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EP0542801B1 - Agents tensio-actifs liquides, coulants et pompables concentres - Google Patents

Agents tensio-actifs liquides, coulants et pompables concentres Download PDF

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Publication number
EP0542801B1
EP0542801B1 EP91913983A EP91913983A EP0542801B1 EP 0542801 B1 EP0542801 B1 EP 0542801B1 EP 91913983 A EP91913983 A EP 91913983A EP 91913983 A EP91913983 A EP 91913983A EP 0542801 B1 EP0542801 B1 EP 0542801B1
Authority
EP
European Patent Office
Prior art keywords
formula
alkyl
weight
surfactant mixture
stands
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
EP91913983A
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German (de)
English (en)
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EP0542801A1 (fr
Inventor
Brigitte Giesen
Andreas Syldath
Ditmar Kischkel
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0542801A1 publication Critical patent/EP0542801A1/fr
Application granted granted Critical
Publication of EP0542801B1 publication Critical patent/EP0542801B1/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
    • 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
    • C11D1/146—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
    • C11D1/66—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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to concentrated surfactant mixtures of alkyl glycosides, long-chain alkyl sulfates, short-chain alkyl sulfates and optionally alcohol ethoxylates as stable, free-flowing and pumpable liquids and their use as premixes (compounds) for the production of liquid washing and cleaning agents.
  • alkyl glycosides with long-chain alkyl groups belong to the nonionic surfactants.
  • the person skilled in the art also knows, for example in A.M. Schwartz, J.W. Perry, Surface Active Agents, Vol. I, Interscience Publishers, 1949, page 372 described that surfactant mixtures generally have synergistic effects and often have better cleaning properties than would result from the sum of the values of the individual components.
  • Detergents which contain alkyl glycosides in combination with at least one customary anionic surfactant are described in European patent application EP 070 074. Detergents which contain alkyl glycosides and anionic surfactants are also known from European patent application EP 092 877. Furthermore, liquid detergents are known from European patent application EP 105 556, which contain alkyl glycosides, certain other nonionic surfactants and anionic surfactants. From international patent application W0 86/02943 alkylglycoside-containing liquid detergents are known which contain conventional anionic surfactants.
  • the individual components are generally used as flowable solutions, each of which contains a substance or which, as premixes, known as compounds, consist of several substances which are customary in the finished agents.
  • the components provided for the mixture into the finished agent should have the highest possible active substance content and at the same time be easy to handle, that is to say they should be as flowable and as possible be easy to pump and have the highest possible storage stability.
  • Alkyl glycosides are usually obtained as highly viscous pastes.
  • the object of the present invention was to develop a storage-stable, liquid, flowable and pumpable surfactant mixture from an alkyl glycoside paste.
  • This object is achieved by an aqueous mixture of certain amounts of alkyl glycoside, synthetic anionic surfactant in the form of a long-chain alkyl sulfate and short-chain alkyl sulfate.
  • long-chain compounds are understood to mean aliphatic compounds with 12 and more carbon atoms, which can be linear or branched one or more times, so that the longest chain of carbon atoms can also be shorter than 12.
  • Short-chain compounds in the context of the present invention are accordingly, regardless of the degree of branching, those having a maximum of 10 carbon atoms.
  • the compounds according to the invention are aqueous mixtures which consist essentially of 50 to 80% by weight, preferably 55 to 70% by weight of water, 5 to 30% by weight, preferably 10 to 25% by weight, of an alkyl glycoside of the formula I, R1-O (G) n (I) in which R1 is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number between 1 and 10, 3 to 20% by weight, preferably 5 to 15% by weight, of a surface-active long-chain alkyl sulfate of the formula II, R2-O-SO3X (II) in which R2 is an alkyl radical having 12 to 22 carbon atoms and X is an alkali metal or ammonium ion, and 1 to 15% by weight, preferably 2 to 10% by weight, of a short-chain alkyl sulfate of the formula III, R3-O-SO3Y (III) in which R3 is an alkyl radical having 6 to 10 carbon
  • the surfactant mixtures according to the invention preferably additionally contain 10 to 20% by weight, in particular 12 to 18% by weight, of an ethoxylated alcohol of the formula IV, R4O- (CH2CH2O) p -H (IV) in which R4 is an alkyl radical having 10 to 22 carbon atoms and p is a number between 1 and 20, in particular between 3 and 10.
  • alkyl glycosides suitable for the surfactant mixtures according to the invention and their preparation are described, for example, in European patent applications EP 92 355, EP 301 298, EP 357 969 and EP 362 671 or the US Pat. No. 3,547,828.
  • the glycoside components ((G) n in formula I) of such alkyl glycosides are oligomers or polymers from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose , Idose, ribose, arabinose, xylose and lyxose.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization.
  • the degree of oligomerization (n in formula I) generally assumes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the alkyl glycosides preferably used below 1.5, in particular between 1.2 and 1.4.
  • the preferred monomer building block is glucose because of its good availability.
  • the alkyl part (R 1 in formula I) of the alkyl glycosides contained in the surfactant mixtures according to the invention preferably also originates from Easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to produce usable alkyl glycosides.
  • the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful.
  • the alkyl glycosides can contain small amounts, for example 1 to 2%, of unconverted free long-chain alcohol, which does not have a disadvantageous effect on the properties of the surfactant mixtures produced therewith.
  • Long-chain alkyl sulfates suitable for use in the surfactant mixtures according to the invention are the sulfation products of linear or branched chain alcohols.
  • the derivatives of fatty alcohols with 12 to 22 C atoms, in particular with 12 to 16 C atoms, are particularly suitable.
  • Such alkyl sulfates have long been known as effective anionic surfactants.
  • Suitable short-chain alkyl sulfates are the sulfation products of linear or branched chain alcohols with 6 to 10 carbon atoms, preferably the derivatives of linear alcohols with 8 to 10 carbon atoms. Such alkyl sulfates are known to have little or no surfactant activity.
  • the alkyl sulfates can be prepared in a known manner by reacting the corresponding long- or short-chain alcohol component with a customary sulfating agent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization, preferably with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • a customary sulfating agent in particular sulfur trioxide or chlorosulfonic acid
  • the ethoxylates suitable for use in the compounds according to the invention are derivatives of linear or branched-chain alcohols having 10 to 22 carbon atoms, preferably 12 to 16 carbon atoms.
  • the degree of ethoxylation the alcohols (p in formula IV) are between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with ethylene oxide.
  • the preparation of the surfactant mixtures according to the invention presents no difficulties. It can be done easily by simply mixing the individual components, which can be present as such or preferably in aqueous solution.
  • the mixtures according to the invention are notable for their low viscosities, their easy flowability and pumpability and their high storage stability.
  • the viscosity of the compounds according to the invention is generally from 20 mPa.s to 7000 mPa.s. They generally have basic pH values, for example from 9.8 to 10.5, but can be adjusted to largely neutral to weakly acidic pH values by adding conventional acids, in particular citric acid, without losing their advantageous properties .
  • the compounds according to the invention are stable in storage over a long period of time, at least 30 days, at temperatures of about 1 ° C. to about 45 ° C.
  • Another unexpected advantage of the compounds according to the invention is that the improvement in the rheological properties of the surfactant alkyl sulfate alkyl glycoside pastes is achieved by the addition of compounds which, despite their low surface activity, have the properties of the alkyl glycoside pastes relevant to use in end products, such as cleaning and Foaming power, do not negatively affect.
  • the compounds according to the invention can be used, directly or after dilution with water, for technical applications, for example as flotation aids or drilling fluids. However, they are preferably used as premixes for the production of liquid detergents and cleaning agents, which include, in particular, mild detergents, wool detergents and dishwashing detergents, but also shampoos. Such agents can be prepared in a simple manner by diluting the compounds with water to the desired active substance concentration.
  • compositions customary in such compositions, to which in particular builder substances, such as zeolites and layered silicates, corrosion inhibitors, bleaching agents, bleach activators, optical brighteners, enzymes, graying inhibitors, antimicrobial agents, water-miscible solvents, abrasives, foam stabilizers, preservatives, pH regulators, colorants and fragrances as well as additional surfactants are possible.
  • builder substances such as zeolites and layered silicates, corrosion inhibitors, bleaching agents, bleach activators, optical brighteners, enzymes, graying inhibitors, antimicrobial agents, water-miscible solvents, abrasives, foam stabilizers, preservatives, pH regulators, colorants and fragrances as well as additional surfactants are possible.
  • the surfactant mixtures M1 to M7 according to the invention characterized below in Table 1 by their composition and the compositions V1 and V2 used in comparative experiments were prepared.
  • the surfactant mixtures M1 to M7 according to the invention had pH values of 9.8 to 10.5, and their pH values in 8.5% by weight aqueous solution were 8.5 to 9.9.
  • Samples of the mixtures M1 to M7 according to the invention were stored at 1 ° C. or 10 ° C. for 30 days without a change in their consistency being found. When stored at 40 ° C for 30 days, slight cloudiness occurred in some cases, which disappeared when cooling to room temperature. If the compounds according to the invention were adjusted to pH values of 6.0 to 8.8 by adding small amounts of citric acid, which did not significantly change their viscosity, they could be stored at temperatures up to 45 ° C. without changing the consistency.

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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)
  • Table Devices Or Equipment (AREA)
  • Cosmetics (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Claims (8)

  1. Mélange tensio-actif aqueux, susceptible de couler et d'être pompé, contenant un alkylglycoside et un agent tensio-actif anionique synthétique, caractérisé en ce qu'il est constitué essentiellement de
    - 50 à 80% en poids d'eau,
    - 5 à 30% en poids d'un alkylglycoside de la formule (I)

            R¹-O(G)n   (I)

    dans laquelle R¹ représente un radical alkyle avec 8 à 22 atomes de carbone, G représente une unité d'ose et n représente un nombre entre 1 et 10,
    - 3 à 20% en poids d'un alkylsulfate à longue chaîne, surfactif, de la formule (II)

            R²-O-SO₃X   (II)

    dans laquelle R² représente un radical alkyle avec 12 à 22 atomes de carbone et X représente un ion alcalin ou ammonium, et
    - 1 à 15% en poids d'un alkylsulfate à courte chaîne de la formule (III),

            R³-O-SO₃Y   (III)

    dans laquelle R³ représente un radical alkyle avec 6 à 10 atomes de carbone et Y représente un ion alcalin ou ammonium.
  2. Mélange tensio-actif selon la revendication 1, caractérisé en ce qu'il contient 55 à 70% en poids d'eau, 10 à 25% en poids d'alkylglycoside selon la formule (I), 5 à 15% en poids d'alkylsulfate à longue chaîne selon la formule (II) et 2 à 10% en poids d'alkylsulfate à courte chaîne selon la formule (III).
  3. Mélange tensio-actif selon l'une quelconque des revendications 1 ou 2, caractérisé en ce qu'il contient de manière additionnelle 10 à 20% en poids, en particulier 12 à 18% en poids, d'un alcool éthoxylé de la formule (IV),

            R⁴O-(CH₂CH₂O)p-H   (IV)

    dans laquelle R⁴ représente un radical alkyle avec 10 à 22 atomes de carbone, en particulier avec 12 à 16 atomes de carbone, et p représente un nombre entre 1 et 20, en particulier entre 3 et 10.
  4. Mélange tensio-actif selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'alkylglycoside de la formule (I) possède un degré d'oligomérisation n inférieur à 1,5, en particulier de 1,2 à 1,4.
  5. Mélange tensio-actif selon l'une quelconque des revendications 1 à 4, caractérisé en ce que l'alkylglycoside de la formule (I) est un alkylglucoside.
  6. Mélange tensio-actif selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'alkylsulfate à longue chaîne de la formule (II) possède un radical alkyle R² avec 12 à 16 atomes de carbone.
  7. Mélange tensio-actif selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'alkylsulfate à courte chaîne de la formule (III) possède un radical alkyle R³ avec 8 à 10 atomes de carbone.
  8. Utilisation du mélange tensio-actif selon l'une quelconque des revendications 1 à 7 comme prémélange stable dans le temps, capable de couler, susceptible d'être pompé pour la préparation d'agents de lessive ou de nettoyage.
EP91913983A 1990-08-08 1991-07-31 Agents tensio-actifs liquides, coulants et pompables concentres Expired - Lifetime EP0542801B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4025065A DE4025065A1 (de) 1990-08-08 1990-08-08 Fluessiges, giess- und pumpfaehiges tensidkonzentrat
DE4025065 1990-08-08
PCT/EP1991/001436 WO1992002604A1 (fr) 1990-08-08 1991-07-31 Agents tensio-actifs liquides, coulants et pompables concentres

Publications (2)

Publication Number Publication Date
EP0542801A1 EP0542801A1 (fr) 1993-05-26
EP0542801B1 true EP0542801B1 (fr) 1994-06-29

Family

ID=6411812

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91913983A Expired - Lifetime EP0542801B1 (fr) 1990-08-08 1991-07-31 Agents tensio-actifs liquides, coulants et pompables concentres

Country Status (10)

Country Link
EP (1) EP0542801B1 (fr)
JP (1) JPH05509347A (fr)
CN (1) CN1058804A (fr)
AT (1) ATE107956T1 (fr)
BR (1) BR9106754A (fr)
DE (2) DE4025065A1 (fr)
ES (1) ES2055994T3 (fr)
MX (1) MX9100568A (fr)
RU (1) RU2056458C1 (fr)
WO (1) WO1992002604A1 (fr)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2667865B1 (fr) * 1990-10-12 1992-12-11 Saint Gobain Isover Resine phenolique, procede de preparation de la resine et composition d'encollage de fibres minerales la contenant.
DE4117689A1 (de) * 1991-05-29 1992-12-03 Henkel Kgaa Fluessige, giess- und pumpfaehige tensidzubereitung
TW211595B (fr) * 1991-12-07 1993-08-21 Hoechst Ag
CA2127255A1 (fr) * 1992-04-21 1993-10-28 Gerhard Wolf Methode de preparation d'alkylglycosides et leur utilisation
NZ247676A (en) * 1992-06-08 1995-04-27 Colgate Palmolive Co Anionic surfactant compositions containing alkyl sulphates as viscosity modifiers; hair shampoo
DE4236506A1 (de) * 1992-10-29 1994-05-05 Henkel Kgaa Verfahren zur Herstellung wäßriger Lösungen anionischer Tenside mit verbesserter Kältestabilität
WO1994010272A1 (fr) * 1992-11-03 1994-05-11 The Procter & Gamble Company Nettoyage a l'aide d'agents tensio-actifs a courtes chaines
EP0616026A1 (fr) * 1993-03-19 1994-09-21 The Procter & Gamble Company Compositions de nettoyage concentrées
EP0616027A1 (fr) * 1993-03-19 1994-09-21 The Procter & Gamble Company Compositions de nettoyage concentrées
ES2159304T3 (es) * 1993-09-20 2001-10-01 Procter & Gamble Composiciones detergentes acuosas espesadas, con comportamiento de limpieza mejorado.
DE4344991A1 (de) * 1993-12-30 1995-07-06 Huels Chemische Werke Ag Verfahren zur Umwandlung hexagonal flüssig-kristalliner wäßriger Tensidphasen
DK0693548T3 (da) * 1994-07-18 2002-02-11 Procter & Gamble Stabil koncentreret præmix og dens anvendelse til fremstilling af vandige detergentsammensætninger
EP0893710B1 (fr) * 1995-05-19 2003-08-27 Bridgestone Corporation Guide d'ondes optiques tubulaire
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
EP0916718A1 (fr) * 1997-10-14 1999-05-19 The Procter & Gamble Company Compositions de nettoyage et de désinfection
DE19908563C2 (de) * 1999-02-27 2002-11-14 Cognis Deutschland Gmbh Reinigungsmittel für harte Oberflächen
SG11201510594YA (en) * 2013-07-03 2016-01-28 Basf Se Mixtures of compounds, their preparation, and uses
CN105062705A (zh) * 2015-08-14 2015-11-18 浙江赞宇科技股份有限公司 一种无水乙氧基化烷基硫酸盐浓缩物及其制备方法与装置

Family Cites Families (3)

* 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
US4483787A (en) * 1983-12-28 1984-11-20 The Procter & Gamble Company Concentrated aqueous detergent compositions
DE3838808A1 (de) * 1988-11-17 1990-05-23 Henkel Kgaa Wasch- und reinigungsmittel, enthaltend ein tensidgemisch aus alkylglykosiden und aniontensiden

Also Published As

Publication number Publication date
ES2055994T3 (es) 1994-09-01
MX9100568A (es) 1992-04-01
RU2056458C1 (ru) 1996-03-20
ATE107956T1 (de) 1994-07-15
BR9106754A (pt) 1993-06-29
JPH05509347A (ja) 1993-12-22
EP0542801A1 (fr) 1993-05-26
DE4025065A1 (de) 1992-02-13
CN1058804A (zh) 1992-02-19
DE59102082D1 (de) 1994-08-04
WO1992002604A1 (fr) 1992-02-20

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