EP0486784B2 - Détergent liquide moussant à viscosité augmentée - Google Patents

Détergent liquide moussant à viscosité augmentée Download PDF

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Publication number
EP0486784B2
EP0486784B2 EP91115711A EP91115711A EP0486784B2 EP 0486784 B2 EP0486784 B2 EP 0486784B2 EP 91115711 A EP91115711 A EP 91115711A EP 91115711 A EP91115711 A EP 91115711A EP 0486784 B2 EP0486784 B2 EP 0486784B2
Authority
EP
European Patent Office
Prior art keywords
alkyl
liquid
fatty alcohol
weight
mixtures
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
EP0486784A2 (fr
EP0486784A3 (en
EP0486784B1 (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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Filing date
Publication date
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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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    • 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 are aimed at the manual cleaning of hard surfaces, especially in the Household, such as B. ceramics, porcelain, glass, metal and plastic.
  • Household such as B. ceramics, porcelain, glass, metal and plastic.
  • the most important application area is manual Dishwashing liquid 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).
  • sulfonates such as. B. alkylbenzenesulfonates or sec-alkanesulfonates, both combined with fatty alcohol ether sulfates or fatty alcohol sulfates (EP-A-0 112 047).
  • fatty alcohol ether sulfates or fatty alcohol sulfates
  • Other common ingredients are solubilizers, Dyes 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 role considerable role, for example in the sense that the longer the cleaning solution foams during the rinsing process, the more their cleaning power is also greater.
  • 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. Medium viscosities between 150 and 300 mPa ⁇ s with 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 common cleaning agents usually show sufficient cleaning power and a strong one Foaming power, suitable flow behavior and sufficient compatibility with the hardness constituents of the water.
  • these mixtures are not very skin-friendly because 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 has all the desired properties implies, at the same time high skin tolerance and excellent environmental compatibility.
  • the object was achieved by a liquid cleaning agent which, as a surfactant, was largely only alkyl polyglycoside contains.
  • alkyl polyglycosides in detergents and cleaning agents is in combination with other surfactants known.
  • 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 are used in combination with builder substances, such as nitrilotriacetic acid or sodium tripolyphosphate, as a detergent.
  • the EP-A-0 claims a combination of alkyl polyglycosides with fatty alcohol oxyethylates as a liquid detergent 105 556.
  • DE-OS 35 34 082 also has analogous content, fatty alkyl glycosides having 1 to 1.4 glycoside units per Fatty alkyl radical can be called.
  • Alkyl sulfate or alkyl ether sulfates are used in combination in each case as cosurfactants with fatty acid alkanolamides.
  • EP-A-0 199 765 describes a liquid detergent or detergent with the like Claim.
  • EP-0 199 765 describes cleaning liquids with a minimum content of anionic cosurfactant 3%.
  • alkyl polyglycoside as the only surfactant component of the cleaning liquid.
  • Defacto pure alkyl polyglycoside solutions also have excellent cleaning effects, provided they are sufficiently hydrophobic. The latter succeeds through a longer chain hydrophobic alkyl radical or by 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 based on renewable methods using known methods Raw materials are manufactured. For example, dextrose in the presence of an acid catalyst with n-butanol converted to butyl polyglycoside mixtures, which also with long-chain alcohols in the presence of a acid catalyst to the desired alkyl polyglycoside mixtures umglycosidiert.
  • the structure of the products can be varied within certain limits.
  • the alkyl radical R is selected by the choice of the long chain Alcohol.
  • the commercially available surfactant alcohols are favorable for economic reasons with 10 to 18 carbon atoms, especially 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 junctions between two saccharide residues are also negligible.
  • Alkyl polyglycosides used according to the invention can also be mixed with alkyl polyglycosides Prepare alkyl monoglycosides.
  • the latter can e.g. B. according to EP-A-0 092 355 using polar solvents such as acetone, gain from alkyl polyglycosides or rich.
  • 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 friendly.
  • the degree of biodegradation determined by means of a sewage plant simulation model / DOC analysis for the alkyl polyglycosides according to the invention at 96 ⁇ 3%. This number can be seen against the background that with this test method (total degradation) a degree of degradation> 70% indicates that the substance is readily degradable.
  • Acute oral toxicity LD 50 (rat) and 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 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 setting.
  • 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 weight, mono- and polyhydric alcohols and glycol ethers significantly increase solubility, especially at low temperatures.
  • Particularly suitable solvents are Ethanol, isopropanol, propylene glycol-1,2 etc.
  • Typical concentrations in the detergent 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 be used in small amounts (0.1 to 3 percent by weight) Usual dyes and perfume oils as well as alkanolamines or hydrotropics, 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 be added.
  • 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 effect of the detergent.
  • 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 wash-active substance was 1 g / l each.
  • 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 leads one Clarify the liquid.
  • foaming and viscosity increase significantly and reach very soon the level of commercially available cleaning agents (Example 7 (V).
  • the cleaning effect is due to the addition of anionic Surfactants are not affected by the measurement error and are fully in line with the market standard.
  • Foaming power increases very strongly with the addition of ether sulfate, the clear point changes only relatively little.
  • Completely unexpected is the pronounced viscosity maximum in the range of low anionic surfactant concentrations.
  • This - the present Property co-founding the invention was also observed when other anionic surfactants were added.
  • Such a diagram can also be used to tailor cleaning agents with regard to optimal environmental compatibility.

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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'additifs non tensioactifs usuels et d'eau jusqu'à 100 % en poids, le tensioactif anionique étant choisi dans le groupe comprenant les (alcools gras)sulfates éthers, les (alcools gras) sulfates, les (alcools gras)étherphosphates, les produits d'éthoxylation carboxyméthylés d'alcools gras, les paraffinesulfonates, les oléfinesulfonates, les alkylbenzènesulfonates et leurs mélanges, et dans lequel l'alkylpolyglycoside correspond à la formule I, R-O-Zn dans laquelle R signifie un radical alkyle saturé ou non saturé, ramifié ou non ramifié ayant de 10 à 18 atomes de carbone et Zn signifie un radical polyglycosyle avec n = 1,0 à 1,5 unités d'hexose ou de pentose ou les mélanges de ceux-ci.
  2. Détergent moussant liquide selon la revendication 1,
    caractérisé en ce que
    l'alkylpolyglycoside correspond à la formule I R-O-Zn dans laquelle R est un radical alkyle à chaíne droite ou ramifiée, saturé ou insaturé, ayant de 10 à 18 atomes de carbone et Zn est un radical polyglycosyle avec n = 1,1 à 1,5 motifs ou constituants hexose ou de 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 substances hydrotropes, des polymères, des colorants et des parfums.
  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
DE4036663A DE4036663A1 (de) 1990-11-17 1990-11-17 Fluessiges, schaeumendes reinigungsmittel mit erhoehter viskositaet
DE4036663 1990-11-17

Publications (4)

Publication Number Publication Date
EP0486784A2 EP0486784A2 (fr) 1992-05-27
EP0486784A3 EP0486784A3 (en) 1992-10-07
EP0486784B1 EP0486784B1 (fr) 1996-08-14
EP0486784B2 true 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
US5025069A (en) * 1988-12-19 1991-06-18 Kao Corporation Mild alkyl glycoside-based detergent compositions, further comprising terpene and isothiazolone derivatives
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
EP0486784A2 (fr) 1992-05-27
CA2055650A1 (fr) 1992-05-18
EP0486784A3 (en) 1992-10-07
DE59108078D1 (de) 1996-09-19
ATE141321T1 (de) 1996-08-15
EP0486784B1 (fr) 1996-08-14
JPH04292696A (ja) 1992-10-16
NO179289B (no) 1996-06-03
DE4036663A1 (de) 1992-05-21
NO179289C (no) 1996-09-11
NO914470D0 (no) 1991-11-14
NO914470L (no) 1992-05-18
GR3021025T3 (en) 1996-12-31

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