EP0391392B1 - Compositions aqueuses détergentes peu moussantes et stables au froid comprenant des agents tensioactifs non ioniques, anioniques et cationiques et leur application - Google Patents

Compositions aqueuses détergentes peu moussantes et stables au froid comprenant des agents tensioactifs non ioniques, anioniques et cationiques et leur application Download PDF

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EP0391392B1
EP0391392B1 EP90106442A EP90106442A EP0391392B1 EP 0391392 B1 EP0391392 B1 EP 0391392B1 EP 90106442 A EP90106442 A EP 90106442A EP 90106442 A EP90106442 A EP 90106442A EP 0391392 B1 EP0391392 B1 EP 0391392B1
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surfactant
weight
ethylene oxide
oxide units
anionic
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EP0391392A3 (fr
EP0391392A2 (fr
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Wolfgang Klinger
Eckhard Milewski
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • 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
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • 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
    • 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
    • C11D1/18—Sulfonic acids or sulfuric acid esters; Salts thereof derived from amino alcohols
    • C11D1/20—Fatty acid condensates
    • 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols

Definitions

  • the invention relates to low-foaming and cold-stable liquid surfactant compositions which consist essentially of water and nonionic, anionic and cationic surfactants.
  • the invention further relates to the use of these surfactant compositions.
  • anionic surfactants and cationic surfactants in a molar ratio of about 1: 1 in the presence of water.
  • These compositions with an anionic surfactant and a cationic surfactant are described as an aqueous suspension or emulsion and, in the case of higher concentrations, as a gel-like mass.
  • a surfactant composition which essentially consists of an ether sulfate as anionic surfactant and dodecylbenzyltrimethylammonium chloride as a cationic surfactant in a ratio of 1: 1 and from more than 99% by weight of water.
  • compositions containing an anionic surfactant and a cationic surfactant have very advantageous surfactant properties, it would be extremely desirable to have such compositions available that are liquid and therefore easy to handle even at a relatively high surfactant concentration.
  • Such surfactant compositions are described in the more recent GB-A-2 195 653. These are aqueous emulsions consisting essentially of 10 parts of an anionic surfactant and a cationic surfactant in a molar ratio of about 1: 1, 0.5 to 10 parts of an emulsifier and 15 to 100 parts of water.
  • the emulsion is prepared, in brief, by mixing together the cationic and anionic surfactant in the stated molar ratio, heating the mixture until it melts, mixing the cooled, solidified melt with the emulsifier, heating this mixture until it is liquid, and adding Water until the desired oil-in-water emulsion is present.
  • Contain the liquid surfactant formulations described in GB-A-2 195 653 Although, at least in part, a considerably higher amount of surfactant than that of the US patent mentioned, they, like this one, have a high emulsion-like or suspension-like character, ie they are not a clear liquid composition.
  • the emulsions according to British patent application mentioned is also disadvantageous that its production is complex and complicated.
  • cationic surfactant is a quaternary ammonium salt of the formula N+ (R1, R2, R3, R4) X ⁇ (1), in which R1 and R2 represent an alkyl radical with 1 to 4 carbon atoms or an oxalkylene radical with 1 to 10 ethylene oxide units, propylene oxide units or ethylene oxide units and propylene oxide units, R3 is an alkyl radical or an alkenyl radical with 6 to 22 C atoms, R4 is an alkyl radical or an alkenyl radical with 6 to 22 C atoms or the benzyl radical and X ⁇ an anion of an inorganic or organic acid.
  • R1 and R2 represent an alkyl radical with 1 to 4 carbon atoms or an oxalkylene radical with 1 to 10 ethylene oxide units, propylene oxide units or ethylene oxide units and propylene oxide units
  • R3 is an alkyl radical or an alkenyl radical with 6 to 22 C atoms
  • R4 is an alkyl radical or an
  • surfactant compositions are produced in the way that at least one anionic surfactant and at least one cationic surfactant in a molar ratio of 1: (0.3 to 10) with water in an amount of 50 to 80 wt .-%, based on the total weight of anionic surfactant , Cationic surfactant and water, mixed at a temperature of 25 to 95 ° C to form two phases, waiting for the separation of the two phases and separating the upper targeted surfactant phase from the lower salt phase.
  • compositions are known from the prior art which contain water and nonionic, anionic and cationic surfactants. Such compositions result, for example, from the fact that in addition to the large amount of water, the surfactants in question are also present in a laundry washing machine.
  • FR-A-2 388 882 discloses solid surfactant compositions composed of nonionic, anionic and cationic surfactants. It goes without saying that all these surfactant mixtures are far removed from those according to the invention.
  • the low-foaming and cold-stable liquid surfactant compositions according to the invention are characterized in that they have been prepared by mixing together 1 part by weight of at least one nonionic surfactant and 0.3 to 9 parts by weight, preferably 0.4 to 4 parts by weight , in particular 0.4 to 2.5 parts by weight, of a surfactant formulation consisting of 20 to 60% by weight of water, preferably 20 to 50% by weight, and 40 to 80% by weight, preferably 50 to 80% by weight of at least one anionic surfactant and at least one cationic surfactant in a molar ratio of 1: (0.3 to 5), preferably 1: (0.4 to 2), the cationic surfactant being a quaternary ammonium salt of the formula N+ (R1, R2, R3, R4) X ⁇ (1), in which R1 and R2 represent an alkyl radical having 1 to 4 carbon atoms or an oxalkylene radical having 1 to 10 ethylene oxide units, propylene oxide units or ethylene oxide Units and propylene
  • surfactant formulations are generally clear liquids with a high content of usually an anionic and a cationic surfactant, so they are concentrated solutions of water-containing anionic / cationic surfactant complexes.
  • anion and cation surfactants to be used for the preparation of the surfactant formulations are known and commercially available.
  • the anionic surfactants used are preferably those of the sulfonate and sulfate type (preferably with an alkali metal or with ammonium as the cation).
  • C6 to C22 alkanesulfonates C6 to C22- ⁇ -olefin sulfonates, (C6 to C22-alkyl) benzenesulfonates, N-C6 to C22-acyl-N-methyl-1-aminoethane-2-sulfonates (these are taurine derivatives), Sulfosuccinic acid mono- or sulfosuccinic acid di-C6 to C22-alkyl esters, C6 to C22 fatty alcohol sulfates or ethoxylated C6 to C22 fatty alcohol sulfates with 1 to 20 ethylene oxide units, the alkanesulfonates, ⁇ -olefin sulfonates, fatty alcohol sulfates and ethoxylated fatty alcohol sulfates mentioned being particularly preferred.
  • the C8 to C18 radicals are preferred (it goes without saying that the hydrophobic groups mentioned having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, can also contain double bonds) usually 1 to 3).
  • Suitable anionic surfactants are mentioned below in detail: sodium C13 to C17 alkanesulfonate (primary or secondary alkanesulfonate), sodium C14 to C16 ⁇ -olefinsulfonate, Sodium dodecylbenzenesulfonate, the sodium salt of N-oleyl-N-methyl-taurine, sodium dioctyl-sulfosuccinate, the sodium salt of ⁇ -sulfo-C14 to C18-fatty acid methyl ester, sodium lauryl sulfate, sodium palmitylsulfate, sodium cocosalkylsulfate, sodium mono-sulfonate, sodium mono4 ethoxylated with 3 mol ethylene oxide, sodium t
  • anionic surfactant While the type of anionic surfactant is generally not critical, certain quaternary ammonium salts are suitable as cationic surfactants (for example, those quaternary ammonium salts are unsuitable which have three or more short aliphatic radicals on the nitrogen atom, such as lauryl trimethyl, tallow alkyl trimethyl and dodecylbenzyl trimethyl ammonium chloride (see above-mentioned US-A-3,684,736).
  • the quaternary ammonium salts to be used according to the invention correspond to formula 1 given above wherein R1 to R4 and X ⁇ have the meanings given.
  • Preferred representatives of cationic surfactants are those of the formula 1 when R 1 and R 2 (which may be the same or different) are an alkyl radical with 1 to 4 carbon atoms or an oxalkylene radical with 1 to 10, preferably 1 to 5, ethylene oxide units, propylene oxide Units or ethylene oxide units and Propylene oxide units mean, R3 is an alkyl radical having 8 to 14 carbon atoms, preferably 8 to 10 carbon atoms, R4 has one of the meanings of R3 or the benzyl radical and X ⁇ is an anion of an inorganic or organic acid (which for R1 and R2 mentioned C1 to C4 alkyl radicals are preferably methyl or ethyl).
  • anion X ⁇ in the cationic surfactant examples include inorganic acid residues, such as halide, preferably chloride or bromide, borate, phosphate and sulfate, organic acid residues of mono- or polyvalent, saturated or unsaturated, aliphatic or aromatic acids, such as formate, acetate, propionate , Laurate, stearate, oleate, lactate, citrate, sorbate, benzoate, salicylate and C1 to C3 alkosulfate anions, preferably the methosulfate anion.
  • inorganic acid residues such as halide, preferably chloride or bromide, borate, phosphate and sulfate
  • organic acid residues of mono- or polyvalent, saturated or unsaturated, aliphatic or aromatic acids such as formate, acetate, propionate , Laurate, stearate, oleate, lactate, citrate, sorbate, benzoate, salicylate and C
  • cationic surfactants dioctyl Octyldecyldimethyl-, Didecyldimethyl-, Dilauryldimethyl-, Dioleyldimethyl-, Dicocosalkyldimethyl- and ditallowalkyldimethylammonium, Myristyldimethylbenzyl- and stearyl dimethyl, didecyl-methyl-oxethylammoniumpropionat, dioctyl polyoxethylammoniumpropionat, Ditalgalkyl-methyl-oxpropylammoniumchlorid.
  • the surfactant formulations to be used according to the invention are the result of a special procedure when bringing the components water, anion and cation surfactant together.
  • Anion surfactant, cation surfactant and water at a temperature of 25 to 95 ° C, preferably 40 to 85 ° C, mixed to form two phases, the separation of the two phases is awaited and the upper desired concentrated surfactant phase separated from the lower salt phase .
  • anion surfactants and cation surfactants to be used are often present as solids or as a gel-like surfactant-water mixture.
  • anionic surfactant, cationic surfactant and water preferably demineralized water, are mixed in the stated amount in a reaction vessel at a temperature of 25 to 95 ° C., preferably 40 to 85 ° C., preferably with stirring, whereby it Formation of two phases comes.
  • the order in which the three components are introduced into the reaction vessel is not critical. It is crucial that the three components are mixed well at the specified temperature.
  • the mixing time is usually 5 to 90 minutes.
  • the mixing time is advantageously 20 to 60 minutes.
  • the upper phase represents the desired concentrated and liquid and at the same time clear, water-containing surfactant formulation
  • the lower phase essentially consists of the anion of the cationic surfactant and the cation of the anionic surfactant formed salt contains dissolved in water.
  • the desired surfactant phase (which in addition to the components water and surfactant may also contain some salt) can be obtained simply by pouring, for example.
  • the low-foaming and cold-stable liquid surfactant composition according to the invention comprises, in addition to the surfactant formulation described above, at least one nonionic surfactant as a further component.
  • the nonionic surfactants used are preferably those from the group of polyglycol ethers (generally only one nonionic surfactant is used).
  • Preferred representatives of this group are (a) the oxalkylates of C8 to C18 alcohols (fatty alcohols, oxo alcohols), (C4 to C12 alkyl) phenols (mono-, di- or trialkyl-substituted), C8 to C18 fatty acids, C8 to C18 -Fatty amines, C8 to C18 fatty acid amides and (C8 to C18 fatty acid) ethanolamides with (each) 2 to 30, preferably 4 to 15, ethylene oxide units, propylene oxide units or ethylene oxide and propylene oxide units (in the oxalkylate group) and (b) the ethylene oxide / propylene oxide block polymers, also known as nonionic surfactants, which consist of a propylene oxide inner block with a molecular weight of 1,000 to 3,000 and 5 to 50% by weight (condensed) ethylene oxide exist, percentages by weight based on the block polymer.
  • nonionic surfactants consist of a propy
  • nonionic surfactants are the oxalkylates mentioned in the form of the polyethylene glycol ethers (oxethylates) and ethylene oxide / propylene oxide block polymers, which consist of a propylene oxide inner block with a molecular weight of 1,500 to 2,500 and 10 to 30% by weight of ethylene oxide, weight percentages based on the block polymer.
  • Those nonionic surfactants are preferably used which have a cloud point - measured in butyl diglycol according to DIN 53 917 - from 30 to 100 ° C.
  • the nonionic surfactants to be used according to the invention are known and commercially available. They are usually in the form of water-free, more or less viscous liquids, sometimes with a content of about 10 to 20% by weight of water.
  • the low-foaming and cold-stable liquid surfactant compositions according to the invention are prepared in that the two components nonionic surfactant and surfactant formulation in a weight ratio of 1: (0.3 to 9), preferably 1: (0.4 to 4), in particular 1: (0.4 to 2.5), preferably brought together with stirring.
  • the two components are mixed at room temperature or with heating to a temperature of 30 to 80 ° C., preferably 40 to 60 ° C.
  • the two components mix relatively quickly to a homogeneous and essentially clear liquid (especially if they are mixed while heated).
  • the order in which the components are brought together is not critical. The only decisive factor is that the weight ratios mentioned are observed.
  • the mixing time is generally 5 to 30 minutes, depending on the type of components and the mixing temperature.
  • the surfactant compositions according to the invention essentially consist of an anionic and a cationic surfactant (anion / cation-surfactant complex), a nonionic surfactant and water.
  • the amount of water essentially results from the surfactant formulation used and, depending on the surfactant formulation and the mixing ratio of surfactant formulation and nonionic surfactant, is 5 to 50% by weight, preferably 10 to 30% by weight, based on the surfactant composition.
  • the surfactant compositions according to the invention have a number of advantages. They are concentrated and generally clear liquids on surfactants, which are characterized in particular by relatively low foaming (favorable foaming behavior), good wetting behavior and low pour points (favorable low-temperature behavior). Even when using relatively highly viscous and cloudy-looking nonionic surfactant concentrates, mixing with the surfactant formulations described gives clear and liquid compositions which are therefore easy to handle. They show only a slight tendency to foam and good network values. These values are particularly good if the cationic surfactant has a relatively short-chain hydrocarbon residue in the surfactant formulation used.
  • the surfactant compositions according to the invention are distinguished in particular by their surprisingly favorable cold behavior.
  • the mixing according to the invention can be used to produce, as it were, tailor-made surfactant compositions which, compared to the two surfactants used, often have greatly improved properties and thus possible uses.
  • mixtures can be produced which are characterized in particular by one or more of the following properties: favorable foam and wetting behavior, low surface tension, high clarity and excellent low-temperature behavior.
  • the surfactant compositions according to the invention can be used as such or diluted with solvents such as water or alcohols.
  • the surfactant compositions according to the invention are advantageously used for the preparation of low-foam and low-temperature surfactant concentrates by being mixed with surfactant products in need of improvement in order to impart low foam and low-temperature stability (low pour point) to them.
  • a mixture of 70% by weight of water and 30% by weight of anionic surfactant 1 and cationic surfactant 1 in a molar ratio of 1: 1 was stirred well at 80 ° C. for 30 minutes. After this time, stirring and heating were stopped and the contents of the beaker (in which the formation of two phases was seen) were left to stand at room temperature for 5 hours. After this time, two distinct phases had formed.
  • the upper clear phase, that is the desired surfactant phase or surfactant formulation 1 was obtained by pouring off the lower phase, that is the aqueous salt phase (NaCl).
  • the liquid and somewhat cloudy surfactant formulation 1 consisted of 26% by weight of water and 74% by weight of anionic surfactant 1 plus cationic surfactant 1 in a molar ratio of 1: 1 (the salt content was below 0.1% by weight) . If the above-mentioned standing (standing time) of the contents of the beaker takes place after stopping the stirring while maintaining the temperature of 80 ° C., the formation of the two sharply separated phases is already over after one hour; by allowing the mixture to stand in the heat, the separation into the two phases is considerably accelerated.
  • a mixture of 70% by weight of water and 30% by weight of anionic surfactant 2 and cationic surfactant 2 in a molar ratio of 1: 1 was stirred well at 70 ° C. for 30 minutes and as at Treated surfactant formulation 1.
  • the liquid and clear surfactant formulation 2 consisted of 45% by weight of water and 55% by weight of anionic surfactant 2 and cationic surfactant 2 in a molar ratio of 1: 1 (the salt content was below 0.1% by weight).
  • a mixture of 70% by weight of water and 30% by weight of anionic surfactant 3 and cationic surfactant 3 in a molar ratio of 1: 1 was stirred well at 80 ° C. for 45 minutes and treated as in surfactant formulation 1.
  • the liquid and clear surfactant formulation 3 consisted of 32% by weight of water and 68% by weight of anionic surfactant 3 and cationic surfactant 3 in a molar ratio of 1: 1 (the salt content was below 1% by weight).
  • a mixture of 70% by weight of water and 30% by weight of anionic surfactant 4 and cationic surfactant 4 in a molar ratio of 1: 1 was stirred well at 60 ° C. for 30 minutes and treated as in surfactant formulation 1.
  • the liquid and clear surfactant formulation 4 consisted of 27% by weight of water and 73% by weight of anionic surfactant 4 and cationic surfactant 4 in a molar ratio of 1: 1 (the salt content was below 1% by weight; also in the other surfactant formulations, the salt content was more or less below 1% by weight).
  • a mixture of 70% by weight of water and 30% by weight of anionic surfactant 5 and cationic surfactant 5 in a molar ratio of 1: 0.4 was stirred well at 80 ° C. for 1 hour and treated as in surfactant formulation 1.
  • the liquid and clear surfactant formulation 5 consisted of 55% by weight of water and 45% by weight of anionic surfactant 5 and cationic surfactant 5 in a molar ratio of 1: 0.4.
  • a mixture of 70% by weight of water and 30% by weight of anionic surfactant 6 and cationic surfactant 6 in a molar ratio of 1: 0.7 was stirred well at 70 ° C. for 30 minutes and treated as in surfactant formulation 1.
  • the liquid and clear surfactant formulation 6 consisted of 58% by weight of water and 42% by weight of anionic surfactant 6 and cationic surfactant 6 in a molar ratio of 1: 0.7.
  • a mixture of 70% by weight of water and 30% by weight of anionic surfactant 7 and cationic surfactant 7 in a molar ratio of 1: 1.5 was stirred well at 80 ° C. for 1 hour and treated as in surfactant formulation 1.
  • the liquid and clear surfactant formulation 7 consisted of 41% by weight of water and 59% by weight of anionic surfactant 7 and cationic surfactant 7 in a molar ratio of 1: 1.5.
  • a mixture of 70% by weight of water and 30% by weight of anionic surfactant 8 and cationic surfactant 8 in a molar ratio of 1: 1.7 was stirred well at 80 ° C. for 90 minutes and treated as in surfactant formulation 1.
  • the liquid and clear surfactant formulation 8 consisted of 30% by weight of water and 70% by weight of anionic surfactant 8 and cationic surfactant 8 in a molar ratio of 1: 1.7.
  • a mixture of 70% by weight of water and 30% by weight of anionic surfactant 9 and cationic surfactant 9 in a molar ratio of 1: 4 was stirred well at 80 ° C. for 1 hour and treated as in surfactant formulation 1.
  • the liquid and clear surfactant formulation 9 consisted of 48% by weight of water and 52% by weight of anionic surfactant 9 and cationic surfactant 9 in a 1: 4 molar ratio.
  • a mixture of 70% by weight of water and 30% by weight of anionic surfactant 10 and cationic surfactant 10 in a molar ratio of 1: 2 was stirred well at 60 ° C. for 30 minutes and treated as in surfactant formulation 1.
  • the liquid and clear surfactant formulation 10 consisted of 32% by weight of water and 68% by weight of anionic surfactant 10 and cationic surfactant 10 in a molar ratio of 1: 2.
  • nonionic surfactant 1 and 700 g of surfactant formulation 4 were placed in a beaker and stirred at room temperature for 20 minutes, after which there was a liquid and clear mixture.
  • This surfactant composition according to the invention was thus prepared by adding 1 part by weight of the nonionic surfactant mentioned with 2.3 parts by weight of a surfactant formulation consisting of 27% by weight of water and 73% by weight of the anion / cation mentioned.
  • Surfactant in a molar ratio of 1: 1 were mixed together at room temperature.
  • Examples 4 to 15 in which a liquid (easily pourable) and more or less clear surfactant composition according to the invention were also obtained, are summarized in Table 1 below.
  • Table 1 provides information on the nonionic surfactants and surfactant formulations used and on the weight ratio of nonionic surfactant to surfactant formulation. For the sake of completeness, Table 1 also contains the corresponding information from Examples 1 to 3: Table 1 Example No. Nonionic surfactant no. Surfactant Formulation No.
  • Table 2 below shows the properties of the 15 surfactant compositions according to the invention from Examples 1 to 15, namely the pour points, the foam values, the wetting values and the surface tension values. Table 2 also shows (to allow a direct comparison) the pour points, foam values, network values and surface tension values of the 12 nonionic surfactants and 10 surfactant formulations used to prepare the surfactant compositions.
  • the 12 nonionic surfactants used are designated A1 to A12, the 10 surfactant compositions used B1 to B10 and the 15 surfactant compositions according to the invention C1 to C15.
  • the pour points of the surfactant compositions according to the invention are in some cases far below the pour points of the nonionic surfactants and surfactant formulations used. Because of this obviously high synergistic effect, the new surfactant compositions have an extremely favorable cooling behavior. The other properties tested, in particular the foam behavior, also show good values.
  • the pour point was determined according to DIN ISO 3016. 50 to 80 g of the surfactant composition were placed in a beaker and cooled until the composition which was liquid and readily pourable at room temperature was no longer pourable. The temperature present is referred to as the pour point of the composition.
  • the foam value was determined in accordance with DIN 53 902. 1 g of the surfactant composition was dissolved in one liter of deionized water. About 200 ml of this solution were added to the 1000 ml measuring cylinder and beaten thirty times with the perforated beating disc. The resulting foam height in the measuring cylinder, expressed in milliliters, represents the foam value.
  • the surface tension was determined in accordance with DIN 53 914. 0.1 g of the surfactant composition was dissolved in one liter of deionized water. The surface tension of this solution was measured in mN / m using a conventional tensiometer using the ring tearing method.
  • the wetting capacity was determined in accordance with DIN 53 901. 1 g of the surfactant composition was dissolved in one liter of deionized water. A cotton plate was immersed in the solution. The time was measured after the plate had been immersed until it began to sink further into the solution. This time in seconds represents the wetting ability (if the cotton plate is wetted quickly, which means high wetting ability, it drops after a few seconds).

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Claims (10)

  1. Procédé de préparation de compositions d'agents tensioactifs liquides peu moussantes et stables au froid, constituées essentiellement d'eau et d'agents tensioactifs non ioniques, anioniques et cationiques, caractérisé par le mélange de 1 partie en masse d'au moins un agent tensioactif non ionique et de 0,3 à 9 parties en masse d'une formulation d'agents tensioactifs constituée de 20 à 60 % en masse d'eau et de 40 à 80 % en masse d'au moins un agent tensioactif anionique et d'au moins un agent tensioactif cationique dans un rapport molaire de 1 : (0,3 à 5), l'agent tensioactif cationique étant un sel d'ammonium quaternaire de formule N⁺(R¹,R²,R³,R⁴)X⁻ (1), dans laquelle R¹ et R² représentent un reste alkyle de 1 à 4 atomes de carbone ou un reste oxyalkylène de 1 à 10 unités d'oxyde d'éthylène, unités d'oxyde de propylène ou unités d'oxyde d'éthylène et unités d'oxyde de propylène, R³ représente un reste alkyle ou un reste alcényle de 6 à 22 atomes de carbone, R⁴ représente un reste alkyle ou un reste alcényle de 6 à 22 atomes de carbone ou le reste benzyle et X⁻ représente un anion d'un acide inorganique ou organique, et la formulation d'agents tensioactifs ayant été préparée par un procédé selon lequel on mélange les constituants qui sont l'agent tensioactif anionique, l'agent tensioactif cationique et l'eau à une température de 25 à 95°C en formant deux phases, on attend la séparation des deux phases et on sépare de la phase saline inférieure la phase d'agents tensioactifs concentrée supérieure qui représente la formulation d'agents tensioactifs.
  2. Procédé selon la revendication 1, caractérisé par le mélange de 1 partie en masse d'au moins un agent tensioactif non ionique et de 0,4 à 4 parties en masse de la formulation d'agents tensioactifs.
  3. Procédé selon la revendication 1, caractérisé par le mélange de 1 partie en masse d'au moins un agent tensioactif non ionique et de 0,4 à 2,5 parties en masse de la formulation d'agents tensioactifs.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que la formulation d'agents tensioactifs est constituée de 20 à 60 % en masse d'eau et de 40 à 80 % en masse d'au moins un agent tensioactif anionique et d'au moins un agent tensioactif cationique dans un rapport molaire de 1 : (0,4 à 2).
  5. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que la formulation d'agents tensioactifs est constituée de 20 à 50 % en masse d'eau et de 50 à 80 % en masse d'au moins un agent tensioactif anionique et d'au moins un agent tensioactif cationique dans un rapport molaire de 1 : (0,4 à 2).
  6. Procédé selon l'une ou plusieurs des revendications 1 à 5, caractérisé en ce que l'agent tensioactif anionique est un alcanesulfonate en C₆-C₂₂, un α-oléfinesulfonate en C₆-C₂₂, un (alkyl en C₆-C₂₂)benzènesulfonate, un N-(acyl en C₆-C₂₂)-N-méthyl-1-aminoéthane-2-sulfonate, un mono- ou diester d'alkyle en C₆-C₂₂ de l'acide sulfosuccinique, un sulfate d'alcool gras en C₆-C₂₂ ou un sulfate d'alcool gras en C₆-C₂₂ éthoxylé contenant 1 à 20 unités d'oxyde d'éthylène, et l'agent tensioactif cationique est un composé de formule 1 dans laquelle R¹ et R² représentent un reste alkyle de 1 à 4 atomes de carbone ou un reste oxyalkylène de 1 à 10 unités d'oxyde d'éthylène, unités d'oxyde de propylène ou unités d'oxyde d'éthylène et unités d'oxyde de propylène, R³ représente un reste alkyle de 8 à 14 atomes de carbone, R⁴ a l'une des significations de R³ ou est le reste benzyle et X⁻ est un anion d'un acide inorganique ou organique.
  7. Procédé selon l'une ou plusieurs des revendications 1 à 6, caractérisé en ce que l'agent tensioactif non ionique appartient au groupe des éthers de polyglycols.
  8. Procédé selon l'une ou plusieurs des revendications 1 à 6, caractérisé en ce que l'agent tensioactif non ionique est un oxyalkylate d'alcools en C₈-C₁₈, d'(alkyl en C₄-C₁₂)phénols, d'acides gras en C₈-C₁₈, d'amines grasses en C₈-C₁₈, d'amides d'acides gras en C₈-C₁₈ ou d'éthanolamides d'acides gras en C₈-C₁₈, comprenant 2 à 30 unités d'oxyde d'éthylène, unités d'oxyde de propylène ou unités d'oxyde d'éthylène et d'oxyde de propylène, ou un polymère à blocs oxyde d'éthylène/oxyde de propylène constitué d'un bloc intérieur d'oxyde de propylène ayant une masse moléculaire de 1 000 à 3 000 et de 5 à 50 % en masse d'oxyde d'éthylène, les pourcentages en masse étant rapportés au polymère à blocs.
  9. Procédé selon l'une ou plusieurs des revendications 1 à 6, caractérisé en ce que l'agent tensioactif non ionique est un oxyéthylate d'alcools en C₈-C₁₈, d'(alkyl en C₄-C₁₂)phénols, d'acides gras en C₈-C₁₈, d'amines grasses en C₈-C₁₈, d'amides d'acides gras en C₈-C₁₈ ou d'éthanolamides d'acides gras en C₈-C₁₈, comprenant 2 à 30 unités d'oxyde d'éthylène, ou un polymère à blocs oxyde d'éthylène/oxyde de propylène constitué d'un bloc intérieur d'oxyde de propylène ayant une masse moléculaire de 1 500 à 2 500 et de 10 à 30 % en masse d'oxyde d'éthylène, les pourcentages en masse étant rapportés au polymère à blocs.
  10. Utilisation des compositions d'agents tensioactifs préparées selon les revendications 1 à 9 pour la préparation de concentrés d'agents tensioactifs peu moussants et stables au froid.
EP90106442A 1989-04-06 1990-04-04 Compositions aqueuses détergentes peu moussantes et stables au froid comprenant des agents tensioactifs non ioniques, anioniques et cationiques et leur application Expired - Lifetime EP0391392B1 (fr)

Applications Claiming Priority (2)

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DE3911098 1989-04-06
DE3911098A DE3911098A1 (de) 1989-04-06 1989-04-06 Schwachschaeumende und kaeltestabile fluessige tensidzusammensetzungen aus wasser und nichtionischen, anionischen und kationischen tensiden und deren verwendung

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EP0391392A2 EP0391392A2 (fr) 1990-10-10
EP0391392A3 EP0391392A3 (fr) 1991-01-16
EP0391392B1 true EP0391392B1 (fr) 1995-07-26

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JP (1) JPH02284639A (fr)
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CA (1) CA2013920A1 (fr)
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AT103U1 (de) * 1992-04-16 1995-02-27 Purator Umwelttechnik Gmbh Verfahren zum waschen und trocknen sowie gegebenenfalls wachsen in kraftfahrzeugwaschanlagen
US6180740B1 (en) 1998-02-27 2001-01-30 E. I. Du Pont De Nemours And Company Stabilization of fluorochemical copolymer emulsions
AU2495400A (en) * 1999-01-11 2000-08-01 Huntsman Petrochemical Corporation Surfactant compositions containing alkoxylated amines
BR0015923A (pt) * 1999-11-22 2003-06-24 Huntsman Spec Chem Corp Adjuvantes de surfactante úteis em composições de herbicidas
DE10203225A1 (de) 2002-01-28 2003-07-31 Weigert Chem Fab Reinigung chirurgischer Instrumente
DE10316001A1 (de) * 2003-04-07 2004-10-21 Goldschmidt Ag Wässrige Formulierungen enthaltend Kombinationen aus anionischen und kationischen Tensiden zur Erzeugung einer Fließgrenze
DE102004039727A1 (de) * 2004-08-16 2006-02-23 Bode Chemie Gmbh & Co. Kg Reinigungs- und Desinfektionsmittel für medizinische Instrumente mit verbesserter Wirksamkeit gegen Hepatitis-B-Viren
ATE547170T1 (de) * 2008-05-20 2012-03-15 Cognis Ip Man Gmbh Wässrige tensid-zusammensetzungen mit niedrigem pourpoint
EP2455156B1 (fr) 2010-11-18 2013-06-05 Cognis IP Management GmbH Compositions aqueuses à viscosité réduite
FR3095558B1 (fr) 2019-04-24 2021-04-30 Niedax France Element de fixation de couvercle pour chemin de cables

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EP0391392A3 (fr) 1991-01-16
ATE125564T1 (de) 1995-08-15
ES2076984T3 (es) 1995-11-16
US5298193A (en) 1994-03-29
JPH02284639A (ja) 1990-11-22
EP0391392A2 (fr) 1990-10-10
CA2013920A1 (fr) 1990-10-06
DE59009425D1 (de) 1995-08-31
BR9001527A (pt) 1991-04-23
DE3911098A1 (de) 1990-10-11

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