EP0457965A1 - 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
EP0457965A1
EP0457965A1 EP90124032A EP90124032A EP0457965A1 EP 0457965 A1 EP0457965 A1 EP 0457965A1 EP 90124032 A EP90124032 A EP 90124032A EP 90124032 A EP90124032 A EP 90124032A EP 0457965 A1 EP0457965 A1 EP 0457965A1
Authority
EP
European Patent Office
Prior art keywords
liquid
foaming
low
machine detergent
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
EP90124032A
Other languages
German (de)
English (en)
Other versions
EP0457965B1 (fr
EP0457965B2 (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
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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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6407153&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0457965(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Huels AG, Chemische Werke Huels AG filed Critical Huels AG
Publication of EP0457965A1 publication Critical patent/EP0457965A1/fr
Publication of EP0457965B1 publication Critical patent/EP0457965B1/fr
Application granted granted Critical
Publication of EP0457965B2 publication Critical patent/EP0457965B2/fr
Anticipated expiration legal-status Critical
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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.
  • surfactants which essentially consists of alkyl polyglycosides, ether carboxylates and soap.
  • the invention therefore relates to a low-foaming, liquid or powdered machine detergent, which is characterized in that the surfactant component consists of 5 to 30% alkyl polyglycoside, 5 to 30% alkanol ether carboxylate, 5 to 30% soap and 0 to 3% other surfactants consists.
  • 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.
  • 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 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 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. are used will.
  • 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 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 treatment 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 / 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.
  • Fatty alcohol ether carboxylates are compounds of either formula II or III, (R'-O (CH2-CH2-O) x CH2COO) m M m + II, in which R 'is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 preferably 10 to 18 carbon atoms, x 1 to 40, preferably 3 to 30, m 1 or 2 and M is hydrogen, alkali, alkaline earth metal, ammonium or alkanolammonium or ([R '' - O (CH2-CH2-O) y ] 2CHCOO) z N z + III in which R '' is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22, preferably 10 to 18 carbon atoms, y 1 to 4, preferably 3 to 30, z 1 or 2 and NH, alkali, alkaline earth metal, ammonium, alkanolammonium.
  • 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 (CH2-CH2-O) n H with chloroacetic acid or a salt of chloroacetic acid in the presence of alkali metal 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.
  • Bisalkanol ethoxylate acetates can be e.g. B. according to DE-OS 39 02 663 from oxyethylates and dichloroacetic acid.
  • 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 carried out with the appropriate driving style be complete so that the fatty alcohol ether carboxylates are purely anionic surfactants.
  • 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, a degree of implementation can be defined. 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 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.
  • Fatty acid salts or their acids according to the invention correspond to formula IV R '''COOP IV, 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%, preferably 7 to 20% soap, which will usually be a mixture of different components.
  • anionic, nonionic, zwitterionic and ampholytic surfactants are to be used according to the invention.
  • these are alkanesulfonates, olefinsulfonates, alkylbenzenesulfonates, ⁇ -sulfo fatty acid esters, fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic acid esters, alkanoloxethylates, fatty acid alkanolamides, amine oxides, betaines, sulfobetaines, etc.
  • builders should be mentioned as non-surfactant components.
  • water-soluble builders such as different polyphosphates, phosphonates, carbonates, polycarboxylates, citronates, polyacetates such as NTA and DETA, 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 mono- or dihydric alcohols, alkyl ethers of polyhydric alcohols, hydrotropics such as alkylbenzenesulfonates with 1 to 3C atoms in the alkyl radical, alkanolamines or urea, enzymes such as in particular proteases and enzyme stabilizers, corrosion inhibitors such as alkali silicates, optical brighteners may be used according to the invention especially based on and stilbene and pyrazoline, foam regulators, graying inhibitors such.
  • 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 / l, the foam volume was registered after 5 minutes.
  • the washability was measured both in the Linitest laboratory washing machine (i.e. with moderate mechanical stress) and in a normal household machine.
  • 11 x 18 cm rags made of WFK test fabric with skin fat pigment soiling served as model fabric: polyester (PE), mixed fabric (MG) and cotton (BW), and drinking water (13 ° dH) as water.
  • Polyester was washed at 30 ° C, blended fabrics and cotton at 60 ° C.
  • the active ingredient concentration was 1 g / l, in the household washing machine 5 g / l, 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 also 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%.
  • Example 20 Apart from a much higher bulk density, typical of agglomerated washing powders compared to the spray-dried brand product (example 20), 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 of 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)
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 true EP0457965A1 (fr) 1991-11-27
EP0457965B1 EP0457965B1 (fr) 1995-06-21
EP0457965B2 EP0457965B2 (fr) 2002-04-24

Family

ID=6407153

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90124032A Expired - Lifetime EP0457965B2 (fr) 1990-05-25 1990-12-13 Détergents pour machine à laver qui forment peu de mousse

Country Status (8)

Country Link
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)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997042299A1 (fr) * 1996-05-08 1997-11-13 Henkel Corporation Carboxylates d'alkyl polyglycoside ether
WO1999024538A1 (fr) * 1997-11-10 1999-05-20 Henkel Corporation Ether carboxylates d'alkyl polyglycoside

Families Citing this family (5)

* 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
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0070075A2 (fr) * 1981-07-13 1983-01-19 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
DE3702286A1 (de) * 1986-01-30 1987-08-06 Colgate Palmolive Co Fluessige waschmittelzusammensetzung zum gleichzeitigen reinigen und weichmachen von textilien
GB2206602A (en) * 1987-07-09 1989-01-11 Sandoz Ltd Liquid laundry detergent compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0070075A2 (fr) * 1981-07-13 1983-01-19 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
DE3702286A1 (de) * 1986-01-30 1987-08-06 Colgate Palmolive Co Fluessige waschmittelzusammensetzung zum gleichzeitigen reinigen und weichmachen von textilien
GB2206602A (en) * 1987-07-09 1989-01-11 Sandoz Ltd Liquid laundry detergent compositions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997042299A1 (fr) * 1996-05-08 1997-11-13 Henkel Corporation Carboxylates d'alkyl polyglycoside ether
US5908928A (en) * 1996-05-08 1999-06-01 Henkel Corporation Alkyl polyglycoside ether carboxylates
WO1999024538A1 (fr) * 1997-11-10 1999-05-20 Henkel Corporation Ether carboxylates d'alkyl polyglycoside

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
EP0457965B1 (fr) 1995-06-21
ATE124083T1 (de) 1995-07-15
EP0457965B2 (fr) 2002-04-24
ES2075873T3 (es) 1995-10-16
NO178233C (no) 1996-02-14

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