EP0444262B1 - Détergent liquide moussant - Google Patents

Détergent liquide moussant Download PDF

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Publication number
EP0444262B1
EP0444262B1 EP90123844A EP90123844A EP0444262B1 EP 0444262 B1 EP0444262 B1 EP 0444262B1 EP 90123844 A EP90123844 A EP 90123844A EP 90123844 A EP90123844 A EP 90123844A EP 0444262 B1 EP0444262 B1 EP 0444262B1
Authority
EP
European Patent Office
Prior art keywords
weight
liquid
cleaning formulation
cleaning
alkyl
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
EP90123844A
Other languages
German (de)
English (en)
Other versions
EP0444262A2 (fr
EP0444262B2 (fr
EP0444262A3 (en
Inventor
Dieter Dr. Balzer
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.)
Sasol Germany GmbH
Original Assignee
Huels AG
Chemische Werke Huels AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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Application filed by Huels AG, Chemische Werke Huels AG filed Critical Huels AG
Publication of EP0444262A2 publication Critical patent/EP0444262A2/fr
Publication of EP0444262A3 publication Critical patent/EP0444262A3/de
Application granted granted Critical
Publication of EP0444262B1 publication Critical patent/EP0444262B1/fr
Publication of EP0444262B2 publication Critical patent/EP0444262B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—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

Definitions

  • the invention relates to an environmentally compatible, 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.
  • Modern products consist of neutral aqueous formulations based on foaming surfactants.
  • 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. Of particular importance because of the long skin contact of the user 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.
  • Generally recognized test methods are a) the plate test, 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 lead to very similar results (see G. Jakobi in H. Stache, Tensid Taschenbuch , 2nd edition, Kunststoff 1981, pp. 252 ff.).
  • the object of the invention was therefore to provide a very skin-compatible cleaning agent with an excellent cleaning action and moderate foaming power, the cleaning surfactants of which are largely biodegradable.
  • liquid cleaning agent which, as cleaning surfactants, contains exclusively a mixture of alkyl polyglycosides of different alkyl chain lengths.
  • 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 ricin oil 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 alkyl polyglycosides with fatty alcohol oxyethylates as a liquid detergent.
  • dishwashing detergents which contain only alkyl polyglycosides as cleaning surfactants achieve excellent cleaning effects if these alkyl polyglycosides have a sufficient detergent content have hydrophobic structure. This is achieved by using fatty alcohols with relatively long hydrocarbon chains in the synthesis, the proportions of fatty alcohol to monosaccharide units being chosen so that the average degree of glycosidation (glycoside units per fatty alkyl radical) is not too high.
  • Alkyl polyglycosides used according to the invention satisfy the general formula RO-Zn, in which R is a linear or branched, saturated or unsaturated aliphatic alkyl radical and Z n is a polyglycosyl radical.
  • 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 commercially available surfactant alcohols in particular native fatty alcohols from the hydrogenation of fatty acids or fatty acid derivatives, are favorable for economic reasons. 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 lie 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 using polar solvents, such as acetone, from alkyl polyglycosides.
  • polar solvents such as acetone
  • the degree of glycosidation is expediently determined by 1 H NMR certainly.
  • the cleaning agents according to the invention usually contain 3 to 50 percent by weight, preferably 5 to 30 percent by weight, of total alkyl polyglycoside in aqueous solution.
  • the total polyglycoside consists of at least two components, a hydrophilic component I and a hydrophobic component II.
  • I has no or very little cleaning action and serves to increase the solubility in water or to lower the clear point.
  • the hydrophobic component II is the actual cleaning agent. It is completely surprising with the mixture that the cleaning action of component II is largely retained, although I itself has practically no cleaning action.
  • the measure for adjusting the hydrophilicity is primarily the hydrophobic remainder of the alkyl polyglycoside.
  • hydrophobic alkyl radical is in the range ⁇ C10.
  • the adjustment of the hydrophobic component is a little more subtle.
  • the alkyl radical should be> C10, at the same time the degree of glycosidation must be reduced to such an extent that the cleaning effect is optimal.
  • the quantitative ratio of the two components I / II should be between 1: 1 and 1:10, preferably between 1: 2 and 1: 5.
  • 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 sewage plant simulation mode II / 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 fall as synthesis-related about 50% aqueous amber colored solutions.
  • 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.
  • the ratio of alkyl polyglycoside / solvent can be 1: 1 to 4: 1.
  • solubility can be increased considerably, especially at low temperatures.
  • Alkali and alkaline earth halides have proven to be suitable electrolytes.
  • the ratio of solvent / electrolyte can be 1: 1 to 4: 1.
  • constituents of the cleaning agents according to the invention in small amounts are conventional dyes and perfume oils, and also alkanolamines or hydrotropes, such as non-surfactant alkylbenzenesulfonates having 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.
  • Citric acid, EDTA, NTA and other complexing agents have proven to be further suitable additives.
  • 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). Pork lard served as soiling, which was applied to the glasses at 50.0 ° C, which are then subject to a defined cooling process to 23 ° C (room temperature). The initial rinse temperature is also 50 ° C.
  • Table 1 compares the cleaning effect of individual surfactants, which increases sharply with increasing molecular hydrophobicity in the case of alkyl polyglycosides.
  • Table 2 demonstrates that even a strong increase in the surfactant concentration only gives unsatisfactory cleaning effects if the alkyl polyglycoside is too hydrophilic, as in the case of Triton CG 110.
  • Table 3a compares the cleaning action of the alkyl polyglycosides according to the invention with those of optimized branded products depending on the detergent concentration for a medium water hardness; Table 3b the analogous conditions for soft water.

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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)

Claims (6)

  1. Produit nettoyant moussant liquide,
    caractérisé par le fait qu'il est constitué
    de 3 à 40 % en poids d'un alkylpolyglycoside I,
    de 3 à 40 % en poids d'un alkylpolyglycoside II,
    de 0 à 10 % en poids d'un tiers-solvant,
    de 0 à 10 % en poids d'un électrolyte,
    de 0 à 3 % d'additifs, et
    le complément à 100 % en poids étant constitué d'eau,
    où l'alkylpolyglycoside I correspond à la formule (I)

            R₁-O-Zn1     (I)

    dans laquelle R₁ est un radical alkyle saturé ou insaturé, à chaîne droite ou ramifiée, ayant en moyenne de 7 à 10 atomes de carbone, et Zn1 est un radical polyglycosyle dans lequel n1 = 1 à 3 motifs hexose ou pentose, ou leurs mélanges,
    et l'alkylpolyglycoside II correspond à la formule (II)

            R₂-O-Zn2     (II)

    dans laquelle R₂ est un radical alkyle saturé ou insaturé, à chaîne droite ou ramifiée, ayant de 11 à 18 atomes de carbone, et Zn2 est un radical polyglycosyle dans lequel n2 = 1 à 3 motifs hexose ou pentose, ou leurs mélanges.
  2. Produit nettoyant moussant liquide selon la revendication 1,
    caractérisé par le fait que R₂ est un radical alkyle gras ayant de 12 à 18 atomes de carbone, et Zn2 est un radical polyglycosyle dans lequel n2 = 1,1 à 2 motifs glycoside.
  3. Produit nettoyant moussant liquide selon l'une des revendications précédentes,
    caractérisé par le fait que le rapport pondéral de R₁-O-Zn1 à R₂-O-Zn2 est compris entre 1 : 1 et 1 : 10.
  4. Produit nettoyant moussant liquide selon l'une des revendications précédentes,
    caractérisé par le fait qu'on utilise comme tiers-solvant des monoalcools et polyalcools à faible masse moléculaire, des éthers de polyalcool, des alcanolamines et/ou des substances hydrotropes.
  5. Produit nettoyant moussant liquide selon l'une des revendications précédentes,
    caractérisé par le fait qu'on utilise comme électrolytes des halogénures de métaux alcalins ou des halogénures de métaux alcalino-terreux, ou encore leurs mélanges.
  6. Utilisation du produit nettoyant moussant liquide selon l'une des revendications précédentes, comme agent de rinçage à la main.
EP90123844A 1990-02-26 1990-12-11 Détergent liquide moussant Expired - Lifetime EP0444262B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4005958 1990-02-26
DE19904005958 DE4005958A1 (de) 1990-02-26 1990-02-26 Fluessiges, schaeumendes reinigungsmittel

Publications (4)

Publication Number Publication Date
EP0444262A2 EP0444262A2 (fr) 1991-09-04
EP0444262A3 EP0444262A3 (en) 1992-01-22
EP0444262B1 true EP0444262B1 (fr) 1996-02-28
EP0444262B2 EP0444262B2 (fr) 2004-10-06

Family

ID=6400955

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90123844A Expired - Lifetime EP0444262B2 (fr) 1990-02-26 1990-12-11 Détergent liquide moussant

Country Status (3)

Country Link
EP (1) EP0444262B2 (fr)
DE (2) DE4005958A1 (fr)
DK (1) DK0444262T3 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4110506A1 (de) * 1991-03-30 1992-10-01 Huels Chemische Werke Ag Emulgatoren zur herstellung von in der kosmetik oder medizin verwendbaren oel-in-wasser-emulsionen etherischer oele
EP0607198B1 (fr) * 1991-10-10 2001-02-14 Cognis Corporation Preparation de melanges ameliores contenant des agents tensio-actifs alkylpolyglycosides
US5449763A (en) * 1991-10-10 1995-09-12 Henkel Corporation Preparation of alkylpolyglycosides
DE4225224A1 (de) * 1992-07-30 1994-02-03 Henkel Kgaa Verfahren zur Herstellung von lagerstabilen nichtionischen Tensiden
DE4319700A1 (de) * 1993-06-16 1994-12-22 Henkel Kgaa Ultramilde Tensidmischungen
DE4319699A1 (de) * 1993-06-16 1994-12-22 Henkel Kgaa Ultramilde Tensidmischungen
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
DE19944543C2 (de) * 1999-09-17 2002-04-18 Cognis Deutschland Gmbh Tensidgemische
MY165645A (en) * 2010-07-19 2018-04-18 Colgate Palmolive Co Cleansing composition with decyl and coco glucosides

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3547828A (en) * 1968-09-03 1970-12-15 Rohm & Haas Alkyl oligosaccharides and their mixtures with alkyl glucosides and alkanols
EP0136844A2 (fr) * 1983-09-06 1985-04-10 Henkel Kommanditgesellschaft auf Aktien Détergents contenant des glycosides

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USH171H (en) * 1985-06-24 1986-12-02 A. E. Staley Manufacturing Company Branched chain glycosides
US4725489A (en) † 1986-12-04 1988-02-16 Airwick Industries, Inc. Disposable semi-moist wipes
DE3706015A1 (de) † 1987-02-25 1988-11-17 Henkel Kgaa Fluessiges reinigungsmittel
US5449763A (en) † 1991-10-10 1995-09-12 Henkel Corporation Preparation of alkylpolyglycosides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3547828A (en) * 1968-09-03 1970-12-15 Rohm & Haas Alkyl oligosaccharides and their mixtures with alkyl glucosides and alkanols
EP0136844A2 (fr) * 1983-09-06 1985-04-10 Henkel Kommanditgesellschaft auf Aktien Détergents contenant des glycosides

Also Published As

Publication number Publication date
DE59010166D1 (de) 1996-04-04
EP0444262A2 (fr) 1991-09-04
EP0444262B2 (fr) 2004-10-06
DK0444262T3 (da) 1996-07-01
DE4005958A1 (de) 1991-08-29
EP0444262A3 (en) 1992-01-22

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