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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0094—High foaming 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
  • C11D1/66—Non-ionic compounds
  • C11D1/662—Carbohydrates or derivatives
• • 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
  • C11D1/83—Mixtures of non-ionic with anionic 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
  • C11D1/14—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
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

• the invention relates to an environmentally friendly, foaming, liquid cleaning agent.
• Liquid, foaming cleaning agents aim at the manual cleaning of hard surfaces, especially in the household, such as. B. ceramics, porcelain, glass, metal and plastic.
• the most important area of application are manual dishwashing detergents for cleaning dishes.
• the main components are sulfonates, such as. B. alkylbenzenesulfonates or sec-alkanesulfonates, both combined with fatty alcohol ether sulfates or fatty alcohol sulfates (EP-A-0 112 047). Small amounts of fatty acid alkanolamides and, more rarely, oxyethylates are added. Other common ingredients are solubilizers, colors and fragrances, preservatives etc.
• the criteria for the quality of the detergent are primarily the rinsing effect and the skin and environmental compatibility. Other characteristics include the foaming power and finally the viscosity of the detergent concentrate.
• Generally recognized methods for determining the cleaning effect are a) the plate test with foaming detergents, the end point of which is determined by the foam disintegration, and b) the fat titration, as a measure of the cleaning power, both of which have very similar results (see G. Jakobi in H. Stache, Tensid Taschenbuch, 2nd edition, Kunststoff 1981, pp. 252 ff.
• the currently customary cleaning agents usually have a good cleaning effect, degrading flow behavior and a pronounced, possibly excessive foaming power.
• these mixtures have a low skin-friendliness, since their essential components - namely the anionic surfactants of the sulfonate or sulfate type - are highly irritating to the skin.
• Another disadvantage with regard to the scarcity of raw material reserves is the predominantly petrochemical basis of the anionic surfactants mentioned, combined with incomplete biodegradability.
• the object of the invention was therefore to provide a cleaning agent which implies all the advantages mentioned, but at the same time offers high skin compatibility and excellent environmental compatibility.
• the object was achieved by a liquid cleaning agent, the surfactant combination of which contains highly environmentally compatible alkyl polyglycosides.
• Other constituents are alternatively fatty alcohol ether sulfates, fatty alcohol sulfates and alkylbenzenesulfonates.
• the other constituents of these cleaning concentrates are conventional solubilizers, hydrotropics, complexing agents, dyes, perfume oils, etc.
• the surfactant content in the cleaning agent in aqueous solution is 3 to 40%.
• alkyl polyglycosides in detergents and cleaning agents is known in combination with other surfactants.
• AT-PS 135 333 already describes the effect of lauryl glycoside combined with the sodium salt of ricinol sulfuric acid ester as a wool detergent.
• alkyl polyglycosides in combination with builder substances, such as nitrilotriacetic acid or sodium tripolyphosphate are described as detergents.
• EP-A-0 105 556 claims the combination of alkypolyglycosides with fatty alcohol oxyethylates as the liquid detergent.
• the cleaning agent formulations according to the invention therefore not only mean less environmentally harmful surfactants due to the recipe, but also lower use concentrations.
• Alkyl polyglycosides used according to the invention satisfy formula I.
• the alkyl polyglycosides used according to the invention can be produced by known processes based on renewable raw materials. For example, dextrose is reacted with n-butanol to give butylpolyglycoside mixtures in the presence of an acidic catalyst, which are re-glycosidated with long-chain alcohols in the presence of an acidic catalyst to give the desired alkylpolyglycoside mixtures.
• the structure of the products can be varied within certain limits.
• the alkyl radical R is determined by the choice of the long-chain alcohol.
• the industrially accessible surfactant alcohols with 10 to 18 carbon atoms, in particular native fatty alcohols from the hydrogenation of fatty acids or fatty acid derivatives.
• Ziegler alcohols or oxo alcohols can also be used.
• the polyglycosyl radical Z n is determined, on the one hand, by the selection of the carbohydrate and, on the other hand, by setting the average degree of polymerization n. B. according to DE-OS 19 43 689.
• polysaccharides e.g. B. starch, maltodextrins, dextrose, galactose, mannose, xylose etc.
• the industrially available carbohydrates starch, maltodextrins and especially dextrose are preferred.
• alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They exist side by side with ⁇ - and ⁇ -glycosidic bonds in pyranose and furanose form. The links between two saccharide residues are also different.
• Alkyl polyglycosides used according to the invention can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides.
• the latter can e.g. B according to EP-A-0 092 355 by means of polar solvents, such as acetone, from alkylpolyglycosides.
• the degree of glycosidation is advantageously determined by means of 1 H-NMR.
• the cleaning agents according to the invention contain 3 to 30%, preferably 5 to 20%, of alkyl polyglycoside in aqueous solution.
• the alkyl polyglycosides are considered to be extremely environmentally compatible.
• the degree of biodegradation for the alkyl polyglycosides according to the invention determined by means of a sewage treatment plant simulation model / DOC analysis, is 96 ⁇ 3%. This number can be seen against the background that with this test method (total degradation) a degree of degradation> 70% already indicates that the substance is readily degradable.
• the acute oral toxicity LD 50 (rat) as well as the aquatic toxicity LC 50 (gold orfe) and EC 50 (daphnia) and values of> 10,000 mg / kg, 12 or 30 mg / l are three to five times cheaper as the corresponding values of the most important surfactants today. The same applies to the skin and mucous membrane compatibility, which is particularly important for flushing agents.
• the alkyl polyglycosides according to the invention are obtained as an approximately 50% aqueous solution due to the synthesis.
• Suitable anionic surfactants are fatty alcohol ether sulfates - alone and as a mixture with fatty alcohol sulfates - and alkylbenzenesulfonates.
• Anionic surfactants with alkyl radicals of 10 to 20 carbon atoms in the hydrophobic part of the molecule are preferred.
• Preferred fatty alcohol ether sulfates contain 1 to 4 mol ethylene oxide / mol.
• the cleaning agents according to the invention contain 3 to 25%, preferably 5 to 20%, of anionic surfactant in aqueous solution.
• solvents such as low-molecular, mono- and polyhydric alcohols and glycol ethers
• the solubility can be increased significantly, especially at low temperatures.
• Particularly suitable solvents are ethanol, isopropanol, propylene glycol-1.2 etc.
• Typical concentrations in the cleaning agent are 3 to 12% in the aqueous solution.
• the solubility can be achieved especially at low temperatures, e.g. T. increase significantly.
• Alkali and alkaline earth metal halides have proven to be suitable electrolytes.
• the ratio of solvent / electrolyte can be 1: 1 to 8: 1.
• additives are nonionic, ampholytic and / or zwitterionic surfactants with total concentrations between 0 and 5% in the aqueous solution.
• the cleaning liquid according to the invention can contain small amounts (0.1 to 5 percent by weight) of conventional dyes and Perfume oils and alkanolamines or hydrotropes, such as non-surfactant alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical - usually in the form of sodium salts - and urea.
• conventional dyes and Perfume oils and alkanolamines or hydrotropes such as non-surfactant alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical - usually in the form of sodium salts - and urea.
• Water-soluble polymers such as carboxymethyl cellulose, hydroxyethyl cellulose, xanthans, polyethylene oxide, polyacrylate, etc., can optionally be added to adjust the viscosity.
• Citric acid EDTA, NTA and other complexing agents have proven to be further suitable additives.
• the mini-plate test (cf. RM Anstett and EJ Schuck JAOCS 43, 576 (1966) was carried out to test the detergent effect.
• watch glasses loaded with fat are cleaned manually with a brush in the surfactant solution at elevated temperature.
• the test conditions (preparations, geometries, Quantities and concentrations of substances, temperatures, temperature gradients, times) are precisely defined.
• the test is carried out by several people and provides reproducible results. Vanishing foam shows the number of cleaned plates (watch glasses). Pork lard, which at 50, 0 ° C. was applied to the glasses, which are then subjected to a defined cooling process to 23 ° C. (room temperature), and the initial rinse temperature is also 50 ° C.
• the foaming power of the cleaning agent was determined in accordance with DIN 53 902, Part 1.
• the concentration of detergent substance was 1 g / l in each case.
• the foam volume was registered after 5 minutes.
• the viscosity of the cleaning liquid was measured in a rotary viscometer (Haake RV 20) at 25 ° C under defined shear rates (D approx. 10 sec ⁇ 1).
• Another advantage is the more favorable flow behavior of the formulations according to the invention, which is particularly noticeable when ether sulfates are used as anionic surfactants.
• significantly higher amounts of electrolyte (Examples 1, 2 and 3 compared to Examples 5 and 6) have to be added to the formulation according to EP-A-0 070 074 in order to set a similarly favorable flow behavior.
• APG 1 ⁇ alkyl polyglycoside, alkyl chain C 12/13 and G 1.7
• APG 2 ⁇ alkyl polyglycoside, alkyl chain C 12/14 and G 1.5
• SECTION ⁇ alkylbenzenesulfonate, alkyl chain C 10/13
• Alkyl ether sulfate ⁇ alkyl chain C 12/14 , 2 mol ethylene oxide / mol

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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)
• Molecular Biology (AREA)
• Detergent Compositions (AREA)

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Cited By (6)

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Citations (4)

• 1990
  • 1990-11-17 DE DE19904036662 patent/DE4036662A1/de not_active Withdrawn
• 1991
  • 1991-09-21 EP EP91116086A patent/EP0486786A1/fr not_active Withdrawn

Patent Citations (4)

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