EP0349906B1 - Mélange détergent contenant des agents tensioactifs non ioniques et anioniques, et son utilisation - Google Patents

Mélange détergent contenant des agents tensioactifs non ioniques et anioniques, et son utilisation Download PDF

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Publication number
EP0349906B1
EP0349906B1 EP89111881A EP89111881A EP0349906B1 EP 0349906 B1 EP0349906 B1 EP 0349906B1 EP 89111881 A EP89111881 A EP 89111881A EP 89111881 A EP89111881 A EP 89111881A EP 0349906 B1 EP0349906 B1 EP 0349906B1
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EP
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Prior art keywords
detergent mixture
iii
alkyl
carbon atoms
hydroxysulfonate
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
EP89111881A
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German (de)
English (en)
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EP0349906A3 (en
EP0349906A2 (fr
Inventor
Bernd Dr. Fabry
Brigitte Giesen
Karlheinz Dr. Hill
Martina Dr. Kihn-Botulinski
Robert Dr. Piorr
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT89111881T priority Critical patent/ATE92096T1/de
Publication of EP0349906A2 publication Critical patent/EP0349906A2/fr
Publication of EP0349906A3 publication Critical patent/EP0349906A3/de
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Publication of EP0349906B1 publication Critical patent/EP0349906B1/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
    • 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
    • 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
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/143—Sulfonic 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
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives

Definitions

  • the invention relates to detergent mixtures of nonionic surfactants such as alkyl glycosides and anionic surfactants such as hydroxysulfonates, which are used as a component of reduced phosphate detergents or cleaning agents.
  • detergents with reduced phosphate refer to those detergents which contain at most 30% by weight of alkali metal tripolyphosphates, but which can also be phosphate-free.
  • EP 0 070 074A2 describes a detergent mixture of alkyl glycosides and anionic surfactants.
  • EP 0 075 995A2 describes a detergent mixture of alkyl glycosides and nonionic surfactants.
  • EP 0 105 556A1 describes a liquid detergent mixture, the anionic surfactants, alkyl glycosides, selected nonionic Contains surfactants and optionally other additives.
  • ABS alkylbenzenesulfonates
  • ABS has good wetting and foaming power, but is only partially compatible with the skin, which can lead to allergies. Furthermore, ABS is only partially biodegradable.
  • the present invention has for its object to provide a detergent mixture of a nonionic surfactant, such as an alkyl glycoside, and an anionic surfactant, such as a hydroxysulfonate, which is composed entirely of native, ie renewable, fat-chemical raw materials.
  • This detergent mixture is intended to replace detergents such as ABS, which are made exclusively from petrochemical, i.e. non-renewable raw materials, in phosphate-reduced detergents and cleaning agents.
  • the detergent mixtures according to the invention show a significantly better biodegradability compared to ABS in the closed bottle test and also a significantly better one Skin tolerance in the epidermal swelling test, as can be shown in the examples.
  • phosphate-reduced detergents which contain the detergent mixture according to the invention have better washability than commercially available phosphate-reduced detergents based on ABS.
  • the detergent mixtures according to the invention can be mixed in any ratio to one another, preferably the mixing ratio of alkyl glycoside to hydroxysulfonate is 10 to 90% to 90 to 10%.
  • the products according to the invention remain liquid up to a content of 75% washing active substance (WAS), whereas products based on ABS already form precipitates at a content of 60% WAS and can no longer be pumped.
  • WAS washing active substance
  • Alkyl glycosides suitable for the purposes of this invention are described, for example, in US Pat. Nos. 3,547,828 and 3,839,318.
  • Typical alkyl glycosides are those in which alkyl is octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and mixtures thereof.
  • Particularly suitable alkyl glycosides contain a coconut fatty alkyl residue, ie dodecyl and tetradecyl residues.
  • the sugar component comes from the usual aldoses or ketoses, such as glucose, fructose, mannose, galactose, talose, gulose, allose, old rose, idose, arabinose, xylose, lyxose and ribose.
  • aldoses or ketoses such as glucose, fructose, mannose, galactose, talose, gulose, allose, old rose, idose, arabinose, xylose, lyxose and ribose.
  • the particularly preferred alkyl glycosides are the alkyl glucosides because of the good reactivity and easy accessibility of the glucose.
  • the index number x is any number between 1 and 10, which indicates the degree of oligomerization, ie the distribution of monoglycosides and oligoglycosides.
  • the value x for a specific alkylglycoside process product is an analytically determined arithmetic parameter, usually one is a fractional number.
  • the alkyl glycosides are represented by the formula RO (G) x , the percentage of fatty alcohol is neglected. In principle, this fatty alcohol portion can largely be controlled by gentle distillative treatment of the alkyl glycoside, ie the excess fatty alcohol resulting from the reaction can be removed from the product except for residual values that are less than 1% total.
  • alkyl glycosides with essentially C12-C22-alkyl or alkenyl radicals belong to the type of nonionic surfactants.
  • the hydrophobic part comes from renewable raw materials if it is derived from fatty alcohols and the hydrophilic part is made up of ethylene oxide units and thus from a petrochemical raw material, the alkyl glycosides as fatty alkyl glycosides can be made entirely from renewable ones Raw materials, namely fat on the one hand and sugars or starches on the other hand, are produced.
  • Alkyl glycosides whose alkyl radical is derived from synthetic primary alcohols, in particular the so-called oxo alcohols, i.e. those primary alkanols, which have a certain percentage, mostly 20 to 40%, of branched isomers, mostly with a 2-methyl residue.
  • oxo alcohols i.e. those primary alkanols, which have a certain percentage, mostly 20 to 40%, of branched isomers, mostly with a 2-methyl residue.
  • surfactants are less preferred if the focus is on the intended use of surfactants with a natural raw material base, including the hydrophobic part.
  • the group R2-CO can be a formyl, acetyl, propionyl or butyryl group; the acetyl group is preferred.
  • the group R 1 is preferably an oleyl group or a fatty alkyl radical consisting predominantly of oleyl groups.
  • Preferred values for the sum (y + z + p) in the compounds (II) and (III) are consequently 12 to 18, preferably 12 to 14.
  • auxiliaries or additives in the sense of this invention are conventional constituents such as Builder substances, bleaching agents, foam stabilizers, complexing agents, optical brighteners, thickeners, dirt suspending agents, graying inhibitors, dyes, perfume oils, enzymes, bactericides and fungicides.
  • surfactants can also be added to the mixture, provided that they do not interfere with the synergistic effect of the detergent mixture according to the invention.
  • the detergents according to the invention have a significantly improved washing capacity. Especially with fat-pigment soiling and mineral oil pollution, this effect occurs in an unexpected way.
  • the reflectance values obtained for the detergent mixtures according to the invention in a phosphate-free formulation even exceed the reflectance values documented in application example 2 for a phosphate-containing formulation.
  • the detergent mixture according to the invention has better washing power.
  • the substances used had the chemical composition defined in Application Example 1. HOS% by weight HOES5% by weight AG wt% ABS weight% Remiss. 1) % by weight Remiss. 2) % by weight 100 34.0 41.6 100 0 31.9 41.7 90 10th 32.8 40.8 75 25th 33.7 39.2 50 50 33.0 36.5 25th 75 31.4 32.2 10th 90 28.3 28.6 0 100 25.7 26.7 100 0 31.9 41.7 90 10th 33.1 41.2 75 25th 35.4 42.3 50 50 35.9 41.6 25th 75 36.4 39.8 10th 90 35.4 37.2 0 100 34.3 35.5 Recipe: The specified reflectance measurements refer to the following builder-containing or builder-free recipes: 1) 0.5 g AS / I + 2.0 g sodium sulfate 2) 0.5 g AS / I + 1.5 g NaTPP / zeolite NaA (1: 1)
  • ABS washability according to the prior art
  • a builder If one compares the washability according to the prior art (ABS) with the washability of the detergent mixtures according to the invention, an improved washability is found in particular in the case of alkoxylated hydroxysulfonates in the presence or absence of a builder.
  • the degradability of surfactants can be assessed based on the biochemical oxygen demand (BOD) in microbial oxidation.
  • BOD biochemical oxygen demand
  • test was carried out over a period of 30 days in a closed system at a test concentration of 2 mg AS / I (for the test method see "Fette Seifen Anstrm.” 65 (1963) 37).
  • the example shows that the detergent mixtures claimed according to the invention are significantly easier to degrade than ABS.
  • a pig epidermis is placed in an aqueous solution of the surfactant to be tested and the swelling compared to pure water.
  • the swelling factors for anionic surfactants and systems containing anionic surfactants found using this method correlate very well with measurements of skin tolerance in vivo (cf. J. Soc. Cosmet. Chem. Jap. 20 (1986) 17).

Landscapes

  • 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)
  • Cosmetics (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Claims (7)

  1. Mélange de détergents contenant :
    A) au moins un alcoylglucoside de formule générale (I):



            RO(G)x   (I)



    dans laquelle :
    R   signifie un radical aliphatique ayant au moins 8 atomes de carbone, en particulier le radical d'un alcool primaire et tout particulièrement un radical alcoyle gras ou alcényle gras ayant de 8 à 22 - de préférence de 12 à 18 atomes de carbone,
    G   est un symbole qui représente une unité de glycose c'est-à-dire qui dérive d'un saccharide réducteur ayant 5 ou 6 atomes de carbone, et
    x   représente un nombre entre 1 et 10,
    B) est un agent tensio-actif anionique
    C) des substances auxiliaires et des additifs usuels,
    mélange qui est caractérisé en ce que l'agent tensioactif B est au moins un hydroxysulfonate qui est composé totalement ou principalement de composés de formule (II) ou de formule (III) :
    Figure imgb0007
     ou de leurs sels alcalins , alcalino-terreux ou d'ammonium,
    dans laquelle y et z = 0 ou des nombres allant de 1 à 18, p = 0, 1 ou 2 et la somme (y+z+p) est un nombre allant de 4 à 18, x = 0 ou un nombre allant jusqu'à 30, et n peut être un nombre entier allant de 2 à 4.
  2. Mélange de détergents selon la revendication 1, caractérisé en ce que dans l'hydroxysulfonate de formule (II) ou de formule (III) la somme (y+z+p) est un nombre allant de 12 à 18, de préférence de 12 à 14, et x et n ont les significations fournies ci-dessus.
  3. Mélange de détergents selon la revendication 1 ou 2, caractérisé en ce que dans l'hydroxysulfonate de formule (II) et de formule (III), x = 0 à 20 - de préférence 1 à 10 - et la somme (y+z+p) et n ont les significations fournies ci-dessus.
  4. Mélange de détergents selon l'une quelconques des revendications 1 à 3, caractérisé en ce que dans l'hydroxysulfonate de formule (II) et de formule (III), n représente 2, et la somme (y+z+p) ainsi que n ont les significations fournies ci-dessus.
  5. Mélange de détergents selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les hydroxysulfonates de formule générale (II) et de formule générale (III) ont été produits à partir d'alcool oleylique ou à partir de radicaux alcoyle gras contenant de l'alcool oleylique.
  6. Mélange de détergents selon l'une quelconques des revendications 1 à 5, caractérisé en ce que dans l'hydroxysulfonate, qui consiste totalement ou principalement de composés de formule (II) et de formule (III), la somme (y+z+p) est un nombre allant de 12 à 18, de préférence de 12 à 14, x = 0 à 20 - de préférence 1 à 10 et n représente 2.
  7. Utilisation d'un mélange de détergents selon l'une quelconques des revendications 1 à 6 comme constituant d'agents de lavage ou d'agents de nettoyage à teneur réduite en phosphates qui renferment de 0 à au maximum 30 % en poids de tripolyphosphate alcalin.
EP89111881A 1988-07-07 1989-06-29 Mélange détergent contenant des agents tensioactifs non ioniques et anioniques, et son utilisation Expired - Lifetime EP0349906B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89111881T ATE92096T1 (de) 1988-07-07 1989-06-29 Detergensmischung aus nichtionischen und anionischen tensiden und deren verwendung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3822997 1988-07-07
DE3822997A DE3822997A1 (de) 1988-07-07 1988-07-07 Detergensmischung aus nichtionischen und anionischen tensiden und deren verwendung

Publications (3)

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EP0349906A2 EP0349906A2 (fr) 1990-01-10
EP0349906A3 EP0349906A3 (en) 1990-03-14
EP0349906B1 true EP0349906B1 (fr) 1993-07-28

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EP89111881A Expired - Lifetime EP0349906B1 (fr) 1988-07-07 1989-06-29 Mélange détergent contenant des agents tensioactifs non ioniques et anioniques, et son utilisation
EP89907163A Pending EP0423165A1 (fr) 1988-07-07 1989-06-29 Melange detergent de tensio-actifs non ioniques et anioniques et son utilisation

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EP89907163A Pending EP0423165A1 (fr) 1988-07-07 1989-06-29 Melange detergent de tensio-actifs non ioniques et anioniques et son utilisation

Country Status (7)

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US (1) US5104585A (fr)
EP (2) EP0349906B1 (fr)
JP (1) JPH03505746A (fr)
AT (1) ATE92096T1 (fr)
DE (2) DE3822997A1 (fr)
ES (1) ES2041897T3 (fr)
WO (1) WO1990000592A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3902048A1 (de) * 1989-01-25 1990-07-26 Henkel Kgaa Oberflaechenaktive mischungen
US6042837A (en) * 1989-09-20 2000-03-28 Kalland; Terje Methods of staphylococcal enterotoxin directed cell-mediated cytotoxicity (SDCC)
US6126945A (en) * 1989-10-03 2000-10-03 Pharmacia Ab Tumor killing effects of enterotoxins, superantigens, and related compounds
DE4019790A1 (de) * 1990-06-21 1992-01-02 Henkel Kgaa Fluessige alkylglykosidhaltige tensidmischung
US6197299B1 (en) 1990-07-20 2001-03-06 Pharmacia & Upjohn Ab Antibody conjugates
DE4029035A1 (de) * 1990-09-13 1992-03-19 Huels Chemische Werke Ag Waschmittel
US5599789A (en) * 1991-12-24 1997-02-04 Amrad Corporation Limited Method for the treatment of tumours and sarcomas
US5352376A (en) * 1993-02-19 1994-10-04 Ecolab Inc. Thermoplastic compatible conveyor lubricant
DE4409321A1 (de) * 1994-03-18 1995-09-21 Henkel Kgaa Detergensgemische
US5516747A (en) * 1994-04-18 1996-05-14 Henkel Corporation Pesticidal surfactant mixtures comprising alkyl polyglycosides and alkyl naphthalene sulfonates
FR2723858B1 (fr) * 1994-08-30 1997-01-10 Ard Sa Procede de preparation d'agents tensioactifs a partir de sous-produits du ble et nouveaux xylosides d'alkyle
DE19524973A1 (de) * 1995-07-08 1997-01-09 Huels Chemische Werke Ag Sauer spaltbare Tenside auf Basis von Alkylglykosiden
SE9601245D0 (sv) 1996-03-29 1996-03-29 Pharmacia Ab Chimeric superantigens and their use
US6786223B2 (en) * 2001-10-11 2004-09-07 S. C. Johnson & Son, Inc. Hard surface cleaners which provide improved fragrance retention properties to hard surfaces
US9926486B2 (en) 2014-03-31 2018-03-27 Ecolab Usa Inc. Surfactant assisted oil recovery using alcohol ether sulfonates and cationic surfactants
AR103817A1 (es) 2015-03-03 2017-06-07 Ecolab Usa Inc Extracción de líquido asistida por espuma utilizando sulfonatos de alcohol éter

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU556758B2 (en) * 1981-07-13 1986-11-20 Procter & Gamble Company, The Foaming compositions based on alkylpolysaccharide
US4663069A (en) * 1982-04-26 1987-05-05 The Procter & Gamble Company Light-duty liquid detergent and shampoo compositions
US4536318A (en) * 1982-04-26 1985-08-20 The Procter & Gamble Company Foaming surfactant compositions
US4565647B1 (en) * 1982-04-26 1994-04-05 Procter & Gamble Foaming surfactant compositions
US4732696A (en) * 1984-11-06 1988-03-22 A. E. Staley Manufacturing Company Monoglycosides as viscosity modifiers in detergents
DE3577878D1 (de) * 1984-11-06 1990-06-28 Henkel Kgaa Monoglykoside als viskositaetsregler in detergenzien.

Also Published As

Publication number Publication date
EP0349906A3 (en) 1990-03-14
WO1990000592A1 (fr) 1990-01-25
US5104585A (en) 1992-04-14
JPH03505746A (ja) 1991-12-12
EP0423165A1 (fr) 1991-04-24
DE3822997A1 (de) 1990-01-18
ES2041897T3 (es) 1993-12-01
EP0349906A2 (fr) 1990-01-10
ATE92096T1 (de) 1993-08-15
DE58905025D1 (de) 1993-09-02

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