EP0490040A2 - Détergent liquide - Google Patents

Détergent liquide Download PDF

Info

Publication number
EP0490040A2
EP0490040A2 EP91117180A EP91117180A EP0490040A2 EP 0490040 A2 EP0490040 A2 EP 0490040A2 EP 91117180 A EP91117180 A EP 91117180A EP 91117180 A EP91117180 A EP 91117180A EP 0490040 A2 EP0490040 A2 EP 0490040A2
Authority
EP
European Patent Office
Prior art keywords
liquid detergent
fatty alcohol
carbon atoms
mixtures
detergent according
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.)
Granted
Application number
EP91117180A
Other languages
German (de)
English (en)
Other versions
EP0490040B1 (fr
EP0490040A3 (en
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
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
Application filed by Huels AG, Chemische Werke Huels AG filed Critical Huels AG
Publication of EP0490040A2 publication Critical patent/EP0490040A2/fr
Publication of EP0490040A3 publication Critical patent/EP0490040A3/de
Application granted granted Critical
Publication of EP0490040B1 publication Critical patent/EP0490040B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D1/02—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
    • C11D1/14—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
    • 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

Definitions

  • the present invention relates to liquid preparations for washing textiles.
  • Liquid detergents today mainly consist of anionic surfactants, especially alkylbenzenesulfonate, fatty alcohol oxyethylate and soap. These surfactants, which are common in detergent formulations, are mainly based on petrochemicals. In view of the future raw material situation (oil shortage), this petrochemical basis is a considerable disadvantage. Another disadvantage is that the biodegradability and ecotoxicity of these surfactants often do not reach the corresponding level of surfactants on a native basis.
  • the object of the invention was therefore to find a surfactant mixture for liquid detergents which contains a high proportion of surfactants which are obtained from renewable raw materials; In addition to excellent washing results, high biodegradability was required.
  • This object was achieved by a mixture which, in addition to fatty alcohol oxyethylate and soap and small amounts of anionic surfactant, contains 3 to 30% alkyl polyglycoside.
  • EP-0 075 994, EP-0 075 995 and EP-0 075 996 claim surfactant mixtures which, in addition to APG, contain anionic and nonionic surfactants, although the degree of glycosidation of the APG is ⁇ 1.5.
  • DE-37 02 286 claims alkyl polyglycosides in addition to anionic and nonionic surfactants as detergents with the restrictions that the anionic content should be ⁇ 50% of that of the oxyethylate.
  • EP-0 199 765 describes alkylpolyglycoside mixtures with anionic and nonionic surfactants, the content of nonionic surfactants should be ⁇ 10% and the degree of glycosidation of the alkylpolyglycoside ⁇ 1.4.
  • the formulation according to the invention delivers excellent washing results with an extremely low anionic surfactant content.
  • the alkyl polyglycosides used according to the invention can be produced by known processes based on renewable raw materials.
  • dextrose is reacted with n-butanol to give butylpolyglycoside mixtures in the presence of an acidic catalyst, which are transglycosidated with long-chain alcohols in the presence of an acidic catalyst to give the desired alkylpolyglycoside mixtures.
  • dextrose is immediately reacted with the desired long-chain alcohol.
  • 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 alcohols with 8 to 18 carbon atoms, in particular native alcohols from the hydrogenation of carboxylic acids or carboxylic acid derivatives.
  • Ziegler alcohols or oxo alcohols can also be used.
  • the polyglycosyl radicals Z n are determined, on the one hand, by the selection of the carbohydrate and, on the other hand, by setting the average degree of polymerization n z. 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 Saccachrid 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.
  • the degree of glycosidation is advantageously determined by means of 1 H-NMR.
  • the detergents according to the invention contain 3 to 30% alkyl polyglycoside, preferably 5-20%.
  • 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 figure can be seen against the background that with this test method (total degradation) a degree of degradation ⁇ 70% already indicates the substance to be readily degradable.
  • the acute oral toxicity LD 50 (rat) with> 10,000 mg / kg as well as the aquatic toxicity LC 50 (gold orfe) with approx. 12 mg / l and EC 50 (daphnia) with 30 mg / l are by a factor of 3 to 5 cheaper than the corresponding values of today's most important surfactants. The same applies to skin and mucous membrane compatibility.
  • Anionic surfactants used are alkylbenzene sulfate, alkane sulfonates, olefin sulfonates, fatty alcohol sulfates and fatty alcohol ether sulfates having 9 to 18 carbon atoms in the alkyl or alkylene group.
  • Na, K, NH4, Mg and mixtures are the counterions.
  • These anionic surfactants, which can be present in the mixtures according to the invention in amounts of 0 to 7% by weight, are not to be understood as soap. Quantities of 0 to 5% by weight are preferred.
  • the fatty alcohol oxyethylates used according to the invention correspond to compounds of the formula II R '' - O- (CH2-CH2-O) x H II, in which R ′′ is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22, preferably 10 to 20 carbon atoms and x 2 to 20, preferably 3 to 15.
  • the compounds are generally prepared by addition of ethylene oxide onto longer-chain alcohols in the presence of basic or acidic catalysts.
  • basic or acidic catalysts For economic reasons, commercially available alcohols with 8 to 22 carbon atoms from the hydrogenation of carboxylic acids or carboxylic acid derivatives are favorable.
  • Ziegler alcohols or oxo alcohols can also be used.
  • the alcohol oxyethylates are known to be readily biodegradable; Their data are also favorable with regard to aquatoxicity, skin and mucous membrane compatibility.
  • liquid detergents according to the invention contain 11 to 30% fatty alcohol oxyethylates, which can also be mixtures. Contents of 12 to 25% by weight are preferred.
  • Fatty acid salts or their acids according to the invention correspond to formula III R '''COOP III, in which R '''is a saturated or unsaturated alkyl radical having 8 to 22 carbon atoms and P is hydrogen, alkali, ammonium or alkanolammonium.
  • the detergents according to the invention contain 5 to 30% soap, which will usually be a mixture of different components. Contents of 7 to 25% are preferred.
  • water-soluble builders such as different polyphosphates, phosphonates, carbonates, polycarboxylates, citronates, polyacetates such as NTA and EDTA, etc. or mixtures thereof are used. These compounds are usually used as alkali salts, preferably as sodium salts. Although not complex, too To mention sodium sulfate here.
  • water-insoluble builders such as aluminosilicates of suitable particle size, is also according to the invention (cf. EP-A 0 075 994).
  • concentration of the builders in the detergent is 0 to 70%, preferably 0 to 50%.
  • Bleaching agents such as sodium perborate, optionally combined with bleach activators such as tetraacetylethylene diamine etc. or percarbonate, are also used according to the invention; Other bleaching agents are of course also possible (cf. K. Engel, Tenside Surfactants 25, S. (1988).
  • concentration of the bleaching agents is 0 to 40%, preferably 0 to 30%.
  • Adjusting agents such as low molecular weight mono- or dihydric alcohols, alkyl ethers of polyhydric alcohols, hydrotropics such as alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical, alkanolamines or urea, enzymes such as in particular proteases and enzyme stabilizers, corrosion inhibitors such as alkali silicates, optical, may be used according to the invention
  • the total use concentration in the liquid detergents according to the invention is 0.3-20 g / l for the surfactant fraction according to the invention. 0.5-10 g / l are preferred.
  • the invention is illustrated by the following examples.
  • the liquid detergent formulations listed in Table 1 each contain 6% triethanolamine, 12% ethanol, 6% 1,2-propylene glycol and water ad 100% in addition to the surfactant components mentioned according to the invention.
  • the viscosity of the cleaning liquid was measured in a rotary viscometer (Haake RV 20) at 25 ° C under shear rates of approx. 10 sec. ⁇ 1.
  • the table shows the comparison of the properties of the detergents according to the invention as a liquid formulation with those of other known combinations and with a liquid brand detergent, in which one can presuppose a formulation optimization.
  • the clear point, viscosity and foaming capacity correspond approximately to the standard customary for liquid detergents.
  • the detergents according to the invention behave significantly superior in their washing activity.
  • the results at low temperatures and problematic fabrics are almost outstanding like PE and MG: The tests show the superiority of the formulations according to the invention over the use of alkypolyglycosides with too high degrees of glycosidation or overly high levels of anionic surfactant at the expense of the oxyethylates.

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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)
  • Cleaning Or Drying Semiconductors (AREA)
EP91117180A 1990-12-08 1991-10-09 Détergent liquide Expired - Lifetime EP0490040B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4039223A DE4039223A1 (de) 1990-12-08 1990-12-08 Fluessige waschmittel
DE4039223 1990-12-08

Publications (3)

Publication Number Publication Date
EP0490040A2 true EP0490040A2 (fr) 1992-06-17
EP0490040A3 EP0490040A3 (en) 1992-10-21
EP0490040B1 EP0490040B1 (fr) 1997-08-13

Family

ID=6419889

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91117180A Expired - Lifetime EP0490040B1 (fr) 1990-12-08 1991-10-09 Détergent liquide

Country Status (5)

Country Link
EP (1) EP0490040B1 (fr)
AT (1) ATE156855T1 (fr)
DE (2) DE4039223A1 (fr)
ES (1) ES2106043T3 (fr)
NO (1) NO178267C (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0592947A1 (fr) * 1992-10-12 1994-04-20 ALBRIGHT & WILSON UK LIMITED Préparations de nettoyage
EP0634480A1 (fr) * 1993-07-14 1995-01-18 The Procter & Gamble Company Compositions détergentes
US5866530A (en) * 1995-11-25 1999-02-02 Henkel Kommanditgesellschaft Auf Aktien Non-aqueous liquid mixtures of alkyl polyglycoside and alkyl polyalkylene glycol ether useful in various detergent applications
US6384010B1 (en) 2000-06-15 2002-05-07 S.C. Johnson & Son, Inc. All purpose cleaner with low organic solvent content

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4236506A1 (de) * 1992-10-29 1994-05-05 Henkel Kgaa Verfahren zur Herstellung wäßriger Lösungen anionischer Tenside mit verbesserter Kältestabilität
US5759979A (en) * 1993-04-05 1998-06-02 Henkel Kommanditgesellschaft Auf Aktien Detergent mixtures comprising APG and fatty alcohol polyglycol ether
DE19844004A1 (de) * 1998-09-25 2000-03-30 Cognis Deutschland Gmbh Tensidmischungen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0075995A2 (fr) * 1981-09-28 1983-04-06 THE PROCTER & GAMBLE COMPANY Compositions détergentes contenant de mélanges d'alcylpolysaccharide et d'agents tensio-actifs non-ioniques
WO1990015855A1 (fr) * 1989-06-22 1990-12-27 Henkel Kommanditgesellschaft Auf Aktien Produits liquides de lavage
WO1992002607A1 (fr) * 1990-07-27 1992-02-20 Henkel Kommanditgesellschaft Auf Aktien Liquide de lavage blanchissant
WO1992003527A1 (fr) * 1990-08-22 1992-03-05 Henkel Kommanditgesellschaft Auf Aktien Produit liquide de lavage a viscosite accrue

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0075995A2 (fr) * 1981-09-28 1983-04-06 THE PROCTER & GAMBLE COMPANY Compositions détergentes contenant de mélanges d'alcylpolysaccharide et d'agents tensio-actifs non-ioniques
WO1990015855A1 (fr) * 1989-06-22 1990-12-27 Henkel Kommanditgesellschaft Auf Aktien Produits liquides de lavage
WO1992002607A1 (fr) * 1990-07-27 1992-02-20 Henkel Kommanditgesellschaft Auf Aktien Liquide de lavage blanchissant
WO1992003527A1 (fr) * 1990-08-22 1992-03-05 Henkel Kommanditgesellschaft Auf Aktien Produit liquide de lavage a viscosite accrue

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0592947A1 (fr) * 1992-10-12 1994-04-20 ALBRIGHT & WILSON UK LIMITED Préparations de nettoyage
EP0634480A1 (fr) * 1993-07-14 1995-01-18 The Procter & Gamble Company Compositions détergentes
US5866530A (en) * 1995-11-25 1999-02-02 Henkel Kommanditgesellschaft Auf Aktien Non-aqueous liquid mixtures of alkyl polyglycoside and alkyl polyalkylene glycol ether useful in various detergent applications
US6384010B1 (en) 2000-06-15 2002-05-07 S.C. Johnson & Son, Inc. All purpose cleaner with low organic solvent content

Also Published As

Publication number Publication date
NO914816D0 (no) 1991-12-06
EP0490040B1 (fr) 1997-08-13
EP0490040A3 (en) 1992-10-21
ES2106043T3 (es) 1997-11-01
DE59108822D1 (de) 1997-09-18
DE4039223A1 (de) 1992-06-11
ATE156855T1 (de) 1997-08-15
NO914816L (no) 1992-06-09
NO178267C (no) 1996-02-21
NO178267B (no) 1995-11-13

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