EP0486784B1 - Détergent liquide moussant à viscosité augmentée - Google Patents

Détergent liquide moussant à viscosité augmentée Download PDF

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Publication number
EP0486784B1
EP0486784B1 EP91115711A EP91115711A EP0486784B1 EP 0486784 B1 EP0486784 B1 EP 0486784B1 EP 91115711 A EP91115711 A EP 91115711A EP 91115711 A EP91115711 A EP 91115711A EP 0486784 B1 EP0486784 B1 EP 0486784B1
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EP
European Patent Office
Prior art keywords
alkyl
liquid
fatty alcohol
foaming detergent
weight
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.)
Expired - Lifetime
Application number
EP91115711A
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German (de)
English (en)
Other versions
EP0486784A3 (en
EP0486784B2 (fr
EP0486784A2 (fr
Inventor
Dieter Dr. Balzer
Heinz Prof. Dr. Hoffmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huels AG
Original Assignee
Huels AG
Chemische Werke Huels AG
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Application filed by Huels AG, Chemische Werke Huels AG filed Critical Huels AG
Publication of EP0486784A2 publication Critical patent/EP0486784A2/fr
Publication of EP0486784A3 publication Critical patent/EP0486784A3/de
Publication of EP0486784B1 publication Critical patent/EP0486784B1/fr
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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
    • 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
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • 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
    • C11D1/143—Sulfonic 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
    • C11D1/14—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
    • C11D1/22—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
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives

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. As 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 rinsing process usually takes place at a slightly elevated temperature (30 to 50 ° C) in dilute solutions.
  • a slightly elevated temperature (30 to 50 ° C)
  • the skin compatibility of the detergent is the skin compatibility of the detergent.
  • the foaming power of the solution plays a significant role, for example in the sense that the longer the cleaning solution foams during the rinsing process, the greater its cleaning power.
  • Another important consumer property of the cleaning liquid is the flow behavior. Too high and too low viscosities make manual dosing of the cleaning concentrate difficult. Very low viscosities also lead to the impression of a low active substance content. Average viscosities between 150 and 300 mPa ⁇ s at shear rates of approx. 10 sec -1 are ideal for household products. Another important property is the compatibility of the active ingredients with drinking water, clear solutions are desirable.
  • the currently customary cleaning agents usually show sufficient cleaning action and a high foaming power, suitable flow behavior and sufficient compatibility with the hardness constituents of the water.
  • 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.
  • the object of the invention was therefore to provide a cleaning agent which implies all the desired properties, with high skin tolerance and excellent environmental compatibility.
  • the object was achieved by a liquid cleaning agent which largely contains only alkyl polyglycoside as the surfactant.
  • 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.
  • DE-OS 35 34 082 also has analogous content, fatty alkyl glycosides having 1 to 1.4 glycoside units per fatty alkyl radical being mentioned.
  • Alkyl sulfate or alkyl ether sulfates in each case in combination with fatty acid alkanolamides serve as cosurfactants.
  • EP-A-0 199 765 describes a liquid detergent or dishwashing detergent with a similar claim.
  • EP-0 199 765 describes cleaning liquids with a minimum anionic cosurfactant content of 3%.
  • alkyl polyglycoside as the only surfactant component in the cleaning liquid.
  • Defacto pure alkyl polyglycoside solutions also have excellent cleaning effects, provided they are sufficiently hydrophobic. The latter is achieved through a longer-chain hydrophobic alkyl radical or through a less pronounced hydrophilic part of the molecule.
  • 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 transglycosidated with long-chain alcohols, likewise 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 the setting of 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 linkages 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 alkyl polyglycosides.
  • the degree of glycosidation is expediently determined by means of 1 H-NMR.
  • the cleaning agents according to the invention contain 5 to 40%, preferably 10 to 30%, 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 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 3 to 5 times cheaper than the corresponding values of the most important surfactants today. The same applies to the skin and mucous membrane compatibility, which is particularly important for detergents.
  • the alkyl polyglycosides according to the invention are obtained as an approximately 50% aqueous solution due to the synthesis.
  • the solubility in water is not too high due to the hydrophobic structure adjustment.
  • Suitable anionic surfactants are fatty alcohol ether sulfates, fatty alcohol sulfates, fatty alcohol ether phosphates, carboxymethylated fatty alcohol oxethylates, paraffin sulfonates, olefin sulfonates, alkylbenzenesulfonates and mixtures thereof.
  • Anionic surfactants with alkyl or alkylene radicals of 10 to 20 carbon atoms in the hydrophobic part of the molecule are particularly suitable.
  • Fatty alcohol ether sulfates with 1 to 4 mol ethylene oxide / mol, carboxymethylated fatty alcohol oxethylates with 2 to 10 mol ethylene oxide / mol and fatty alcohol sulfates are preferred.
  • Preferred cations are Na, K, NH 4 and Mg or mixtures thereof.
  • the cleaning concentrates according to the invention contain 0.1 to 2.9% anionic surfactant in aqueous solution. 0.15 to 2.5% are preferred.
  • 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, 1,2-propylene glycol 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 halides have proven to be suitable electrolytes.
  • the solvent / electrolyte ratio can be 1: 1 to 8: 1.
  • additives are nonionic, ampholytic and / or zwitterionic surfactants with total concentrations between 0 and 3% in the aqueous solution.
  • the cleaning liquid according to the invention can contain small amounts (0.1 to 3 percent by weight) of customary dyes and perfume oils, and also alkanolamines or hydrotropes, such as non-surfactant alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical - usually as 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 dish test (cf. RM Anstett and EJ Schuck JAOCS 43, 576 (1966) was carried out to test the detergent effect.
  • Watch glasses loaded with grease are manually cleaned at elevated temperature with a brush in the surfactant solution.
  • the test conditions (preparations, geometries, amounts and concentrations of substances, temperatures, temperature gradients, times) are precisely defined.
  • the test is carried out by several people and provides well reproducible results.
  • Disappearing foam shows the number of cleaned plates (watch glasses). Lard served as soiling, which was applied to the glasses at 50.0 ° C, which are then subjected to a defined cooling process to 23 ° C (room temperature).
  • 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) under defined shear rates (D approx. 10 sec -1 ).
  • Tables 1 a and 1 b show the properties of the preparations according to the invention.
  • the addition of small amounts of anionic surfactant to solutions of hydrophobically adjusted alkyl polyglycoside brings about a clarification of the liquid.
  • foaming power and viscosity increase sharply and very soon reach the level of commercially available cleaning agents (Example 7 (V).
  • the cleaning effect is not influenced by the addition of anionic surfactants within the scope of the measurement error and corresponds completely to the standard on the market.

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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)
  • Detergent Compositions (AREA)

Claims (4)

  1. Détergent moussant liquide à haute viscosité, caractérisé en ce qu'il est constitué
    de 5 à 40 % en poids d'un alkylpolyglycoside,
    de 0,1 à 2,9 % en poids d'un tensioactif anionique,
    de 0 à 3 % en poids d'autres tensioactifs,
    ainsi que d'autres additifs non tensioactifs, et d'eau jusqu'à 100 % en poids, le tensioactif anionique étant choisi parmi l'ensemble comprenant les (alcools gras)sulfates éthoxylés, les (alcools gras)sulfates, les (alcools gras)phosphates éthoxylés, les produits d'éthoxylation carboxyméthylés d'alcools gras, les paraffinesulfonates, les oléfinesulfonates, les alkylbenzènesulfonates et leurs mélanges.
  2. Détergent moussant liquide selon la revendication 1, caractérisé en ce que l'alkylpolyglycoside correspond à la formule I

            R-O-Zn     (I)

    dans laquelle R est un radical alkyle à chaîne droite ou ramifiée, saturé ou insaturé, ayant de 10 à 18 atomes de carbone, et Zn est un radical polyglycosyle dans lequel n = 1,1 à 1,5 motifs hexose ou pentose, ou leurs mélanges.
  3. Détergent moussant liquide selon l'une des revendications précédentes, caractérisé en ce qu'on utilise comme additifs supplémentaires des solvants tels que des mono- et polyalcools, des électrolytes, des complexants, des hydrotropes, des polymères, des colorants et des aromatisants.
  4. Utilisation du détergent moussant liquide selon l'une des revendications précédentes comme agent de rinçage à la main.
EP91115711A 1990-11-17 1991-09-17 Détergent liquide moussant à viscosité augmentée Expired - Lifetime EP0486784B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4036663 1990-11-17
DE4036663A DE4036663A1 (de) 1990-11-17 1990-11-17 Fluessiges, schaeumendes reinigungsmittel mit erhoehter viskositaet

Publications (4)

Publication Number Publication Date
EP0486784A2 EP0486784A2 (fr) 1992-05-27
EP0486784A3 EP0486784A3 (en) 1992-10-07
EP0486784B1 true EP0486784B1 (fr) 1996-08-14
EP0486784B2 EP0486784B2 (fr) 1999-08-18

Family

ID=6418450

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91115711A Expired - Lifetime EP0486784B2 (fr) 1990-11-17 1991-09-17 Détergent liquide moussant à viscosité augmentée

Country Status (7)

Country Link
EP (1) EP0486784B2 (fr)
JP (1) JPH04292696A (fr)
AT (1) ATE141321T1 (fr)
CA (1) CA2055650A1 (fr)
DE (2) DE4036663A1 (fr)
GR (1) GR3021025T3 (fr)
NO (1) NO179289C (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4216380A1 (de) * 1992-05-18 1993-11-25 Henkel Kgaa Verfahren zur Reinigung von Badezimmerarmaturen
DE4239679A1 (de) * 1992-11-26 1994-06-01 Henkel Kgaa Viskose wäßrige Tensidzubereitungen
US5597406A (en) * 1993-11-02 1997-01-28 Henkel Corporation Method of thickening aqueous formulations
US5501813A (en) * 1993-11-02 1996-03-26 Henkel Corporation Thickener for aqueous compositions
AU675833B2 (en) * 1994-03-23 1997-02-20 Amway Corporation Concentrated all-purpose light duty liquid cleaning composition and method of use
DE19933404A1 (de) * 1999-07-21 2001-01-25 Henkel Kgaa Reinigungsmittel für harte Oberflächen

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4396520A (en) * 1982-04-26 1983-08-02 The Procter & Gamble Company Detergent compositions
DE3577878D1 (de) * 1984-11-06 1990-06-28 Henkel Kgaa Monoglykoside als viskositaetsregler in detergenzien.
DE3708330A1 (de) * 1987-03-14 1988-09-22 Henkel Kgaa Fluessige, alkalische reinigerkonzentrate
DE3838808A1 (de) * 1988-11-17 1990-05-23 Henkel Kgaa Wasch- und reinigungsmittel, enthaltend ein tensidgemisch aus alkylglykosiden und aniontensiden
MY106599A (en) * 1988-12-19 1995-06-30 Kao Corp Detergent composition
DE3905939A1 (de) * 1989-02-25 1990-08-30 Huels Chemische Werke Ag Tensidkombination
US5118440A (en) * 1990-03-05 1992-06-02 The Procter & Gamble Company Light-duty liquid dishwashing detergent composition containing alkyl polysaccharide and alpha-sulfonated fatty acid alkyl ester surfactants

Also Published As

Publication number Publication date
EP0486784A3 (en) 1992-10-07
EP0486784B2 (fr) 1999-08-18
DE59108078D1 (de) 1996-09-19
CA2055650A1 (fr) 1992-05-18
JPH04292696A (ja) 1992-10-16
DE4036663A1 (de) 1992-05-21
NO179289B (no) 1996-06-03
ATE141321T1 (de) 1996-08-15
EP0486784A2 (fr) 1992-05-27
NO179289C (no) 1996-09-11
NO914470D0 (no) 1991-11-14
NO914470L (no) 1992-05-18
GR3021025T3 (en) 1996-12-31

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