EP0457965B2 - 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
EP0457965B2
EP0457965B2 EP90124032A EP90124032A EP0457965B2 EP 0457965 B2 EP0457965 B2 EP 0457965B2 EP 90124032 A EP90124032 A EP 90124032A EP 90124032 A EP90124032 A EP 90124032A EP 0457965 B2 EP0457965 B2 EP 0457965B2
Authority
EP
European Patent Office
Prior art keywords
foaming
low
fatty alcohol
liquid detergent
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
EP90124032A
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German (de)
English (en)
Other versions
EP0457965B1 (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
Sasol Germany GmbH
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Application filed by Sasol Germany GmbH filed Critical Sasol Germany GmbH
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Publication of EP0457965B1 publication Critical patent/EP0457965B1/fr
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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 preparations for Washing of textiles, the tensides 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 powder in addition to the surfactants alkyl benzene sulfonate and fatty alcohol oxyethylate as essential active ingredients, builder substances, bleaching agents and other electrolytes contain.
  • anionic surfactants especially alkylbenzenesulfonate, Fatty alcohol oxyethylate and soap
  • washing powder in addition to the surfactants alkyl benzene sulfonate and fatty alcohol oxyethylate as essential active ingredients, builder substances, bleaching agents and other electrolytes contain.
  • surfactants in particular those based on petrochemicals are used.
  • the object of the invention was therefore to provide a surfactant combination for low-foaming detergents find that are largely made from renewable raw materials that are exceptionally organic are degradable and achieve very good washing results.
  • the invention therefore relates to a low-foaming, liquid machine washing detergent, which is characterized in that the surfactant component consists of 5 to 30% alkyl polyglycoside, 5 to 30% fatty alcohol ether carboxylate, 5 to 30% soap and 0 to 3% other surfactants consists.
  • alkyl polyglycoside in combination with anionic surfactants is known. So 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.
  • Other components 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.
  • RON n in which R represents a linear or branched, saturated or unsaturated aliphatic alkyl radical having 10 to 18 carbon atoms or mixtures thereof and Z n represents a polyglycosyl radical with n 1.0 to 3 hexose or pentose units or mixtures thereof.
  • Alkyl polyglycosides with fatty alkyl radicals having 10 to 16 carbon atoms and one are preferred Polyglycosyl radical from n 1.1 to 2. Alkylpolyglucosides are particularly preferred.
  • the alkyl polyglycosides used according to the invention can be based on known processes renewable raw materials are produced. For example, dextrose is in the presence of an acid Catalyst with n-butanol converted to butyl polyglycoside mixtures, which with long-chain alcohols also glycosidated in the presence of an acid catalyst to give the desired alkyl polyglycoside mixtures become. 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 selected of long chain alcohol.
  • the industrially accessible ones 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 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 are 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 mixed by mixing alkyl polyglycosides with alkyl monoglycosides.
  • the latter can e.g. B. according to EP-A 0 092 355 by means of polar Obtain or enrich 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 Compared to almost all other surfactants used in detergents, the alkyl polyglycosides apply as extremely environmentally friendly. So lies the one determined by means of a sewage treatment plant simulation model / DOC analysis degree of biodegradation for the alkyl polyglycosides according to the invention at 96 ⁇ 3%. That number is before Background to see that with this test method (total degradation) already a degree of degradation> 70% Substance indicated as readily degradable.
  • the acute oral toxicity LD 50 (rat) with> 10,000 mg / kg and the aquatic toxicity LC 50 (Gold orfe) with approx. 12 mg / l and EC 50 (daphnia) with 30 mg / l are cheaper by a factor of 3 to 5 than that corresponding values of the most important surfactants today. The same applies to skin and mucous membrane compatibility.
  • Fatty alcohol ether carboxylates are compounds of either formula II (R'-O (CH 2 -CH 2 -O) x CH 2 COO) m M m + 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 hydrogen, alkali, alkaline earth metal, ammonium or alkanolammonium is, or III ([R "-O (CH 2 -CH 2 -O) y ] 2 CHCOO) z N z + 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 40, preferably 3 to 30, z 1 or 2 and MH, alkali, alkaline earth metal, ammonium or 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 (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 Ziegleral alcohols, in exceptional cases also oxo alcohols.
  • the one following the oxethylation Carboxymethylation can be complete if the procedure is appropriate, so that the fatty alcohol ether carboxylates are purely anionic surfactants.
  • the carboxymethylation is incomplete, they contain Products certain amounts of unreacted oxyethylate. With formulas II and III is therefore usually a Mixture with different amounts of unreacted oxethylates meant. 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. So using a sewage treatment plant simulation model / DOC analysis biodegradation rates found above 90%.
  • the acute oral Toxicity LD 50 (rat) and aquatic toxicity LC 50 (gold orfe) are about as favorable as that the alkyl polyglucoside. The same applies to skin and mucous membrane compatibility.
  • the detergents according to the invention contain 5 to 30% fatty alcohol ether carboxylates, which also include mixtures could be. 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 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%, most of the soap will be a mixture of different components.
  • alkanesulfonates are alkanesulfonates, olefinsulfonates, alkylbenzenesulfonates, ⁇ -sulfofatty 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, Citrates, polyacetates such as NTA and EDTA etc. or their mixtures. These connections will be usually used as alkali salts, preferably as sodium salts. Although not complex, too To mention sodium sulfate here.
  • Builders such as aluminosilicates of suitable particle size (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 are also optionally combined with bleach activators such as tetraacetylethylene diamine etc. or percarbonate; of course also come into question other bleaching agents (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 1- or 2-valent alcohols may be used according to the invention, Alkyl ethers of polyhydric alcohols, hydrotropes 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 brighteners, in particular based on stilbene and pyrazoline, Foam regulators, graying inhibitors such as B. carboxymethyl cellulose, perfume oils, dyes and further ingredients customary for liquid or powder detergents.
  • hydrotropes 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 brighteners in particular based
  • Liquid detergent formulations contain, in addition to the surfactants mentioned, used according to the invention Each contains 6% triethanolamine, 12% ethanol, 6% 1,2-propylene glycol and water ad 100 %.
  • the foaming power was determined in accordance with DIN 53 902, Part 1.
  • the concentration on detergent substance was 1 g / l, the foam volume was registered after 5 minutes.
  • the Washing ability was both in the Linitest laboratory washing machine (i.e. with moderate mechanical stress) as well as measured 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 mixed at 30 ° C and cotton washed at 60 ° C.
  • the active substance concentration was in the Linitest laboratory washing machine at 1 g / l, in the household washing machine at 5 g / l, the pH at about 7, the liquor ratio at 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 brand detergent, in which one can presuppose a formulation optimization.
  • the clear point and viscosity fully correspond to the standard customary for liquid detergents.
  • the formulations according to the invention behave far more effectively here than other known combinations, their surfactant content also consists of anionic surfactant, alkyl polyglucoside and soap (Comparative Examples 1 and 2).

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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 (7)

  1. Détergent pour machine, liquide, 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, peu moussant, selon la revendication 1,
    caractérisé en ce que l'alkylpolyglycoside a 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, 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, 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, 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) [R'-O(CH2-CH2-O)xCH2COO]m Mm+ ([R''-O(CH2-CH2-O)y]2CHCOO)z Nz+ où R' et R'' sont des radicaux alkyle à chaíne 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 , peu moussant, selon la revendication 4,
    caractérisé en ce que le carboxylate d'alcool gras polyéthoxylé est un produit d'éthoxylation carboxyméthylé 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 , peu moussant, selon les revendications 1 à 5,
    caractérisé en ce que le savon a la formule (IV) R''' COOP 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, 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.
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 EP0457965B1 (fr) 1995-06-21
EP0457965B2 true 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)

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
EP0457965B1 (fr) 1995-06-21
ATE124083T1 (de) 1995-07-15
ES2075873T3 (es) 1995-10-16
NO178233C (no) 1996-02-14
EP0457965A1 (fr) 1991-11-27

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