EP0457965B1 - Détergents pour machine à laver qui forment peu de mousse - Google Patents

Détergents pour machine à laver qui forment peu de mousse Download PDF

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Publication number
EP0457965B1
EP0457965B1 EP90124032A EP90124032A EP0457965B1 EP 0457965 B1 EP0457965 B1 EP 0457965B1 EP 90124032 A EP90124032 A EP 90124032A EP 90124032 A EP90124032 A EP 90124032A EP 0457965 B1 EP0457965 B1 EP 0457965B1
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Prior art keywords
liquid
foaming
low
fatty alcohol
alkyl
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Application number
EP90124032A
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German (de)
English (en)
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EP0457965B2 (fr
EP0457965A1 (fr
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
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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
    • 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
    • C11D1/02—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
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives

Definitions

  • the present invention relates to low-foaming liquid or powdery preparations for washing textiles, the surfactants of which are largely made from renewable raw materials.
  • Liquid detergents today mainly consist of anionic surfactants, especially alkylbenzenesulfonate, fatty alcohol oxyethylate and soap, whereas washing powders contain not only the surfactants alkylbenzenesulfonate and fatty alcohol oxyethylate, but also builder substances, bleaching agents and other electrolytes as essential active ingredients.
  • surfactants in particular those based on petrochemicals, are used.
  • the object of the invention was therefore to find a surfactant combination for low-foaming detergents, which are largely made from renewable raw materials, which are extremely biodegradable and achieve very good washing results.
  • This object has been achieved by a surfactant combination which essentially consists of alkyl polyglycosides, ether carboxylates and soap.
  • alkyl polyglycoside in combination with anionic surfactants is known.
  • DE-OS 593 422 already mentions the washing effect-enhancing effect of alkyl glycoside in soaps.
  • Later documents such as EP-A 0 075 994, 0 105 556, 0 199 765 or DE-OS 37 02 286 describe the use of alkyl polyglycosides in combination with a number of known anionic surfactants in detergents. The most important in terms of quantity is the most important surfactant, alkylbenzenesulfonate.
  • components depending on the state of aggregation are other surfactants in small quantities, complexing agents, bleaching agents, optical brighteners, graying inhibitors, corrosion inhibitors, foam regulators, stabilizers, enzymes, enzyme stabilizers, electrolytes, hydrotropic substances, solubilizers, etc.
  • 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. Or 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 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 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 are present side by side with a- and ß-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 expediently determined by means of 1 H-NMR.
  • the detergents according to the invention contain 5 to 30% alkyl polyglycoside, preferably 7 to 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 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) with> 10,000 mg / kg as well as the aquatic toxicity LC 50 (gold orfe) with approx. 12 mg / I and EC 50 (daphnia) with 30 mg / I 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.
  • the carboxymethylated oxethylates can be according to DE-OS 24 18 444 or EP-A 0 106 018 by reacting oxethylates of the formula R'-O (CH 2 -CH 2 -O) n H with chloroacetic acid or a salt of chloroacetic acid in the presence of alkali hydroxide or other bases. But other manufacturing processes such. B. by means of catalytic oxidation according to EP-A 0 018 681 or 0 039 111 are suitable.
  • Corresponding alcohols for the production of the fatty alcohol ether carboxylates are preferably fatty alcohols or Ziegler alcohols, in exceptional cases also oxo alcohols.
  • the carboxymethylation following the oxethylation can be complete if the procedure is appropriate, so that the fatty alcohol ether carboxylates are purely anionic surfactants.
  • the carboxymethylation is incomplete, the products contain certain amounts of unreacted oxyethylate.
  • the formulas II and III therefore usually mean a mixture with different amounts of unreacted oxethylates. Accordingly define a degree of implementation. A degree of conversion between 70 and 100% is preferred.
  • the fatty alcohol ether carboxylates are also very environmentally friendly surfactants. Biodegradation rates above 90% were determined using a sewage treatment plant simulation model / DOC analysis.
  • the acute oral toxicity LD 50 (rat) and the aquatic toxicity LC 50 (gold orfe) are about as favorable as that of the alkyl polyglucosides. The same applies to skin and mucous membrane compatibility.
  • the detergents according to the invention contain 5 to 30% fatty alcohol ether carboxylates, which can also be mixtures. A content of 7 to 20% fatty alcohol ether carboxylate is preferred.
  • the detergents according to the invention contain 5 to 30%, preferably 7 to 20% soap, which will usually be a mixture of different components.
  • alkanesulfonates are alkanesulfonates, olefinsulfonates, alkylbenzenesulfonates, ⁇ -sulfofatty acid esters, fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic esters, alkanoloxethylates, fatty acid alkanolamides, amine oxides, betaines, sulfobetaines, etc.
  • alkanesulfonates are alkanesulfonates, olefinsulfonates, alkylbenzenesulfonates, ⁇ -sulfofatty acid esters, fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic esters, alkanoloxethylates, fatty acid alkanolamides, amine oxides, betaines, sulfobetaines, etc.
  • Builders are primarily to be mentioned as non-surfactant components.
  • water-soluble builders such as different polyphosphates, phosphonates, carbonates, polycarboxylates, citrates, 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 complexing, sodium sulfate should also be mentioned here.
  • water-insoluble builders such as aluminosilicates of suitable particle size, is also according to the invention (cf. EP-A 0 075 994).
  • the 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, p. 21 (1988).
  • concentration of the bleaching agents is 0 to 40%, preferably 0 to 30%.
  • Adjusting agents such as low molecular weight monohydric 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 are optionally used according to the invention
  • the total use concentration in the machine detergents according to the invention is 0.3-20 g / l for the surfactant fraction. 0.5-10 g / l are preferred.
  • the invention is illustrated by the following examples.
  • the liquid detergent formulations listed in Tables 1 and 2 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 foaming power was determined in accordance with DIN 53 902, Part 1.
  • the concentration of detergent substance was 1 g / I in each case, the foam volume was registered after 5 minutes.
  • the washability was measured both in the Linitest laboratory washing machine (ie with moderate mechanical stress) and in a normal household machine. 11 x 18 cm served as the model fabric Large rags made of WFK test fabric with skin fat pigment soiling: polyester (PE), mixed fabric (MG) and cotton (BW), as water drinking water (13 ° dH). Polyester was washed at 30 ° C, blended fabrics and cotton at 60 ° C.
  • the active ingredient concentration was 1 g / I, in the household washing machine 5 g / I, the pH in each case about 7, the liquor ratio in about 1: 60 and 1: 4, the washing times in both cases were about 30 minutes .
  • Tables 1 and 2 show the comparison of the properties of the detergents according to the invention as a liquid formulation with those of other known combinations and of a liquid branded detergent, in which one can assume that the formulation has been optimized.
  • the clear point and viscosity fully correspond to the standard customary for liquid detergents.
  • the foaming power of the formulations according to the invention shows - without further regulating additives - very favorable values. This applies in particular to the washing ability.
  • the formulations according to the invention behave far more effectively here than other known combinations, the surfactant content of which likewise consists of anionic surfactant, alkyl polyglucoside and soap (comparative examples 1 and 2).
  • Tab. 3 shows the comparison of the properties of powdery detergent formulations according to the invention with those of a known combination or a branded detergent. Bulk density, angle of repose and foaming power were determined according to DIN methods. The solubility can be estimated by plotting the electrical conductivity over time, 80% of an average final conductivity being taken as the measured value when 1 g of powder is dissolved in 800 ml of drinking water (13 ° dH). The measured values contain an error of ⁇ 5%.
  • the powders according to the invention behave very similarly and better in their washing values. Again, the washing effects, which are greatly improved in contrast to known formulations (example 15) with anionic surfactants, are clear.

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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 (8)

1. Détergent pour machine, liquide ou en poudre, peu moussant,
caractérisé en ce que la partie tensioactive est constituée
de 5 à 30 % d'un alkylpolyglycoside,
de 5 à 30 % d'un carboxylate d'alcool gras polyéhoxylé,
de 5 à 30 % de savon, et
de 0 à 3 % d'autres tensioactifs.
2. Détergent pour machine, liquide ou en poudre, peu moussant, selon la revendication 1,
caractérisé en ce que l'alkylpolyglycoside a la formule (I)
Figure imgb0012
dans laquelle R est un radical alkyle à chaîne droite ou ramifiée, saturé ou insaturé, ayant de 10 à 18 atomes de carbone, ou leurs mélanges, et Zn est un radical polyglycosyle comportant n 1 à 3 motifs hexose ou pentose, ou leurs mélanges.
3. Détergent pour machine, liquide ou en poudre, peu moussant, selon les revendications 1 et 2, caractérisé en ce que l'alkylpolyglycoside est un polyglucoside d'alcool gras dans lequel n vaut de 1,1 à 2.
4. Détergent pour machine, liquide ou en poudre, peu moussant, selon les revendications 1 à 3,
caractérisé en ce que le carboxylate d'alcool gras polyéthoxylé correspond a la formule (II) ou (III)
Figure imgb0013
Figure imgb0014
où R' et R" sont des radicaux alkyle à chaîne droite ou ramifiée, saturés ou insaturés, ayant de 8 à 22 atomes de carbone, x et y valent 1 à 40, m et z valent 1 ou 2, et M et N sont chacun un hydrogène ou un métal alcalin, un métal alcalino-terreux, l'ammonium ou un alcanolammonium.
5. Détergent pour machine, liquide ou en poudre, peu moussant, selon la revendication 4,
caractérisé en ce que le carboxylate d'alcool gras polyéthoxylé est un produit d'éthoxylation carboxy- méthylé d'un alcool gras de formule (II) dans laquelle R' a de 10 à 18 atomes de carbone, x vaut de 3 à 20, m = 1 et M est le sodium, le potassium, l'ammonium ou un alcanolammonium.
6. Détergent pour machine, liquide ou en poudre, peu moussant, selon les revendications 1 à 5,
caractérisé en ce que le savon a la formule (IV)
Figure imgb0015
dans laquelle R'" est un radical alkyle saturé ou insaturé ayant de 8 à 22 atomes de carbone, et P est un hydrogène, un métal alcalin, l'ammonium ou un alcanolammonium.
7. Détergent pour machine, liquide ou en poudre, peu moussant, selon les revendications 1 à 6,
caractérisé en ce qu'il contient, en tant que constituants non tensio-actifs, des adjuvants des agents de blanchiment, des agents de coupage, des enzymes, des stabilisants, des inhibiteurs de grisaillement, des inhibiteurs de corrosion, des azurants optiques, des colorants, des huiles parfumantes et éventuellement d'autres additifs.
8. Détergent pour machine, liquide ou en poudre, peu moussant, selon les revendications 1 à 7,
caractérisé en ce que la concentration de la partie tensioactive est de 0,3 à 20 g/I.
EP90124032A 1990-05-25 1990-12-13 Détergents pour machine à laver qui forment peu de mousse Expired - Lifetime EP0457965B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4016819A DE4016819A1 (de) 1990-05-25 1990-05-25 Schwachschaeumende maschinen-waschmittel
DE4016819 1990-05-25

Publications (3)

Publication Number Publication Date
EP0457965A1 EP0457965A1 (fr) 1991-11-27
EP0457965B1 true EP0457965B1 (fr) 1995-06-21
EP0457965B2 EP0457965B2 (fr) 2002-04-24

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ID=6407153

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EP90124032A Expired - Lifetime EP0457965B2 (fr) 1990-05-25 1990-12-13 Détergents pour machine à laver qui forment peu de mousse

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EP (1) EP0457965B2 (fr)
JP (1) JPH04227998A (fr)
AT (1) ATE124083T1 (fr)
CA (1) CA2043147A1 (fr)
DE (2) DE4016819A1 (fr)
DK (1) DK0457965T3 (fr)
ES (1) ES2075873T3 (fr)
NO (1) NO178233C (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4331297A1 (de) * 1993-09-15 1995-03-16 Henkel Kgaa Stückseifen
JP2000509713A (ja) * 1996-05-08 2000-08-02 ヘンケル コーポレーション アルキルポリグリコシドエーテルカルボン酸
AU1297199A (en) * 1997-11-10 1999-05-31 Henkel Corporation Alkyl polyglycoside ether carboxylates
US6350727B1 (en) * 2000-01-28 2002-02-26 Amway Corporation Non-streaking no-wipe cleaning compositions with improved cleaning capability
JP2004035808A (ja) * 2002-07-05 2004-02-05 Nissan Soap Co Ltd 液体洗浄剤組成物
JP4247086B2 (ja) * 2003-10-06 2009-04-02 花王株式会社 洗浄剤組成物
EP3266859A1 (fr) * 2016-07-05 2018-01-10 Basf Se Composition appropriée comme agent d'élimination de dégraissage et/ou de dépôts de type huile grasse

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0070075B2 (fr) * 1981-07-13 1992-11-04 THE PROCTER & GAMBLE COMPANY Compositions liquides, moussantes de rinçage pour la vaisselle
US4483787A (en) * 1983-12-28 1984-11-20 The Procter & Gamble Company Concentrated aqueous detergent compositions
IL81354A (en) * 1986-01-30 1990-11-05 Colgate Palmolive Co Liquid detergent having improved softening properties
FR2617862B1 (fr) * 1987-07-09 1994-01-07 Sandoz Sa Compositions detergentes exemptes de builders

Also Published As

Publication number Publication date
CA2043147A1 (fr) 1991-11-26
NO911993L (no) 1991-11-26
JPH04227998A (ja) 1992-08-18
DK0457965T3 (da) 1995-11-06
NO911993D0 (no) 1991-05-23
DE59009297D1 (de) 1995-07-27
NO178233B (no) 1995-11-06
DE4016819A1 (de) 1991-12-19
ATE124083T1 (de) 1995-07-15
EP0457965B2 (fr) 2002-04-24
ES2075873T3 (es) 1995-10-16
NO178233C (no) 1996-02-14
EP0457965A1 (fr) 1991-11-27

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