EP0630963A2 - Saure Mikroemulsion - Google Patents

Saure Mikroemulsion Download PDF

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Publication number
EP0630963A2
EP0630963A2 EP94304492A EP94304492A EP0630963A2 EP 0630963 A2 EP0630963 A2 EP 0630963A2 EP 94304492 A EP94304492 A EP 94304492A EP 94304492 A EP94304492 A EP 94304492A EP 0630963 A2 EP0630963 A2 EP 0630963A2
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EP
European Patent Office
Prior art keywords
acid
composition
alpha hydroxy
hydroxy aliphatic
aminoalkylenephosphonic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94304492A
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English (en)
French (fr)
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EP0630963A3 (de
Inventor
Regis Lysy
Maurice Marchal
Claude Blanvalet
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Colgate Palmolive Co
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Colgate Palmolive Co
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Publication date
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Publication of EP0630963A2 publication Critical patent/EP0630963A2/de
Publication of EP0630963A3 publication Critical patent/EP0630963A3/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • 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
    • C11D3/50—Perfumes
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C11D17/0021—Aqueous microemulsions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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

Definitions

  • This invention relates to a cleaner for hard surfaces, such as bathtubs, sinks, tiles, porcelain and enamelware, which removes soap scum, lime scale and grease from such surfaces without harming them. More particularly, the invention relates to an acidic microemulsion that can be sprayed onto the surface to be cleaned, and wiped off without usual rinsing and still leave the cleaned surface bright and shiny. The invention also relates to a method for using such compositions.
  • Hard surface cleaners such as bathroom cleaners and scouring cleansers
  • Scouring cleansers normally include a soap or synthetic organic detergent or surface active agent and an abrasive. Such products can scratch relatively soft surfaces and can eventually cause them to appear dull. These products are often ineffective to remove lime scale (usually encrusted calcium and magnesium carbonates) in normal use. Because lime scale can be removed by chemical reactions with acidic media various acidic cleaners have been produced and have met with various degrees of success. In some instances such cleaners have been failures because the acid employed was too strong and damaged the surfaces being cleaned. At other times, the acidic component of the cleaner reacted objectionably with other components of the product which adversely affected the detergent or perfume.
  • Example 3 of that application discloses an acidic, clear, oil-in-water microemulsion which is therein described as being successfully employed to clean shower wall tiles of lime scale and soap scum that had adhered to them. Such cleaning was effected by applying the cleaner to the walls followed by wiping or minimal rinsing after which the walls were allowed to dry to a good shine.
  • the described microemulsion cleaner of that patent application is effective in removing lime scale and soap scum from hard surfaces and is easy to use, but it has been found that its mixture of acidic agents (succinic, glutaric and adipic acids) could damage the surfaces of some hard fixtures, such as those of materials which are not acid resistant.
  • acidic agents succinic, glutaric and adipic acids
  • One of such materials is an enamel that has been extensively employed in Europe as a coating for bathtubs, herein referred to as European enamel. It has been described as zirconium white enamel or zirconium white powder enamel and has the advantage of being resistant to detergents, which makes it suitable for use on tubs, sinks, shower tiles and bathroom enamelware.
  • zirconium white enamel or zirconium white powder enamel has the advantage of being resistant to detergents, which makes it suitable for use on tubs, sinks, shower tiles and bathroom enamelware.
  • such enamel is sensitive to acids and is severely damaged by use of the microemulsion acidic cleaner based on the
  • the instant compositions of present invention allow the cleaning of European enamel surfaces, as well as any other acid resistant surfaces of bathtubs and other bathroom surfaces.
  • the product can be used on various other materials that are especially susceptible to attack by acidic media, such as marble.
  • the instant compositions employ alpha-hydroxy aliphatic acids in place of the mixture of succinic, glutaric and adipic acids previously used in the acidic microemulsion.
  • the instant compositions which employ the alpha hydroxy aliphatic acids are less detrimental to European enamel or other acid susceptible surfaces such as marble than the mixture of succinic, glutaric and adipic.
  • the instant inventions can be thickened by a xanthan gum such as described in copending U.S. Serial No. 07/950,370 filed September 1992.
  • an acidic aqueous cleaner for bathtubs and other hard surfaced items which are acid resistant or are of zirconium white enamel wherein the cleaner has a pH in the range of 1 to 4 and the cleaner removes lime scale, cap scum and greasy soil from surfaces of such items without damaging such surfaces, comprises: a detersive proportion of at least one synthetic organic detergent which is capable of removing greasy soil from such surfaces; a lime scale and soap scum removing proportion of an alpha-hydroxy aliphatic acid(s) having 2 to 6 preferably 3 to 5 carbon atoms; an aminoalkylenephosphonic acid in such proportion as to prevent damage to zirconium white enamel surfaces of items to be cleaned by the alpha-hydroxy aliphatic acid; phosphoric acid and an aqueous medium for the detergent, alpha hydroxy aliphatic acid, phosphoric acid and aminoalkylenephosphonic acid.
  • the present thickened, acidic microemulsion compositions preferably comprise approximately by weight:
  • the synthetic organic detergent may be any suitable anionic, nonionic, amphoteric, ampholytic, zwitterionic or cationic detergent or mixture thereof, but anionic and nonionic detergents are preferred as well as mixtures thereof.
  • the nonionic surfactant than can be employed in the present liquid detergent composition is present in amounts of about 0 to 5%, preferably 0.5 to 4.5%, most preferably 1 to 4%, by weight of the composition and provides superior performance in the removal of soil.
  • the water soluble nonionic surfactants utilized in this invention are preferably commercially well known and include the primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkylphenol ethoxylates and ethylene-oxide-propylene oxide condensates on primary alkanols, such as Plurafacs (BASF) and condensates of ethylene oxide with sorbitan fatty acid esters such as the Tweens (ICI).
  • the nonionic synthetic organic detergents generally are the condensation products of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups.
  • any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a water soluble nonionic detergent. Further, the length of the polyethenoxy hydrophobic and hydrophilic elements.
  • the nonionic detergent class includes the condensation products of a higher alcohol (e.g., an alkanol containing about 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with about 5 to 30 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 16 moles of ethylene oxide (EO), tridecanol condensed with about 6 to moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.
  • a higher alcohol e.g., an
  • Neodol ethoxylates which are higher aliphatic, primary alcohol containing about 9-15 carbon atoms, such as C9-C11 alkanol condensed with 8 moles of ethylene oxide (Neodol 91-8), C12 ⁇ 13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C12 ⁇ 15 alkanol condensed with 12 moles ethylene oxide (Neodol 25-12), C14 ⁇ 15 alkanol condensed with 13 moles ethylene oxide (Neodol 45-13), and the like.
  • Neodol ethoxylates such as C9-C11 alkanol condensed with 8 moles of ethylene oxide (Neodol 91-8), C12 ⁇ 13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C12 ⁇ 15 alkanol condensed with 12 moles ethylene oxide (Neodol 25
  • Such ethoxamers have an HLB (hydrophobic lipophilic balance) value of about 8 to 15 and give good O/W (oil in water) emulsification, whereas ethoxamers with HLB values below 8 contain less than 5 ethyleneoxide groups and tend to be poor emulsifiers and poor detergents.
  • HLB hydrophobic lipophilic balance
  • Additional satisfactory water soluble alcohol ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide.
  • Examples of commercially available nonionic detergents of the foregoing type are C11-C15 secondary alkanol condensed with either 9 EO (Tergitol 15-S-9) or 12 EO (Tergitol 15-S-12) marketed by Union Carbide.
  • nonionic detergents include the polyethylene oxide condensates of one mole of alkyl phenol containing from about 8 to 18 carbon atoms in a straight- or branched chain alkyl group with about 5 to 30 moles of ethylene oxide.
  • alkyl phenol ethoxylates include nonyl condensed with about 9.5 moles of EO per mole of nonyl phenol, dinonyl phenol condensed with about 12 moles of EO per mole of phenol, dinonyl phenol condensed with about 15 moles of EO per mole of phenol and di-isoctylphenol condensed with about 15 moles of EO per mole of phenol.
  • nonionic surfactants of this type include Igepal CO-630 (nonyl phenol ethoxylate) marketed by GAF Corporation.
  • nonionic detergents are the water-soluble condensation products of a C8-C20 alkanol with a heteric mixture of ethylene oxide and propylene oxide wherein the weight ratio of ethylene oxide to propylene oxide is from 2.5:1 to 4:1, preferably 2.8:1 to 3.3:1, with the total of the ethylene oxide and propylene oxide including the terminal ethanol or propanol group) being from 60 to 85%, preferably 30 to 80%, by weight.
  • Such detergents are commercially available from BASF-Wyandotte and a particularly preferred detergent is a C10-C16 alkanol condensate with ethylene oxide and propylene oxide, the weight ratio of ethylene oxide to propylene oxide being 3:1 and the total alkoxy content being about 75% by weight.
  • Condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri-C10-C20 alkanoic acid esters having a HLB of 8 to 15 also may be employed as the nonionic detergent ingredient in the described shampoo.
  • These surfactants are well known and are available from Imperial Chemical Industries under the Tween trade name. Suitable surfactants include polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate.
  • Suitable water-soluble nonionic detergents which are less preferred are marketed under the trade name "Pluronics". These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the molecular weight of the hydrophobic portion of the molecule is of the order of 950 to 4000 and preferably 200 to 2,500.
  • the addition of polyoxyethylene radicals to the hydrophobic portion tends to increase the solubility of the molecule as a whole so as to make the surfactant water-soluble.
  • the molecular weight of the block polymers varies from 1,000 to 15,000 and the polyethylene oxide content may comprise 20% to 80% by weight.
  • these surfactants will be in liquid form and satisfactory surfactants are available as grades L62 and L64.
  • the anionic surfactant, used in the microemulsion composition constitutes about 1% to 9%, preferably 2% to 8%, most preferably 2% to 7%, by weight.
  • the anionic surfactants which may be used in the instant microemulsion detergent of the invention are water soluble such as triethanolamine salt and include the sodium, potassium, ammonium and ethanolammonium salts of C8 ⁇ 18 alkyl sulfates such as lauryl sulfate, myristyl sulfate and the like; C8-C18 ethoxylated alkyl ether sulfates; linear C8-C16 alkyl benzene sulfonates; C10-C20 paraffin sulfonates; alpha olefin sulfonates containing about 10-24 carbon atoms; C8-C18 alkyl sulfoacetates; C8-C18 alkyl sulfosuccinate esters; C8-C18 acyl isethionates; and C8-C18 acyl taurates.
  • Preferred anionic surfactants are the water soluble alkyl sulfates.
  • the paraffin sulfonates may be monosulfonates or disulfonates and usually are mixtures thereof, obtained by sulfonating paraffins of 10 to 20 carbon atoms.
  • Preferred paraffin sulfonates are those of C12 ⁇ 18 carbon atoms chains, and more preferably they are of C14 ⁇ 17 chains.
  • Paraffin sulfonates that have the sulfonate group(s) distributed along the paraffin chain are described in U.S. Patents 2,503,280; 2,507,088; 3,260,744; and 3,372,188; and also in German Patent 735,096. Such compounds may be made to specifications and desirably the content of paraffin sulfonates outside the C14 ⁇ 17 range will be minor and will be minimized, as will be any contents of di- or poly-sulfonates.
  • Suitable other sulfonated anionic detergents are the well known higher alkyl mononuclear aromatic sulfonates, such as the higher alkylbenzene sulfonates containing 9 to 18 or preferaby 9 or 10 to 15 or 16 carbon atoms in the higher alkyl group in a straight or branched chain, or C8 ⁇ 15 alkyl toluene sulfonates.
  • a preferred alkylbenzene sulfonate is a linear alkylbenzene sulfonate having a higher content of 3-phenyl (or higher isomers and a correspondingly lower content (well below 50%) of 2-phenyl (or lower) isomers, such as those sulfonates wherein the benzene ring is attached mostly at the 3 or higher (for example 4, 5, 6 or 7) position of the alkyl group and the content of the isomers in which the benzene ring is attached in the 2 or 1 position is correspondingly low.
  • Preferred materials are set forth in U.S. Patent 3,320,174, especially those in which the alkyls are of 10 to 13 carbon atoms.
  • the higher alkyl ether sulfates used in the present invention are represented by the formula: RO(C2H4O)nSO3M in which R is a primary or secondary alkyl group that may be straight or branched having from 10 to 18 carbon atoms, preferably 12 to 15, especially 12 to 14, and most preferably 12 to 13 carbon atoms.
  • M is an alkali metal or ammonium cation and n is a number from 1 to 10, preferably 1 to 6, especially 2 or 3.
  • These detergents are produced by sulfating the corresponding ether alcohol and then neutralizing the resulting sulfuric acid ester thereof.
  • the sodium and ammonium salts of the ether sulfates are especially preferred.
  • alkyl sulfate anionic detergent compounds which are useful in the present invention have from 6 to 18 carbon atoms in the alkyl group and can be represented by the following general formula: R2SO4M in which R2 is straight or branched chain alkyl of from 6 to 8, especially from 8 to 14 carbon atom chain length and M is an alkali metal or ammonium carbon, especially sodium.
  • R2SO4M straight or branched chain alkyl of from 6 to 8, especially from 8 to 14 carbon atom chain length
  • M is an alkali metal or ammonium carbon, especially sodium.
  • Straight chain alkyl groups are preferred.
  • the active acidic component of the acidic emulsions is an alpha hydroxy aliphatic acid which is strong enough to lower the pH of the microemulsion to be in the range of one to four.
  • carboxylic acids can perform this function but those which have been found effectively to remove soap scum and lime scale from bathroom surfaces best, while still not destabilizing the emulsion, are alpha hydroxy aliphatic acids having the structure: wherein Y is selected from the group consisting of hydroxy or a COOH group and X is (CH2) n W, wherein W is selected from the group consisting of CH3 or COOH and n is 0, 1, or 2.
  • Preferred alpha hydroxy aliphatic acids are citric acid, lactic acid and malic acid, wherein a mixture of lactic acid and malic acid is preferred, wherein the weight ratio of lactic acid to malic acid is preferred to be about 5:1 to about 1:1, more preferably about 4:1 to about 1:1.
  • the at least one alpha hydroxy aliphatic acid is incorporated in the composition in an amount of about 2 to about 9 wt. %, more preferably about 2 to about 7 wt. %.
  • the alpha hydroxy aliphatic acid after being incorporated in the acidic emulsion, may be partially neutralized to produce the desired pH in the emulsion, for greatest functional effectiveness, with safety.
  • Phosphoric acid is one of the additional acids that helps to protect acid-sensitive surfaces being cleaned with the present emulsion cleaner. Being a tribasic acid, it too may be partially neutralized to obtain an emulsion pH in the desired range. For example. It may be partially neutralized to the biphosphate, e.g., NaH2PO4, or NH4H2PO4.
  • Phosphonic acid the other of the two additional acids for protecting acid-sensitive surfaces from the dissolving action of the dicarboxylic acids of the present thickened emulsions, apparently exists only theoretically, but its derivatives are stable and are useful in the practice of the present invention.
  • the phosphonic acids are of the structure. wherein Y is any suitable substituent, but preferably Y is alkylamino or N-substituted alkylamino.
  • a preferred phosphonic acid component of the present thickened acidic emulsions is aminotri (methylenephosphonic) acid which is of the formula N (CH2PH x O3)
  • aminotri (methylenephosphonic) acid which is of the formula N (CH2PH x O3)
  • other useful phosphonic acids are ethylene diamine tetra-(methylenephosphonic) acid, hexamethylenediamine tetra-(methylenephosphonic) acid, and diethylenetriamine penta-(methylenephosphonic) acid.
  • Such class of compounds may be described as aminoalkylenephosphonic acids containing in the range of 1 to 3 amino nitrogen, 3 or 4 lower alkylenephosphonic acid groups in which the lower alkylene is of 1 or 2 carbon atoms, and 0 to 2 alkylene groups of 2 to 6 carbon atoms each, which alkylene(s) is/are present and join amino nitrogen when a plurality of such amino nitrogen is present in the aminoalkylenephosphonic acid.
  • aminoalkylenephosphonic acids which also may be partially neutralized at the desire pH of the microemulsion cleaner, are of desired stabilizing and protecting effect in the invented cleaner, especially when present with phosphoric acid, preventing harmful attacks on European enamel surfaces by the alpha hydroxy aliphatic components of the cleaner.
  • the thickener which is optionally used in the acidic microemulsion is a xanthan gum called Kelzan T sold by Merck & Co.
  • the xanthan gum is an exocellular hetropolysaccharide having a molecular weight of about 1,000,000 to 10,000,000 and is used in a concentration of o to about 1.0 weight percent, more preferably about 0.1 to about 0.7 weight percent, and most preferably 0.2 to 0.6 weight percent. When used at these concentration levels, the composition retains its microemulsion characteristics in that the essential micellar aggregates are maintained. The composition is still sprayable and will cling nicely to a vertical wall.
  • compositions having the xanthan gum incorporated therein are shear thinning which means that the composition can be easily removed from the surface being cleaned without much mechanical action.
  • Other cellulose, hydroxypropyl cellulose, polyacrylamides and poly vinyl alcohol will create shear thickening compositions.
  • the water that is used in making the present microemulsions may be tap water but is preferably of low hardness, normally being less than 150 parts per million (p.p.m.) of hardness. Still, useful cleaners can be made from tap waters that are higher in hardness, up to 3000 p.p.m. Most preferably the water employed will be distilled or deionized water, in which the content of hardness ions is less than 25 p.p.m.
  • Various other components may desirably be present in the invented cleaners, including preservatives such as sodium benzoate, antioxidants or corrosion inhibitors, cosolvents, cosurfactant, multivalent metal ions, perfumes, colorants and terpenes (and terpineols), but various other adjuvants conventionally employed in liquid detergents and hard surface cleaners may also be present, provided that they do not interfere with the cleaning and scum-and scale-removal functions of the cleaner.
  • preservatives such as sodium benzoate, antioxidants or corrosion inhibitors, cosolvents, cosurfactant, multivalent metal ions, perfumes, colorants and terpenes (and terpineols)
  • cosolvents such as sodium benzoate, antioxidants or corrosion inhibitors, cosolvents, cosurfactant, multivalent metal ions, perfumes, colorants and terpenes (and terpineols
  • the perfumes which, with tarpenes, terpenes and hydrocarbons (which may be substituted for the perfumes or added to them) function as especially effective solvents for greasy soils on hard surfaces being leaned, and form the dispersed phases of oil-in-water (o/w) microemulsions.
  • co-surfactant and polyvalent metal ions are also of functional importance, with the former helping to stabilize the microemulsion and the latter adding in improving detergency, especially for more dilute cleaners, and when the polyvalent salts of the anionic detergent are employed affording more effective detergents against the greasy soil encountered in use.
  • the various perfumes that have been found to be useful in forming the dispersed phase of the thickened acidic microemulsion cleaners may be those normally employed in cleaning products and preferably are normally in liquid state. They include esters, ethers, aldehydes, alcohols and alkanes employed in perfumery but of most importance are the essential oils that are high in terpene content. It appears that the terpenes (and terpineols) coact with the detersive components of microemulsions to improve detergency of the invented compositions, in addition to forming the stable dispersed phase of the microemulsions.
  • the polyvalent metal ion present in the invented cleaners may be any suitable ion including, but not limited to, magnesium (usually preferred) aluminum, copper, nickel, iron or calcium.
  • the ion or mixture thereof may be added in any suitable form, sometimes as an oxide or hydroxide, but usually as a water soluble salt. It appears that the polyvalent metal ion reacts with the anion of the anionic detergent (or replaces the detergent cation, or makes an equivalent solution in the emulsion), which improves detergency and generally improves other properties of the product, too. If the polyvalent metal ion reacts with the detergent anion to form an insoluble product such polyvalent ion should be avoided.
  • the polyvalent metal ion will preferably be magnesium, and such will be added to the other emulsion components as a water soluble salt.
  • a preferred such salt is magnesium sulfate, usually employed as its heptahydrate (Epsom salts), but other hydrates thereof or the anhydride may be used too.
  • the sulfates of the polyvalent metals will be used because the sulfate anion thereof is also the anion of some of the anionic detergents and is found in some such detergents as a byproduct of neutralization.
  • the cosurfactant component(s) of the acidic cleaners reduce the interfacial tension or surface tension between the lipophilic droplets and the continuous aqueous medium to a value that is often close to 10 ⁇ 3 dynes/cm., which results in spontaneous disintegrations of the dispersed phase globules until they become so small as to be invisible to the human eye forming a clear microemulsion.
  • the surface area of the dispersed phase increases greatly and its solvent power and grease removing capability are also increased, so that the acidic microemulsion is significantly more effective as a cleaner for removing greasy soil than when the dispersed phase globules are of ordinary emulsion size.
  • water soluble lower alkanols of 2 to 4 carbon atoms per molecule (sometimes preferably 3 or 4): polypropylene glycols of 2 to 18 propoxy units; monoalkyl lower glycol ethers of the formula RO(X) n H, wherein R is C1 ⁇ 4 alkyl, X is CH2CH2CH2O or CH(CH3)CH2O, and n is from 1 to 4; monoalkyl esters of the formula R1 is C2 ⁇ 4 acyl and X and n are as immediately previously described; aryl substituted alkanols of 1 to 4 carbon atoms; propylene carbonate; alpha hydroxy aliphatic acids of 2 to 6 carbon atoms such as mono- di- and tri hydroxy substituted aliphatic mono- di- and tricarboxylic acids of 2 to 6 carbon atoms; lower alkyl mono- di- and triesters of phosphoric acid wherein the lower alky
  • cosurfactants can be used in combination with the alpha hydroxy aliphatic acids which function as cosurfactants.
  • These non acid cosurfactants will usually be used in conjunction with the alpha hydroxy aliphatic acid cosurfactants in an amount of about 0.1 to about 5 wt. %, more preferably about 0.5 to about 4.0 wt. % depending upon the concentration of the alpha hydroxy aliphatic acid cosurfactant.
  • cosurfactants are lactic. malic and citric acids, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether and diethylene glycol mono-isobutyl ether, which are considered to be the most effective.
  • the proportions of the components are in certain ranges so that the product may be most effective in removing greasy soils, lime scale and soap scum, and other deposits from the hard surfaces subjected to treatment, and so as to protect such surfaces during such treatment.
  • the detergent should be present in detersive proportion, sufficient to remove greasy and oily soils; the proportion(s) of the alpha hydroxy aliphatic acid(s) should be sufficient to remove soap scum and lime scale; the phosphonic acid or phosphoric and phosphonic acids mixture should be enough to prevent damage of acid sensitive surfaces by the alpha hydroxy aliphatic acid(s); and the aqueous medium should be a solvent and suspending medium for the required components and for any adjuvants that may be present, too.
  • such percentages of components will be by weight 0 to 1.0% of xanthan gum, 1 to 9% of synthetic anionic organic detergent(s), 0 to 5% of synthetic organic nonionic detergent(s), 2 to 9% of alpha hydroxy aliphatic acids, 0.05 to .6% of phosphoric acid or mono-salt thereof and 0.005 to 2% of phosphonic acid(s), 0 to 0.6% aminoalkylenephosphonic acid(s), or mono-phosphonic salt(s) thereof; and the balance being water and adjuvant's) if any are present.
  • the alpha hydroxy aliphatic acids it is preferred that a mixture of lactic and malic acids be employed.
  • the ratio of the alpha hydroxy aliphatic acid to the aminoalkylenephosphonic acid in the instant composition is about 5:1 to about 250:1, more preferably about 2:1 to about 10:1 and the ratio of the alpha hydroxy aliphatic acid to the phosphoric acid is about 5:2 to 25:1.
  • the cleaner usually there will be present in the cleaner, especially when an anionic surfactant is present 0.05 to 5%, and preferably 0.1 to 3.0% of polyvalent ion, preferably magnesium or aluminum, and more preferably magnesium.
  • the percentage of perfume will normally be in the 0.2 to 2% range, preferably being in the 0.5 to 1.5% range of which perfume at least 0.1% is terpene or terpineol.
  • the terpineol is alpha-terpineol and is preferably added to allow a reduction in the amount of perfume, with the total perfume (including the alpha-terpineol) being 50 to 90% of terpineol, preferably about 80% thereof.
  • the pH of the various preferred microemulsion cleaners is usually 1 to 4, preferably 1.5 to 3.5 e.g. 3.
  • the water content of the microemulsions will usually be in the range of about 75 to 90%, preferably about 80 to 85% and the adjuvant content will be from 0 to 5%, usually about 1 to 3%. If the pH is not in the desired range it will usually be adjusted with either sodium hydroxide or suitable acid, e.g. sulfuric acid, solution, but normally the pH will be raised, not lowered, and it if is to be lowered more of the alpha hydroxy acid mixture can be used, instead.
  • suitable acid e.g. sulfuric acid
  • the liquid cleaners can be manufactured by mere mixing of the various components thereof, with orders or additions not being critical.
  • such procedure may be varied to prevent any undesirable reactions between components.
  • the cleaner may desirably be packed in manually operated spray dispensing containers, which are usually and preferably made of synthetic organic polymeric plastic material, such as polyethylene, polypropylene or polyvinyl chloride (PVC). Such containers also preferably include nylon or other non-reactive plastic closure, spray nozzle, dip tube and associated dispenser parts, and the resulting packaged cleaner is ideally suited for use in "spray and wipe” applications. However, in some instances, as when lime scale and soap scum deposits are heavy, the cleaner may be left on until it has dissolved or loosened the deposit(s) and may then be wiped off, or may be rinsed off, or multiple applications may be made, followed by multiple removals, until the deposits are gone.
  • synthetic organic polymeric plastic material such as polyethylene, polypropylene or polyvinyl chloride (PVC).
  • PVC polyvinyl chloride
  • Such containers also preferably include nylon or other non-reactive plastic closure, spray nozzle, dip tube and associated dispenser parts, and the resulting packaged cleaner is ideally suited
  • the microemulsion cleaner is made by dissolving the optional xanthan gum and benzoates and then dissolving the detergent in the water, after which the rest of the water soluble materials are added to the detergent solution, with stirring, except for the perfume and the adjusting agent (sodium hydroxide solution).
  • the pH is adjusted to 3.0 and then the perfume is stirred into the aqueous solution, instantaneously generating the desired microemulsion, which is clear blue.
  • the acid cleaner is packed in polyethylene squeeze bottles equipped with polypropylene spray nozzles which are adjustable to closed spray and stream positions.
  • the microemulsion is sprayed onto "bathtub ring" on a bathtub, which also includes lime scale, in addition to soap scum and greasy soil.
  • the rate of application is about 5 ml. per 5 meters of ring (which is about 3 cm. wide). After application and a wait of about two minutes the ring is wiped off with a sponge and is sponged off with water, it is found that the greasy soil, soap scum, and even the lime scale, have been removed effectively.
  • a second application may be desirable, but that is not considered to be the norm.
  • the tub surface may be rinsed because it is so easy to rinse a bathtub (or a shower) but such rinsing is not necessary.
  • the surface may be sponged with water or wiped with a wet cloth but in such case it is not necessary to use more than ten times the weight of cleaner applied. In other words, the surface does not need to be thoroughly doused or rinsed with water, and it still will be clean and shiny (providing that it was originally shiny). In other uses of the cleaner, it may be employed to clean shower tiles, bathroom floor tiles, kitchen tiles, sinks and enamelware, generally, without harming the surfaces thereof.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP94304492A 1993-06-24 1994-06-21 Saure Mikroemulsion. Withdrawn EP0630963A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US8063493A 1993-06-24 1993-06-24
US80634 1993-06-24

Publications (2)

Publication Number Publication Date
EP0630963A2 true EP0630963A2 (de) 1994-12-28
EP0630963A3 EP0630963A3 (de) 1995-05-10

Family

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EP94304492A Withdrawn EP0630963A3 (de) 1993-06-24 1994-06-21 Saure Mikroemulsion.

Country Status (12)

Country Link
EP (1) EP0630963A3 (de)
JP (1) JPH07305100A (de)
KR (1) KR950000852A (de)
CN (1) CN1107509A (de)
AU (1) AU6337694A (de)
BR (1) BR9402493A (de)
CA (1) CA2126626A1 (de)
HU (1) HUT68690A (de)
NZ (1) NZ260608A (de)
PL (1) PL177789B1 (de)
PT (1) PT101531B (de)
ZA (1) ZA944078B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997040133A1 (en) * 1996-04-24 1997-10-30 Colgate-Palmolive Company Thickened acid composition
WO2000071667A1 (en) * 1999-05-21 2000-11-30 Colgate-Palmolive Company Acidic light duty liquid cleaning compositions

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100419752B1 (ko) * 1999-12-28 2004-02-21 주식회사 하이닉스반도체 반도체소자의 제조방법
JP2004075764A (ja) 2002-08-13 2004-03-11 Takasago Internatl Corp 硬質物体表面洗浄液用組成物
KR20020070250A (ko) * 2002-08-20 2002-09-05 홍성칠 건축 구조물의 내외벽 세척을 위한 세제 조성물
JP4884768B2 (ja) * 2005-12-28 2012-02-29 花王株式会社 硬質表面用洗浄剤
CN107057875A (zh) * 2017-04-12 2017-08-18 佛山市德可为装饰材料有限公司 用于清洗瓷砖背面附着物的清洗剂
US12351775B2 (en) 2021-05-14 2025-07-08 Ecolab Usa Inc. Neutralizing instrument reprocessing

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IT951279B (it) * 1971-07-01 1973-06-30 Benckiser Gmbh Joh A Processo per impedire il formarsi di depositi che producono incrosta zioni nei sistemi acquosi
DE2507156A1 (de) * 1975-02-20 1976-09-02 Hoechst Ag Saure allzweck-reinigungsmittel
US4246030A (en) * 1978-12-08 1981-01-20 The Mogul Corporation Corrosion inhibiting compositions and the process for using same
FR2466500A1 (fr) * 1979-10-04 1981-04-10 Produits Ind Cie Fse Procede de nettoyage de vehicules et composition mise en oeuvre
JPH075907B2 (ja) * 1987-04-01 1995-01-25 花王株式会社 浴室用洗浄剤組成物
US5108643A (en) * 1987-11-12 1992-04-28 Colgate-Palmolive Company Stable microemulsion cleaning composition
US5192460A (en) * 1988-02-10 1993-03-09 Colgate-Palmolive Company Safe acidic hard surface cleaner
DE3910042A1 (de) * 1989-03-28 1990-10-04 Sebastian Reinhardt Mittel zur dauerhaften reinigung von metalloberflaechen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997040133A1 (en) * 1996-04-24 1997-10-30 Colgate-Palmolive Company Thickened acid composition
WO2000071667A1 (en) * 1999-05-21 2000-11-30 Colgate-Palmolive Company Acidic light duty liquid cleaning compositions

Also Published As

Publication number Publication date
NZ260608A (en) 1995-02-24
HUT68690A (en) 1995-07-28
PT101531B (pt) 1999-12-31
PT101531A (pt) 1995-03-31
PL177789B1 (pl) 2000-01-31
CN1107509A (zh) 1995-08-30
HU9401898D0 (en) 1994-09-28
ZA944078B (en) 1995-12-11
KR950000852A (ko) 1995-01-03
EP0630963A3 (de) 1995-05-10
AU6337694A (en) 1995-01-05
JPH07305100A (ja) 1995-11-21
PL303966A1 (en) 1995-01-09
CA2126626A1 (en) 1994-12-25
BR9402493A (pt) 1995-01-24

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