 12") pane of glass is sprayed with product (one spray from a standard spray device) and wiped to near dryness with one paper towel.
  • a 550 gram plexiglass block is wrapped with a paper towel by taking one sheet and folding it twice into a square. The towel is taped to the bottom of the block so it is stretched taut with no wrinkles or creases and no tape is on the bottom surface that will be in contact with the glass.
  • the block is placed on the glass toward one end. The end of the glass is raised slowly until the block begins to move. The distance that the glass was raised is measured. The higher the height, the higher the friction and the static friction height.
  • a normal dry clean glass has a high coefficient of friction (0.9-1.0), and therefore a high static friction height (greater than 12.7 cm (5 inches) with this method).
  • formulas 1-3 of the present invention provide lower static friction height than formulas 4-5 which are outside the scope of the present invention while maintaining good end results.
  • the C 14 and longer chainlengths provide the most smoothness (lowest static friction height).
  • Qualitative evaluation shows that Formulas 1-3 provide noticeably improved surface lubricity while wiping to dryness than do Formulas 4-5.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Detergent Compositions (AREA)

Claims (9)

  1. Composition détergente liquide aqueuse pour surface dure ayant d'excellentes caractéristiques de pouvoir lubrifiant de surface et d'effet anti-film/anti-stries, comprenant :
    (A) moins de 1 %, de préférence de 0,01 % à 0,9 %, de préférence encore de 0,02 % à 0,3 % en poids, par rapport à la composition, d'un agent tensioactif détergent sulfate d'alkyle linéaire ayant la formule générale : R-O-SO3M dans laquelle M est un contre-ion approprié ; R est un groupe alkyle ayant une longueur de chaíne en C8 à C18 ou un mélange de tels groupes alkyle; de préférence en C12 à C18, de préférence encore en C14 à C18, plus de 30 %, de préférence encore plus de 35 %, de préférence encore plus de 40 % en poids, par rapport audit agent tensioactif, dudit agent tensioactif ayant une longueur de chaíne en C14;
    (B) de 0,5 % à 30 % en poids, par rapport à la composition, d'un solvant hydrophobe ayant un paramètre de liaison hydrogène de 2 à 7,7 ;
    (C) le reste étant un système solvant aqueux choisi dans le groupe constitué par l'eau et les solvants polaires non aqueux ayant un paramètre de liaison hydrogène supérieur à 7,7 ; et
       ladite composition ayant moins de 2 % en poids, par rapport à la composition, d'alcool gras n'ayant pas réagi et de composés alcanolamines, et ladite composition convenant au nettoyage du verre.
  2. Composition selon la revendication 1, dans laquelle R est un groupe alkyle ayant une longueur de chaíne d'un mélange C12/14 ayant un rapport pondéral C12 à C14 de 1:10 à 2:1.
  3. Composition selon la revendication 1, comprenant en outre jusqu'à 4,9 % en poids, par rapport à la composition, d'un co-agent tensioactif choisi dans le groupe constitué par :
    (A) des agents tensioactif détergents amphocarboxylates en C6 à C10;
    (B) des agents tensioactifs détergents zwittérioniques ;
    (C) des agents tensioactifs détergents anioniques ; et
    (D) des mélanges de ceux-ci.
  4. Composition selon la revendication 1, comprenant en outre de 0 % à 0,5 %, de préférence de 0,001 % à 0,1%, de préférence encore de 0,005 % à 0,5 % en poids, par rapport à la composition, d'un sel carbonate ou bicarbonate de métal alcalin, hydrosoluble, solubilisé, ou de mélanges de ceux-ci.
  5. Composition selon la revendication 4, dans laquelle ledit sel est choisi dans le groupe constitué par la carbonate de sodium, le carbonate de potassium, le bicarbonate de sodium, le bicarbonate de potassium, leurs hydrates respectifs, et des mélanges de ceux-ci.
  6. Composition selon la revendication 1, comprenant en outre de 0 % à 1,0 % d'une matière substantive qui augmente l'hydrophilie du verre, choisie parmi les polymères qui contiennent des groupes hydrophiles, spécialement des groupes carboxylates et sulfonates.
  7. Composition selon la revendication 6, dans laquelle ladite matière substantive est un polymère polycarboxylate, de préférence ayant un poids moléculaire de 1 000 à 3 000 000, de préférence encore ayant un poids moléculaire de 20 000 à 2 500 000, de toute préférence ayant un poids moléculaire de 400 000 à 1 500 000.
  8. Composition détergente liquide aqueuse pour surface dure ayant à la fois d'excellentes caractéristiques de pouvoir lubrifiant de surface et d'excellentes caractéristiques d'effet anti-film et anti-stries, comprenant :
    (A) de 0,01 % à 0,9 % en poids, par rapport à la composition, d'un agent tensioactif détergent sulfate d'alkyle linéaire ayant la formule générale : R-O-SO3M dans laquelle M est un contre-ion sodium ; R est un groupe alkyle ayant une longueur de chaíne d'un mélange C12/14 ayant un rapport pondéral C12 à C14 de 1:10 à 2:1, et plus de 30 % dudit agent tensioactif sulfate d'alkyle étant composés d'une longueur de chaíne en C14 ;
    (B) de 0,005 % à 0,9 % en poids, par rapport à la composition, d'un co-agent tensioactif sulfate d'alkyle en C14 ;
    (C) de 0,001% à 0,1 % en poids, par rapport à la composition, de carbonate de sodium ;
    (D) de 0,5 % à 30% en poids, par rapport à la composition, de butoxypropanol;
    (E) le reste étant un mélange d'éthanol et d'eau ; et
       ladite composition ayant moins de 2 % en poids. par rapport à la composition, d'un alcool gras n'ayant pas réagi et de composés alcanolamines, et ladite composition convenant au nettoyage du verre.
  9. Procédé de nettoyage de verre, comprenant :
    (A) la pulvérisation de la composition 1 sur une surface de verre en utilisant un dispositif de pulvérisation ; et
    (B) l'essuyage de ladite surface jusqu'à ce qu'elle soit presque sèche.
EP96913006A 1995-05-05 1996-04-23 Compositions de nettoyage du verre comportant des agents tensioactifs lineaires sulfates d'alkyle Expired - Lifetime EP0823937B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US43606395A 1995-05-05 1995-05-05
US436063 1995-05-05
PCT/US1996/005561 WO1996034933A1 (fr) 1995-05-05 1996-04-23 Compositions de nettoyage du verre comportant des agents tensioactifs lineaires sulfates d'alkyle

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EP0823937A1 EP0823937A1 (fr) 1998-02-18
EP0823937B1 true EP0823937B1 (fr) 1999-10-13

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EP (1) EP0823937B1 (fr)
AR (1) AR001845A1 (fr)
AT (1) ATE185591T1 (fr)
AU (1) AU5564296A (fr)
BR (1) BR9608216A (fr)
CA (1) CA2220131C (fr)
CO (1) CO4700538A1 (fr)
DE (1) DE69604660T2 (fr)
DK (1) DK0823937T3 (fr)
ES (1) ES2136988T3 (fr)
GR (1) GR3032284T3 (fr)
MX (1) MX9708503A (fr)
WO (1) WO1996034933A1 (fr)

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US5759980A (en) * 1997-03-04 1998-06-02 Blue Coral, Inc. Car wash
AU8457898A (en) 1997-08-13 1999-03-08 Procter & Gamble Company, The Glass cleaner compositions having good surface lubricity and alkaline buffer
WO1999061569A1 (fr) * 1998-05-22 1999-12-02 The Procter & Gamble Company Compositions de nettoyage acides a tensioactif detergent sulfate d'alykle c¿10?
US6013323A (en) * 1998-10-30 2000-01-11 Klayder; Donna W. Silicone gel waxes and silicone gel protectants
ES2276046T3 (es) * 2002-02-22 2007-06-16 Colgate-Palmolive Company Toallita limpiadora antibacteriana.
JP2004271985A (ja) † 2003-03-10 2004-09-30 Fuji Photo Film Co Ltd 感光性平版印刷版用現像液及び平版印刷版の製版方法

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DE2243257A1 (de) * 1972-09-02 1974-03-21 Robert Boschung Reinigungsmittel fuer glasscheiben oder dergleichen
US5252245A (en) * 1992-02-07 1993-10-12 The Clorox Company Reduced residue hard surface cleaner
DK0595383T3 (da) * 1992-10-26 1997-05-05 Procter & Gamble Flydende detergentsammensætninger til hårde overflader ideholdende kortkædet amfocarboxylat-detergent-overfladeaktivt middel
US5531933A (en) * 1993-12-30 1996-07-02 The Procter & Gamble Company Liquid hard surface detergent compositions containing specific polycarboxylate detergent builders

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DK0823937T3 (da) 1999-12-27
DE69604660T2 (de) 2000-05-18
WO1996034933A1 (fr) 1996-11-07
EP0823937A1 (fr) 1998-02-18
AU5564296A (en) 1996-11-21
MX9708503A (es) 1998-02-28
BR9608216A (pt) 1999-05-25
GR3032284T3 (en) 2000-04-27
CA2220131C (fr) 2001-03-27
AR001845A1 (es) 1997-12-10
ATE185591T1 (de) 1999-10-15
CA2220131A1 (fr) 1996-11-07
ES2136988T3 (es) 1999-12-01
CO4700538A1 (es) 1998-12-29
DE69604660D1 (de) 1999-11-18

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