EP0549632B1 - Composition d'agents tensio-actifs non ionique liquide ayant une resistance amelioree au froid - Google Patents

Composition d'agents tensio-actifs non ionique liquide ayant une resistance amelioree au froid Download PDF

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Publication number
EP0549632B1
EP0549632B1 EP91915934A EP91915934A EP0549632B1 EP 0549632 B1 EP0549632 B1 EP 0549632B1 EP 91915934 A EP91915934 A EP 91915934A EP 91915934 A EP91915934 A EP 91915934A EP 0549632 B1 EP0549632 B1 EP 0549632B1
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EP
European Patent Office
Prior art keywords
weight
alcohols
surfactant combination
linear
alcohol
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
EP91915934A
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German (de)
English (en)
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EP0549632A1 (fr
Inventor
Thomas Merz
Khalil Shamayeli
Werner Kuhlmann
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
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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 EP0549632A1 publication Critical patent/EP0549632A1/fr
Application granted granted Critical
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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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • 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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the present invention relates to a liquid, nonionic surfactant combination which is still pourable at low temperatures and is stable in storage in a wide temperature range from minus 10 to plus 40 ° C.
  • Such surfactant combinations are used in particular as liquid concentrates together with so-called washing alkalis and are particularly suitable for washing oil-soiled textiles and work clothing in laundries.
  • automatically metered liquid concentrates are particularly appreciated which, in addition to the properties mentioned, show a viscosity behavior which is only slightly influenced by temperature fluctuations.
  • Known pourable concentrates used for such purposes usually contain solvents, in particular low molecular weight alcohols, in order to guarantee the required low-temperature stability.
  • solvents in particular low molecular weight alcohols
  • low molecular weight polyglycols or propylene glycol are added to them in order to improve not only the low-temperature stability but also the viscosity behavior in the desired manner.
  • both additives do not contribute to the washing effect.
  • the British patent application GB-A-2 194 955 describes liquid nonionic surfactant combinations which contain ethoxylated and both ethoxylated and propoxylated fatty alcohols, ethoxylated C9-C11 fatty alcohols being an essential component of the mixture.
  • customary anti-gelling agents as stated above and phosphoric acid alkanol esters are used. The temperature range in which these agents are then stable is not disclosed.
  • EP-A-0 235 774 discloses liquid nonionic surfactant combinations based on polyalkoxylated alcohols, which are straight-chain and branched C12-C15 alcohols, which ethoxylates and can optionally be additionally propoxylated, but additionally also contain alkoxylated C9-C11 fatty alcohols and substituted amino alcohols. However, these mixtures are only liquid up to about 10 ° C or have cold cloud points of 9 to 10 ° C.
  • the object was therefore to develop a corresponding liquid concentrate which, despite the absence of solvent additives, is stable in a further temperature range and can be metered easily at different temperatures without significant changes in viscosity.
  • the washing and cleaning properties in particular with regard to soiling containing oil and fat, should not be reduced in comparison to known top products, but should be fully preserved or increased. This object is achieved by the invention described below.
  • alcohol alkoxylates (a) and (b) have a restricted homolog distribution (narrow range ethoxylates, nre).
  • alcohol alkoxylates (b) are preferred in which the propylene oxide distribution also corresponds to a restricted homolog distribution.
  • the nonionic component (a) preferably consists of an alcohol ethoxylate which is derived from primary, saturated and linear alcohols having 12 to 14 carbon atoms, such as are present, for example, in alcohol mixtures which are synthesized by the Ziegler method or from native fatty acids can be obtained by reduction.
  • the preferred alcohol mixtures of native origin may still contain small amounts of C10 or C16 alcohols, but the amount of C16 alcohol should be less than 10% by weight, in particular less than 5% by weight and the amount of C10 alcohol less than 15 wt .-%, in particular less than 10 wt .-%.
  • the specified degree of ethoxylation (EO) of the nonionic component (a) is preferably 2 to 5.
  • the content of the composition in component (a) is preferably 20 to 45% by weight and in particular 25 to 40% by weight.
  • the nonionic component (b) is derived from primary, saturated alcohols having 12 to 15 carbon atoms, in which the alcohol radical can be linear or methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as is customary in oxo alcohol residues available. However, linear residues of alcohols of native origin with 12 to 14 carbon atoms are preferred, which may optionally contain appropriate proportions of C10 and C16 alcohol residues.
  • Component (b) contains both ethylene oxide residues (EO) and propylene oxide residues (PO).
  • R stands for the alcohol residue
  • x for the number of (EO) groups
  • y for the number of (PO) groups.
  • the number of EO groups is preferably 4 to 6 and the number of PO groups is preferably 2 to 5, in particular 2.5, 3 and 4. If the number of EO groups is greater than 5, a higher proportion is also recommended on PO groups, for example 5 to 6.
  • An alkoxylate which has (on average) 4 to 6 EO groups and 2 to 3 PO groups has proven to be particularly suitable ecologically.
  • the proportion of component (b) in the concentrate is preferably 20 to 45% by weight and in particular 25 to 40% by weight.
  • Component (c) is derived from oxo alcohols, which are known to be a mixture of linear and 2-methyl-branched alkanols, the proportion of linear alcohols generally predominating.
  • the alcohol residues have 12 to 15, preferably 13 to 14, carbon atoms.
  • Technical mixtures can additionally contain small proportions of 11 or 15 carbon atoms, but their respective proportions should preferably be less than 10% by weight, based on the technical mixture.
  • the degree of ethoxylation of component (c) is preferably 2 to 5, in particular 2.5 to 4.
  • the proportion of component (c) in the concentrate is preferably 10 to 45% by weight and in particular 15 to 40% by weight.
  • the concentrates can be anhydrous or contain up to 20% by weight, preferably 5 to 15% by weight, of water.
  • the water content only plays a subordinate role for cold stability and dosing.
  • the nonionic surfactants (a), (b) and (c) are technical products that are obtained and offered in different quality and purity, it can happen that the concentrates become cloudy when certain technical product batches are used or also gel-like Form precipitation. This clouding and precipitation are reliably avoided by adding water. Additions of 5 to 10% by weight are generally sufficient for this.
  • the agents can contain further additives, provided that it is ensured that they are soluble and do not change the advantageous properties of the concentrates.
  • this includes dyes and fragrances with which the intrinsic color or odor of the mixtures is covered.
  • Solvents can in principle be added, but for the reasons given they are neither necessary nor appropriate.
  • the concentrates behave like Newtonian liquids, i.e. their viscosity is independent of the shear forces. They are therefore easy to convey and dose, with their viscosity changing comparatively little depending on the temperature. They are stable in storage even after several months of storage in a climatic cabinet with repeatedly changing temperatures between minus 10 ° C and plus 40 ° C, i.e. they do not tend to segregate.
  • the concentrates have a liquid consistency of at least 0 ° C. They can be in liquid or solid form between minus 10 ° C and 0 ° C. The concentrates in solid form at these temperatures also give clear and homogeneous liquids when thawed. These properties make them particularly suitable for fully automatic dosing in commercial laundries.
  • the concentrates can be used without additional additives for the production of wash liquors. However, they are preferably used in combination with customary builder substances, so-called washing alkalis, co-builders and sequestering agents, and other customary detergent additives.
  • Suitable co-builders are polymeric polycarboxylates, in particular homopolymers of Acrylic acid and copolymers of acrylic acid with maleic acid.
  • Suitable complexing agents or sequestering agents are aminopolycarboxylates, such as sodium nitrilotriacetate, ethylenediaminetetraacetate and its higher homologues, phosphonates, such as 1-hydroxyethane-1,1-diphosphonate, aminotri (methylenephosphonate), ethylenediaminetetra- (methylenephosphonate) and its higher homologues, such as diethylamine - (methylene phosphonate).
  • graying inhibitors e.g. Cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses with C2-C4-hydroxyalkyl radicals and mixed ethers such as alkylhydroxyalkyl cellulose.
  • the group of additives also includes optical brighteners, enzymes, bleaches from the per-compound class, which are usually used together with activators, as well as active chlorine compounds, furthermore foam inhibitors and colorants and fragrances.
  • the concentrates according to the invention may also contain conventional anionic and nonionic surfactants.
  • anionic and nonionic surfactants include linear alkylbenzenesulfonates, such as C9-C13 alkylbenzenesulfonate, alkanesulfonates, ⁇ -sulfofatty acids and fatty alcohol sulfates.
  • these agents can also contain customary nonionic surfactants, in particular ethoxylates of C12-C18 fatty alcohols and C12-C16 oxo alcohols.
  • the detergent constituents and additives mentioned are usually stored separately from the surfactant combination according to the invention and - usually as prefabricated mixtures - are added to the wash liquor as required. When used in the commercial sector, softened water is usually used.
  • the nonionic surfactant combination according to the invention is particularly suitable in conjunction with the aforementioned detergent ingredients for Wash heavily soiled work clothing and is characterized by its high washing power compared to soils containing mineral oil.
  • the linear C12-C14 alcohol alkoxylates (components a and b) used to prepare the surfactant combination had the following C chain distribution C10 0.5% by weight C12 72.5% by weight C14 26.0% by weight C16 1.0% by weight
  • the viscosity was independent of the shear rate in the measuring range (5 s ⁇ 1 to 100 s ⁇ 1) (no thixotropy).
  • composition of the washing powder added was (in% by weight): C9-C13 alkylbenzenesulfonate 1.6 C12-C16 fatty alcohol + 7 EO 3.0 Na5P3O10 20.0 soda 25.0 Sodium metasilicate 45.0 Cellulose ether 1.5 Hydroxyethane diphosphonate 0.4 optical brightener 0.1 water rest
  • a surfactant combination had the following composition (in% by weight): C12-C14 alcohol + 3 EO (nre) 40 C12-C14 alcohol + 5 EO + 4 PO (nre) 40 C13-oxo alcohol + 3 EO 10th water 10th
  • the mean was stable in an alternating climate between -10 ° C and 40 ° C. A turbidity which started at 0 ° C disappeared at + 3 ° C.
  • the agent had the following viscosities at the temperatures indicated, regardless of the shear rate: ° C mPas 5 170 10th 116 15 87 20th 63
  • a surfactant combination had the following composition (in% by weight): C12-C14 alcohol + 3 EO (nre) 25th C12-C14 alcohol + 5 EO + 2.5 PO (restricted homolog distribution for EO and PO) 20th C13-oxo alcohol + 8 EO 25th C13-oxo alcohol + 3 EO 20th water 10th
  • the agent was stable in an alternating climate between -10 ° C and + 40 ° C, ie even after several temperature changes there was a clear, homogeneous liquid that did not tend to separate.
  • the agent had the following viscosities at the temperatures indicated, regardless of the shear rate: ° C mPa.s 0 329 5 222 10th 156 15 113 20th 85

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

Claims (10)

  1. Composition d'agents tensioactifs non ionique liquide contenant :
    a) de 20 à 50 % en poids d'un éthoxylate d'alcool, dérivé d'alcool en C₁₂₋C₁₅ linéaires primaires avec en moyenne de 2 à 7 groupes d'oxyde d'éthylène (OE).
    b) de 20 à 50 % en poids d'un alcoxylate d'alcool, dérivé d'alcools en C₁₂-C₁₅ primaires avec en moyenne de 3 à 7 groupes d'oxyde d'éthylène (OE) et de 2 à 8 groupes de propylène (OP).
    c) de 5 à 50 % en poids d'un éthoxylate d'alcool, dérivé de mélanges d'alcools en C₁₂-C₁₅ linéaires primaires et ramifiés par du méthyle en position 2 (oxoalcools) avec en moyenne de 2 à 8 groupes d'oxyde d'éthylène.
  2. Composition d'agents tensioactifs selon la revendication dans laquelle le composant (a) dérive d'alcools linéaires en C₁₂-C₁₄ et comprend en moyenne de 2 à 5 groupes d'oxyde d'éthylène.
  3. Composition d'agents tensioactifs selon les revendications 1 ou 2, dans laquelle la proportion du composant (a) est de 20 à 45 % en poids, en particulier de 25 à 40 % en poids.
  4. Composition d'agents tensioactifs selon une ou plusieurs des revendications 1 à 3, dans laquelle le composant (b) dérive d'alcools en C₁₂-C₁₄ linéaires et correspond à la formule :



            R-(OE)x-(OP)y



    dans laquelle :
    R représente le radical alcool, (OE) des groupes d'oxyde d'éthylène (OP) des groupes d'oxyde de propylène, x et y des valeurs statistiques moyennes avec x = 3 à 7, de préférence 4 à 6, et y = 2 à 8, de préférence 2 à 5.
  5. Composition d'agents tensioactifs selon les revendications 1 et 4, dans laquelle la quote-part du composant (b) va de 20 à 45 % en poids, en particulier de 30 à 40 % en poids.
  6. Composition d'agents tensioactifs selon une ou plusieurs des revendications 1 à 5, dans laquelle le composant (c) dérive d'alcools en C₁₃-C₁₄ et comporte en moyenne de 2,5 à 4 groupes d'oxyde d'éthylène.
  7. Composition d'agents tensioactifs selon les revendications 1 et 6, dans laquelle la proportion du composant (c) se monte de 10 à 45 % en poids.
  8. Composition d'agents tensioactifs selon une ou plusieurs des revendications 1 à 7, contenant jusqu'à 20 % en poids, de préférence de 5 à 15 % en poids d'eau.
  9. Utilisation de la composition des agents tensioactifs selon une ou plusieurs des revendications 1 à 8 comme détergent pour des textiles.
  10. Utilisation de la composition des agents tensioactifs selon la revendication 9 conjointement avec d'autres composants de détergents connus.
EP91915934A 1990-09-20 1991-09-10 Composition d'agents tensio-actifs non ionique liquide ayant une resistance amelioree au froid Expired - Lifetime EP0549632B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4029777 1990-09-20
DE4029777A DE4029777A1 (de) 1990-09-20 1990-09-20 Fluessige, nichtionische tensidkombination mit verbesserter kaeltestabilitaet
PCT/EP1991/001722 WO1992005235A1 (fr) 1990-09-20 1991-09-10 Composition d'agents tensio-actifs non ionique liquide ayant une resistance amelioree au froid

Publications (2)

Publication Number Publication Date
EP0549632A1 EP0549632A1 (fr) 1993-07-07
EP0549632B1 true EP0549632B1 (fr) 1995-02-15

Family

ID=6414610

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91915934A Expired - Lifetime EP0549632B1 (fr) 1990-09-20 1991-09-10 Composition d'agents tensio-actifs non ionique liquide ayant une resistance amelioree au froid

Country Status (9)

Country Link
US (1) US5364552A (fr)
EP (1) EP0549632B1 (fr)
JP (1) JPH06500815A (fr)
AT (1) ATE118537T1 (fr)
DE (2) DE4029777A1 (fr)
DK (1) DK0549632T3 (fr)
ES (1) ES2068604T3 (fr)
GR (1) GR3015078T3 (fr)
WO (1) WO1992005235A1 (fr)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
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WO1993018188A1 (fr) * 1992-03-12 1993-09-16 Henkel Kommanditgesellschaft Auf Aktien Degraissants
DE4332849A1 (de) * 1993-09-27 1995-03-30 Henkel Kgaa Pastenförmiges Waschmittel
DE19523117A1 (de) * 1995-06-26 1997-01-02 Henkel Ecolab Gmbh & Co Ohg Wäßriges saures Reinigungsmittel
DE19548843A1 (de) * 1995-12-27 1997-07-03 Henkel Ecolab Gmbh & Co Ohg Verfahren zum Waschen von Wäsche
DE19636035A1 (de) 1996-09-05 1998-03-12 Henkel Ecolab Gmbh & Co Ohg Pastenförmiges Wasch- und Reinigungsmittel
US6150324A (en) * 1997-01-13 2000-11-21 Ecolab, Inc. Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal
DE19703364A1 (de) * 1997-01-30 1998-08-06 Henkel Ecolab Gmbh & Co Ohg Pastenförmiges Wasch- und Reinigungsmittel
DE19726287A1 (de) * 1997-06-20 1998-12-24 Henkel Ecolab Gmbh & Co Ohg Verfahren zum Waschen von Wäsche, insbesondere von Berufsbekleidung
US5880082A (en) * 1997-07-29 1999-03-09 Welch; Michael C. Aqueous based solvent free cleaning compositions containing alcohol alkoxylates, alkoxylated fatty alcohols and fatty alcohols having oxyethylate moieties
EP0894849A1 (fr) * 1997-07-29 1999-02-03 Basf Corporation Composition détergente à base de l'eau sans solvant contenant deux dérivés tensioactifs nonioniques
DE19738108A1 (de) * 1997-09-01 1999-03-04 Henkel Kgaa Kältestabile Fettalkoholalkoxylate
DE19750456A1 (de) * 1997-11-14 1999-05-27 Henkel Ecolab Gmbh & Co Ohg Mittel zum Reinigen von harten Oberflächen
DE19751859A1 (de) * 1997-11-22 1999-07-29 Henkel Ecolab Gmbh & Co Ohg Mittel zum Reinigen von harten Oberflächen
DE10020145A1 (de) 2000-04-20 2001-10-31 Henkel Ecolab Gmbh & Co Ogh Mikrobizid wirksame Tenside
DE10134441A1 (de) * 2001-07-20 2003-02-06 Basf Ag Lederentfettungsmittel
WO2007064673A2 (fr) 2005-11-30 2007-06-07 Huntsman International Llc Tensioactifs non ioniques liquides pour polymérisation en émulsion et autres applications
CN101389398B (zh) * 2006-02-22 2012-03-21 巴斯夫欧洲公司 含有短链和长链组分的表面活性剂混合物
BRPI0720328B1 (pt) * 2007-01-11 2018-06-12 Dow Global Technologies Inc. Composição tensoativa e detergente ou limpador.
EP2036973A1 (fr) * 2007-09-07 2009-03-18 Cognis IP Management GmbH Systèmes tensio-actifs
US9006166B2 (en) * 2011-09-27 2015-04-14 Dow Global Technologies Llc Branched alkoxylate surfactant composition
DE102012200673A1 (de) * 2012-01-18 2013-07-18 Henkel Ag & Co. Kgaa Wasch-, Reinigungs- oder Vorbehandlungsmittel mit erhöhter Reinigungskraft
US8901063B2 (en) * 2012-11-30 2014-12-02 Ecolab Usa Inc. APE-free laundry emulsifier
GB201222820D0 (en) * 2012-12-18 2013-01-30 Croda Int Plc Woolscouring method and composition
WO2021247177A1 (fr) 2020-06-05 2021-12-09 SCION Holdings LLC Production d'alcools
US20220194886A1 (en) 2020-12-17 2022-06-23 SCION Holdings LLC Branched Products

Family Cites Families (10)

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DE2703998C3 (de) * 1977-02-01 1981-10-01 Henkel KGaA, 4000 Düsseldorf Flüssiges Waschmittelkonzentrat mit geringem Schaumvermögen
DE2817834C2 (de) * 1978-04-24 1983-05-19 Henkel KGaA, 4000 Düsseldorf Flüssiges Waschmittel
US4332692A (en) * 1979-02-28 1982-06-01 The Procter & Gamble Company Laundering with a nonionic detergent system at a temperature between the cloud point and the phase coalescence temperatures
US4743394A (en) * 1984-03-23 1988-05-10 Kaufmann Edward J Concentrated non-phosphate detergent paste compositions
GB8527772D0 (en) * 1985-11-11 1985-12-18 Unilever Plc Non-aqueous built liquid detergent composition
DE3607193A1 (de) * 1986-03-05 1987-10-01 Henkel Kgaa Fluessige tensidmischungen
NZ221525A (en) * 1986-09-08 1989-08-29 Colgate Palmolive Co High foam nonionic liquid surfactant detergent comprising ethoxylated fatty alcohol
DE3643895A1 (de) * 1986-12-22 1988-06-30 Henkel Kgaa Fluessige nichtionische tensidmischungen
DE3719906A1 (de) * 1987-06-15 1988-12-29 Henkel Kgaa Maschinelles waschverfahren
US5209874A (en) * 1989-04-26 1993-05-11 Shell Oil Company Liquid surface active compositions

Also Published As

Publication number Publication date
DK0549632T3 (da) 1995-07-17
WO1992005235A1 (fr) 1992-04-02
DE4029777A1 (de) 1992-03-26
JPH06500815A (ja) 1994-01-27
ES2068604T3 (es) 1995-04-16
US5364552A (en) 1994-11-15
EP0549632A1 (fr) 1993-07-07
DE59104638D1 (de) 1995-03-23
ATE118537T1 (de) 1995-03-15
GR3015078T3 (en) 1995-05-31

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