WO1996034933A1 - 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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Publication number
WO1996034933A1
WO1996034933A1 PCT/US1996/005561 US9605561W WO9634933A1 WO 1996034933 A1 WO1996034933 A1 WO 1996034933A1 US 9605561 W US9605561 W US 9605561W WO 9634933 A1 WO9634933 A1 WO 9634933A1
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Prior art keywords
composition
weight
surfactant
detergent
alkyl sulfate
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PCT/US1996/005561
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English (en)
Inventor
Ronald Anthony Masters
Charles Albert Hensley
Lori Boden Mitchell
Michael Stephen Maile
Nicola John Policicchio
Todd Christian Severson
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to DE69604660T priority Critical patent/DE69604660T2/de
Priority to AU55642/96A priority patent/AU5564296A/en
Priority to CA002220131A priority patent/CA2220131C/fr
Priority to MX9708503A priority patent/MX9708503A/es
Priority to DK96913006T priority patent/DK0823937T3/da
Priority to BR9608216A priority patent/BR9608216A/pt
Priority to EP96913006A priority patent/EP0823937B1/fr
Publication of WO1996034933A1 publication Critical patent/WO1996034933A1/fr
Priority to GR990403373T priority patent/GR3032284T3/el

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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

  • Glass cleaner compositions having linear alkyl sulfate surfactants having linear alkyl sulfate surfactants.
  • This invention pertains to glass cleaning compositions, preferably clear liquid detergent compositions, for use in cleaning glass and, preferably, other hard surfaces.
  • 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., C14 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.
  • 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.
  • the present invention relates to detergent compositions, preferably glass cleaning compositions, that impart good surface lubricity and cleaning without leaving objectionable levels of filming and/or streaking.
  • said compositions contain an effective amount of substantive material 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, comprising:
  • R-O-SO3 M wherein M is a suitable counter ion;
  • R is an alkyl group having a chain length of from about Cg to about Cjg or mixtures thereof; wherein more than about 30%, by weight of said surfactant, of said surfactant has a C14 chainlength;
  • the present invention relates to detergent compositions, preferably aqueous, liquid hard surface detergent compositions having excellent surface lubricity and filming/streaking characteristics, comprising:
  • R-O-SO3 M wherein M is a suitable counter ion;
  • R is an alkyl group having a chain length of from about Cg to about C j g or mixtures thereof; wherein more than about 30%, by weight of said surfactant, of said surfactant has a C14 chainlength;
  • B from about 0.5% to about 30%, by weight of the composition, of a hydrophobic solvent having a hydrogen bonding parameter of from about 2 to 7.7;
  • aqueous solvent system selected from the group consisting of water and non-aqueous polar solvents having a hydrogen bonding parameter of greater than 7.7; and wherein said composition is essentially free of unreacted fatty alcohol and alkanolamine compounds and wherein said composition is suitable for cleaning glass.
  • the aqueous, liquid hard surface detergent compositions herein contain less than about 1%, by weight of the composition, preferably from about 0.01% to about 1%, more preferably from about 0.02% to about 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 - SO3 M wherein M is any suitable counterion, preferably sodium, potassium, etc.; and wherein R is an alkyl group with a chainlength of from about Cg to about C j g and mixtures thereof, preferably from about C12 to about Cjg and mixtures thereof, more preferably from about C14 to about C ⁇ g and mixtures thereof, and wherein R is Cj4 in more than about 30%, preferably more than about 35%, more preferably more than about 40?/o, by weight of the alkyl sulfate.
  • the entire alkyl sulfate surfactant can contain R of C14 and longer chainlength(s), but more than 30%, by weight of the alkyl surfactant must be a C14 chainlength.
  • Compositions containing only alkyl sulfate surfactants with higher chainlengths, i.e., Cj ⁇ i provide good surface lubricity benefits. However, these chain lengths, without the required amount of C14 chainlengths, exhibit poor filming/streaking properties.
  • compositions which are solely made up of lower-chain alkyl sulfate surfactants, i.e., Cg-12 alkyl sulfate surfactants provide acceptable filming/streaking properties but show poor surface lubricity properties.
  • compositions contain from about 0.05% to about 0.25%, by weight of the composition, of a C 12/14 blend in which the C ⁇ to C 14 weight ratio is from about 1:10 to about 2: 1, preferably from about 1:5 to about 1.5: 1, and more preferably from about 1 :3 to about 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 about 2%, by weight of the composition, preferably less than about 1.8%, and more preferably less than about 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 C14 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 about 1: 1 to 1: 10, more preferably from about 1 : 1.5 to 1 :5, and most preferably from about 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: (1) The Amphocarboxylate Detergent Surfactant
  • the aqueous, liquid hard surface detergent compositions (cleaners) herein can contain from 0% to about 0.5%, by weight of the composition, 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%, by weight of the composition, of C f 5-io 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.
  • the "amphocarboxylate" detergent surfactants herein preferably have the generic formula:
  • R' is a Cg.io hydrophobic moiety, typically a fatty acyl moiety containing from about 6 to about 10 carbon atoms which, in combination with the nitrogen atom forms an amido group
  • R is hydrogen (preferably) or a C ⁇ _2 alkyl group
  • R ⁇ is a C ⁇ _3 alkyl or, substituted C1.3 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
  • 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! 5C(O)NH(CH 2 )2N(CH2CH2OH)CH 2 C(O)O(-) Na( + )i
  • aqueous, liquid hard surface detergent compositions herein can contain from about 0% to about 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 about 0.005% to about 0.3% of surfactant, a most preferred range is from about 0.01% to about 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:
  • each Y is preferably a carboxylate (COO") or sulfonate (SO3") group, more preferably sulfonate;
  • each R ⁇ is a hydrocarbon, e.g., an alkyl, or alkylene, group containing from about 8 to about 20, preferably from about 10 to about 18, more preferably from about 12 to about 16 carbon atoms;
  • each (R ⁇ ) 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;
  • each (R ⁇ ) is selected from the group consisting of hydrogen and hydroxy groups with no more than one
  • the R ⁇ 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 ⁇ groups.
  • the R ⁇ 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 C10-14 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 about 0.0% to about 1%, preferably from about 0.005% to about 0.5%, more preferably from about 0.01% to about 0.25%, by weight of the composition, of detergent surfactant.
  • the level can, and should be, higher, typically from about 0% to about 10%, preferably from about 0.005% to about 2%, by weight of the composition.
  • Concentrated products will typically contain from about 0% to about 10%, preferably from about 0.005% to about 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 about 1%.
  • 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.
  • the detergent compositions preferably aqueous, liquid hard surface detergent compositions, herein can contain as the cosurfactant, preferably, from about 0.0% to about 2.0%, more preferably from about 0.005% to about 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 about 6 to about 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.
  • anionic detergent surfactants herein preferably have the generic formula:
  • 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 Ci2-C g acylamido alkylene amino alkylene sulfonates, e.g., compounds having the formula R-C(O)-NH- (C2H4)-N(C2H 4 OH)-CH 2 CH(OH)CH2SO3M 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 Cc-C ⁇ g 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 about 5 to about 17 ethylene oxide groups.
  • Suitable surfactants for use herein in small amounts are one or more of the following: sodium linear Cg-Cig alkyl benzene sulfonate (LAS), particularly 1 l" i2 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 mo
  • R7 — C — N(R8) 2 wherein R 7 is a straight-chain alkyl group containing from about 7 to about 15 carbon atoms and having an average carbon chain length of from about 9 to about 13 carbon atoms and wherein each R ⁇ is a hydroxy alkyl group containing from 1 to about 3 carbon atoms; a zwitterionic surfactant having one of the preferred formulas set forth hereinafter; or a phosphine oxide surfactant.
  • fluorocarbon surfactants examples of which are FC-129®, a potassium fluorinated alkyl carboxylate 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.
  • the total surfactant level can be from about 0.01% to about 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 about 3: 1 to about 1 :3, preferably from about 2: 1 to about 1:2, more preferably about 1: 1.
  • the ratio of the primary C14 alkyl sulfate detergent surfactant to cosurfactant, or cosurfactants, is typically from about 3 : 1 to about 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 TyT c - 0.15848 - Log M)
  • d ⁇ T is the solubility parameter which is obtained from the formula:
  • ⁇ H25 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 D is the boiling point in °K
  • T c is the critical temperature in °K
  • d is the density in g/ml
  • M is the molecular weight.
  • 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.
  • Hydrophobic solvents are typically used at a level of from about 0.5% to about 30%, preferably from about 2% to about 15%, more preferably from about 3% to about 8%.
  • Dilute compositions typically have solvents at a level of from about 1% to about 10%, preferably from about 3% to about 6%.
  • 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.
  • 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 ⁇ -Co. alkyl aromatic solvents especially the Cg-C ⁇ alkyl benzenes, preferably octyl benzene, exhibit excellent grease removal properties and have a low, - 11 - pleasant odor.
  • glycol ethers useful herein have the formula RU O-(R 2 ⁇ -) m lH wherein each R! 1 is an alkyl group which contains from about 3 to about 8 carbon atoms, each R12 is either ethylene or propylene, and ml is a number from 1 to about 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 about 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 l(2-n-butoxy-l- 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-l,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 l(2-n-butoxy-l- methylethoxy)propane-2-ol
  • the 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.
  • 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, etc., and carbonates or sodium bicarbonates.
  • the alkalinity source can be present at a level of 0% to about 0.2%, by weight of the composition. Typically said alkalinity source is present at a level of from about 0.001% to about 0.1%, preferably from about 0.005% to about 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 about 0% to about 0.5%, preferably from about 0.001% to about 0.1%, more preferably from about 0.005% to about 0.05%, by weight of the composition.
  • the pH in the composition at least initially, in use is from about 7 to about 1 1, preferably from about 7.5 to about 10.5, more preferably from about 8 to about 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 rninimizes the formation of, e.g., "rainspots” that form upon drying. Many materials 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 about 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 about 1000 can provide some results.
  • the polymers should have molecular weights of more than 10,000, preferably more than about 20,000, more preferably more than about 300,000, and even more preferably more than about 400,000. It has also been found that higher molecular weight polymers, e.g., those having molecular weights of more than about 3,000,000, are extremely difficult to formulate and are less effective in providing anti-spotting benefits than lower molecular weight polymers.
  • the molecular weight should normally be, especially for polyacrylates, from about 20,000 to about 3,000,000; preferably from about 20,000 to about 2,500,000; more preferably from about 300,000 to about 2,000,000; and even more preferably from about 400,000 to about 1,500,000.
  • 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. Some polymers, especially polycarboxylate polymers, thicken the compositions that are aqueous liquids. This can be desirable.
  • the compositions when the compositions are placed in containers with trigger spray devices, the compositions are desirably not so thick as to require excessive trigger pressure.
  • the viscosity under shear should be less than about 200 cp, preferably less than about 100 cp, more preferably less than about 50 cp. It can be desirable, however, to have thick compositions to inhibit the flow of the composition off the 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 about 0% to about 1.0%, preferably from about 0.01% to about 0.5%, more preferably from about 0.02% to about 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 about 10,000, and especially about 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 about 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 about 0.5% to about 40%, preferably from about 1% to about 10%, more preferably from about 2% to about 8% (especially for "dilute" compositions) and the level of water is from about 50% to about 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:
  • Enzymes such as proteases
  • Hvdrotropes such as sodium toluene sulfonate, sodium cumene sulfonate and potassium xylene sulfonate;
  • Aesthetic-enhancing ingredients such as colorants and perfumes, providing they do not adversely impact on filming/streaking in the cleaning of glass.
  • 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.
  • 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.
  • some of the less volatile, high boiling perfume ingredients 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.
  • the perfumes are preferably those that are more water-soluble and or volatile to rninimize streaking and filming.
  • the perfumes useful herein are described in more detail in U.S. Patent 5, 108,660, Michael, issued April 28, 1992, at col. 8 lines 48 to 68, and col. 9 lines 1 to 68, and col. 10 lines 1 to 24, said patent, and especially said specific portion, being incorporated by reference.
  • Antibacterial agents can be present, but preferably only at low levels to avoid filming/streaking problems. More hydrophobic antibacterial geimicidal agents, like orthobenzyl-para-chlorophenol, are avoided. If present, such materials should be kept at levels below about 0.1%.
  • Stabilizing ingredients can be present typically to stabilize more of the hydrophobic ingredients, e.g., perfume.
  • the stabilizing ingredients include acetic acid and propionic acids, and their salts, e.g., NH4, MEA, Na, K, etc., preferably acetic acid and the C2-C6 alkane diols, more preferably butane diol.
  • the stabilizing ingredients do not function in accordance with any known principle. Nonetheless, the combination of amido zwitterionic detergent surfactant with linear acyl amphocarboxylate detergent surfactant, anionic detergent surfactant, nonionic detergent surfactant, or mixtures thereof, and stabilizing ingredient can create a microemulsion.
  • the amount of stabilizing ingredient is typically from about 0.01% to about 0.5%, preferably from about 0.02% to about 0.2%.
  • the ratio of hydrophobic material, e.g., perfume that can be stabilized in the product is related to the total surfactant and typically is in an amount that provides a ratio of surfactant to hydrophobic material of from about 1:2 to about 2:1.
  • Other detergent builders that are efficient for hard surface cleaners and have reduced filming/streaking characteristics at the critical levels can also be present in the compositions of the invention. Addition of specific detergent builders at critical levels to the present composition further improves cleaning without the problem of filming streaking that usually occurs when detergent builders are added to hard surface cleaners.
  • compositions containing these specific additional detergent builders have exceptionally good cleaning properties. They also have exceptionally good "shine properties, i.e., when used to clean glossy surfaces, without rinsing, they have much less tendency than, e.g., carbonate built products to leave a dull finish on the surface and filming/streaking.
  • Suitable additional optional detergent builders include salts of ethylenediaminetetraacetic acid (hereinafter EDTA), citric acid, nitrilotriacetic acid (hereinafter NT A), sodium carboxymethylsuccinic acid, sodium N-(2- hydroxypropy -iminodiacetic acid, and N-diethyleneglycol-N,N-diacetic acid (hereinafter DID A).
  • EDTA ethylenediaminetetraacetic acid
  • NT A nitrilotriacetic acid
  • DID A N-diethyleneglycol-N,N-diacetic acid
  • the salts are preferably compatible and include ammonium, sodium, potassium and or alkanolammonium salts.
  • the alkanolammonium salt is preferred as described 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).
  • NTA e.g., sodium
  • citrate e.g., sodium or monoethanolamine
  • EDTA e.g., sodium
  • These additional optional detergent builders when present, are typically at levels of from about 0.01% to about 0.5%. more preferably from about 0.02% to about 0.3%, most preferably from about 0.02% to about 0.15%. The levels of these additional builders present in the wash solution used for glass should be less than about 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 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 5 inches with this method).
  • End Result Wipe Test Procedure Five sprays of the product to be tested are applied to a 2ft. x 3ft. glass window (which can be soiled with body oils from a handprint) and wiped with two paper towels to near dryness, simulating actual consumer usage of the product. Grading:
  • 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.
  • C14 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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne une composition détergente aqueuse liquide pour surfaces dures. Cette composition présente de très bonnes caractéristiques en matière de pouvoir lubrifiant superficiel, de formation en pellicule ou de constitution d'irrégularités d'épaisseur. La composition comporte au maximum environ 1 % en poids d'un agent tensioactif détergeant linéaire sulfate d'alkyle en C8-C18. En l'occurrence plus d'environ 30 % du poids dudit agent tensioactif présente une longueur en chaîne de C14. Cet agent tensioactif est en outre sensiblement exempt de composés alcool gras n'ayant pas réagi et de composés alcanolamine. Enfin, cet agent tensioactif convient particulièrement au nettoyage du verre.
PCT/US1996/005561 1995-05-05 1996-04-23 Compositions de nettoyage du verre comportant des agents tensioactifs lineaires sulfates d'alkyle WO1996034933A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
DE69604660T DE69604660T2 (de) 1995-05-05 1996-04-23 Glasreinigerzusammensetzungen enthaltend lineare akylsulfattenside
AU55642/96A AU5564296A (en) 1995-05-05 1996-04-23 Glass cleaner compositions having linear alkyl sulfate surfa ctants
CA002220131A CA2220131C (fr) 1995-05-05 1996-04-23 Compositions de nettoyage du verre comportant des agents tensioactifs lineaires sulfates d'alkyle
MX9708503A MX9708503A (es) 1995-05-05 1996-04-23 Composiciones para limpiar vidrio que tienen agentes tensioactivos de alquil sulfato lineal.
DK96913006T DK0823937T3 (da) 1995-05-05 1996-04-23 Glasrensningssammensætninger med lineært alkylsulfatoverfladeaktive midler
BR9608216A BR9608216A (pt) 1995-05-05 1996-04-23 Composições de limpeza de vidro tendo tensoativos de sulfato de alquila linear
EP96913006A EP0823937B1 (fr) 1995-05-05 1996-04-23 Compositions de nettoyage du verre comportant des agents tensioactifs lineaires sulfates d'alkyle
GR990403373T GR3032284T3 (en) 1995-05-05 1999-12-29 Glass cleaner compositions having linear alkyl sulfate surfactants

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US43606395A 1995-05-05 1995-05-05
US08/436,063 1995-05-05

Publications (1)

Publication Number Publication Date
WO1996034933A1 true WO1996034933A1 (fr) 1996-11-07

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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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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)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5759980A (en) * 1997-03-04 1998-06-02 Blue Coral, Inc. Car wash
WO1999009135A1 (fr) * 1997-08-13 1999-02-25 The Procter & Gamble Company Composition de nettoyage de vitres, a bon pouvoir lubrifiant de surfaces et a tampon alcalin
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
WO2003072696A1 (fr) * 2002-02-22 2003-09-04 Colgate-Palmolive Company Chiffon de nettoyage antibacterien
EP1457836B2 (fr) † 2003-03-10 2016-08-17 FUJIFILM Corporation Solution de développement pour les précurseurs de plaque lithographique et procédé pour la fabrication des plaques lithographiques

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2243257A1 (de) * 1972-09-02 1974-03-21 Robert Boschung Reinigungsmittel fuer glasscheiben oder dergleichen
WO1993016162A1 (fr) * 1992-02-07 1993-08-19 The Clorox Company Nettoyant pour surfaces dures laissant des residus reduits
EP0595383A1 (fr) * 1992-10-26 1994-05-04 The Procter & Gamble Company Composition détergente liquide pour surfaces dures contenant des détergents tension-actifs amphocarboxylate à chaîne courte
WO1995018210A1 (fr) * 1993-12-30 1995-07-06 The Procter & Gamble Company Compositions detergentes liquides pour surfaces dures, contenant des adjuvants

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2243257A1 (de) * 1972-09-02 1974-03-21 Robert Boschung Reinigungsmittel fuer glasscheiben oder dergleichen
WO1993016162A1 (fr) * 1992-02-07 1993-08-19 The Clorox Company Nettoyant pour surfaces dures laissant des residus reduits
EP0595383A1 (fr) * 1992-10-26 1994-05-04 The Procter & Gamble Company Composition détergente liquide pour surfaces dures contenant des détergents tension-actifs amphocarboxylate à chaîne courte
WO1995018210A1 (fr) * 1993-12-30 1995-07-06 The Procter & Gamble Company Compositions detergentes liquides pour surfaces dures, contenant des adjuvants

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5759980A (en) * 1997-03-04 1998-06-02 Blue Coral, Inc. Car wash
WO1999009135A1 (fr) * 1997-08-13 1999-02-25 The Procter & Gamble Company Composition de nettoyage de vitres, a bon pouvoir lubrifiant de surfaces et a tampon alcalin
US6420326B1 (en) 1997-08-13 2002-07-16 The Procter & Gamble Company 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?
US6627590B1 (en) 1998-05-22 2003-09-30 The Procter & Gamble Company Acidic cleaning compositions with C10 alkyl sulfate detergent surfactant
US6013323A (en) * 1998-10-30 2000-01-11 Klayder; Donna W. Silicone gel waxes and silicone gel protectants
WO2003072696A1 (fr) * 2002-02-22 2003-09-04 Colgate-Palmolive Company Chiffon de nettoyage antibacterien
EP1457836B2 (fr) † 2003-03-10 2016-08-17 FUJIFILM Corporation Solution de développement pour les précurseurs de plaque lithographique et procédé pour la fabrication des plaques lithographiques

Also Published As

Publication number Publication date
DE69604660T2 (de) 2000-05-18
DK0823937T3 (da) 1999-12-27
AR001845A1 (es) 1997-12-10
ATE185591T1 (de) 1999-10-15
BR9608216A (pt) 1999-05-25
EP0823937B1 (fr) 1999-10-13
CO4700538A1 (es) 1998-12-29
CA2220131A1 (fr) 1996-11-07
AU5564296A (en) 1996-11-21
EP0823937A1 (fr) 1998-02-18
MX9708503A (es) 1998-02-28
GR3032284T3 (en) 2000-04-27
DE69604660D1 (de) 1999-11-18
CA2220131C (fr) 2001-03-27
ES2136988T3 (es) 1999-12-01

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