EP2267110B1 - Utilisation de substances tensioactives dans des nettoyants - Google Patents

Utilisation de substances tensioactives dans des nettoyants Download PDF

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Publication number
EP2267110B1
EP2267110B1 EP10187277A EP10187277A EP2267110B1 EP 2267110 B1 EP2267110 B1 EP 2267110B1 EP 10187277 A EP10187277 A EP 10187277A EP 10187277 A EP10187277 A EP 10187277A EP 2267110 B1 EP2267110 B1 EP 2267110B1
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carbon atoms
alkyl
radical
mixtures according
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EP2267110A2 (fr
EP2267110A3 (fr
Inventor
Hans-Christian Raths
Manfred Weuthen
Sabine Both
Teresa Alexandre
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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    • 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
    • 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
    • C11D1/721—End blocked ethers

Definitions

  • the present invention relates to the use of selected surface-active substances, alone or in combination, for use in cleaning agents and in particular in dishwashing detergents for automatic dishwashing.
  • the cleaning of hard surfaces and especially the washing of dishes makes special demands on the cleaner used.
  • the three components of the machine system are cleaner, rinse aid and regeneration salt for water softening.
  • the central tasks of the main component cleaners are the soil release, the dirt dispersion, the binding of residual water hardness and the corrosion inhibition.
  • An essential parameter for dishwashing is the rinse aid performance. It is determined how large the proportion of deposits on the dishes, after they were rinsed.
  • the deposits are essentially mineral compounds, in particular Ca and / or Mg salts, but also surfactant residues. However, lime mainly leads to undesirable deposits for the user.
  • common dishwashing agents in particular those for automatic dishwashing, generally contain so-called rinse aid.
  • rinse aids usually comprise mixtures of low foaming nonionic surfactants, typically fatty alcohol polyethylene / polypropylene glycol ethers, solubilizers (eg cumene sulfonate), organic acids (eg citric acid) and solvents (eg ethanol) It is to influence the interfacial tension of the water so that it can run in a very thin, coherent film of items to be washed, so that remain in the subsequent drying process no water droplets, stripes or films. There are differences between two types of deposits. On the one hand, the so-called “spotting”, which is caused by drying drops of water, is examined. On the other hand, the "filming”, which are layers that result from the drying of thin water films, is evaluated.
  • solubilizers eg cumene sulfonate
  • organic acids eg citric acid
  • solvents eg ethanol
  • EP 1254948 A1 are known as gemini surfactants and their use in detergents and cleaners. These are symmetrical hydroxymix ethers with free OH functions.
  • the EP 1321511 A2 describes mixtures of gemini surfactants and fatty alcohol alkoxylates for rinse aid.
  • Gemini surfactants are disclosed in combination with polyethylene glycols.
  • the WO 95/13260 discloses a process for the preparation of blends of low foaming nonionic acetal surfactants. The document discloses its broad use in washing and cleaning processes in industry, commercial enterprises and in the household.
  • the WO 96/00253 discloses hydroxyl-terminated polyoxyalkylenes in combination with acetals or ketals. Mixtures are suitable for various fields of application, including the cleaning of hard surfaces, especially in the industrial segment.
  • combination products are increasingly being used, in which the various functions, such as cleaning, rinsing, water softening and, if appropriate, metal, in particular silver protection or a glass protection function, are combined in a preferably solid form.
  • agents are referred to as multifunctional agents.
  • so-called 3-in-1 products which combine cleaners, rinse aids and water softening in the form of a solid compact ("tabs"), are found in the market. Due to the increased use of such multifunctional agents but the drying performance has become worse compared to the use of a classic rinse aid. Drying performance is to be understood in how far the cleaned items to be washed, after passing through the dishwashing process, still have water, preferably water drops, on the surface.
  • the remaining water on the surface must then either be removed mechanically (eg by dry wiping) or the ware must be allowed to air-dry. The user must wait until the water evaporates. However, residues (eg lime and / or surfactant residues or other residues dissolved or dispersed in the water) remain on the surface which lead to unaesthetic spots or streaks. This applies in particular to shiny or transparent surfaces, such as glass or metal. It is therefore sought ways to improve the drying performance of cleaning agents for hard surfaces, especially dishwashing detergents.
  • the EP 1 306 423 A2 discloses aqueous detergents which contain alkyl ether sulfates and amphoteric glycine compounds and are suitable for improving the drying behavior of dishwashing detergents.
  • the DE 100 45 289 A1 describes hand dishwashing detergents which contain certain quaternary ammonium compounds and alkyl ether sulfates side by side and also show a particularly good drying behavior.
  • additives for cleaning agents must not adversely affect the rinsing and in particular the rinse performance of the cleaner. Ideally, an additive should even improve the overall performance of the cleaner.
  • the present invention is the use of compound of the general formula (Ib) wherein R '"and R"' independently of one another represent saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 4 to 22 C atoms, and the indices n and m independently of one another can assume values between 1 and 40, X ' and X "independently of one another represent saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 1 to 18 C atoms in cleaning agents, in particular dishwashing agents.
  • HME Hydroxy mixed ethers
  • hydroxy mixed ethers are known from the literature and are described, for example, in the German application DE 19738866 described. They are prepared, for example, by reaction of 1,2-epoxyalkanes (R "CHOCH 2 ), where R" is an alkyl and / or alkenyl radical having 2 to 22, in particular 6 to 16, carbon atoms, with alkoxylated alcohols.
  • R "CHOCH 2 ) 1,2-epoxyalkanes
  • Preferred for the purposes of the invention are those hydroxy mixed ethers which are derived from alkoxylates of monohydric alcohols of the formula R'-OH having 4 to 18 carbon atoms, where R 'is an aliphatic, saturated, straight-chain or branched alkyl radical, in particular having 6 to 16 carbon atoms, stands.
  • Suitable straight-chain alcohols are butanol-1, caproic, eananthic, caprylic, pelargonic, capric alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, palmityl alcohol, heptadecanol-1, stearyl alcohol, nonadecanol- 1, arachidyl alcohol, heneicosanol-1, behenyl alcohol and their technical mixtures, as obtained in the high pressure hydrogenation of technical methyl esters based on fats and oils.
  • branched alcohols examples include so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are prepared by the oxo process and so-called Guerbet alcohols which are branched in the 2-position with an alkyl group.
  • Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol.
  • the alcohols are used in the form of their alkoxylates, which are prepared by reaction of the alcohols with ethylene oxide in a known manner.
  • agents which contain 0.1 to 15 wt .-% of the mixtures according to the invention, as well as other ingredients commonly used in detergents and, preferably, dishwashing detergents.
  • the detergents contain the mixtures according to the invention in amounts of from 0.1 to 12% by weight, advantageously from 1 to 10% by weight and in particular from 1.0 to 8% by weight. Particularly preferred is the range of 2.0 to 8.0 wt .-%.
  • compositions according to the invention in the sense of the above description can be, for example, further nonionic, anionic and / or cationic surfactants, builders, enzymes, bleaching agents, such as e.g. Be percarbonates.
  • agents may contain silicates, phosphorus compounds, carbonates, but also special rinse aids and other known and customary auxiliaries and additives, e.g. pH regulators or enzymes.
  • solvents such as water or lower aliphatic alcohols, preferably ethanol or propanol, solubilizers, polymers or organic acids, preferably citric acid and derivatives thereof.
  • the cleaning agents can be both liquid and solid, for example as granules, powders or tablets.
  • Liquid detergents may still contain viscosity builders, e.g. to obtain gel-like agents.
  • machine dishwashing detergents are in solid form, for example as powders or granules or as shaped articles, preferably in tablet form.
  • There may also be several phases next to one another for example a compressed tablet which contains in a bulge a non-compressed part, eg a waxy rinse aid phase.
  • Such multifunctional agents are marketed as 2-in-1 or 3-in-1 products.
  • the preparation is carried out in any manner known to the person skilled in the art, wherein in a preferred embodiment the mixtures according to the invention are present as a compound and are preferably mixed with the other ingredients in any order.
  • Another object of the present application relates to the use of compounds of the general formulas (Ib) without the above-mentioned HME in detergents, preferably dishwashing detergents and particularly preferably in dishwashing detergents for automatic dishwashing.
  • the compounds according to the formula (Ib) can also develop advantageous effect in a cleaning agent without the use of the above-described HME, in particular with regard to an improved drying behavior of the rinsed articles, and preferably those articles which have plastic surfaces or consist of plastics.
  • Precursor fatty alcohol ethoxylate 1 mol of decanol and 0.03 mol of KOH as a 45% solution are placed in a stirred autoclave under nitrogen. The mixture is then evacuated at 120 ° C for 30 min. The vacuum is then quenched with nitrogen and heated to 160-180 ° C. At 160 ° C, the addition of 9 moles of ethylene oxide begins at a maximum pressure of 5 bar. After the reaction is cooled to 120 ° C and evacuated for 30 min. For subsequent storage or reuse, the product is neutralized after cooling (preferably with lactic acid or acetic acid).
  • the fatty alcohol ethoxylate prepared in accordance with 1. is reacted with excess di-butyl glycol formal in the presence of an acidic catalyst, preferably methanesulfonic acid.
  • an acidic catalyst preferably methanesulfonic acid.
  • a Brüdentemperatur of about 121-137 ° C distilled butyl glycol and excess formal.
  • the product is then cooled to 50-70 ° C and neutralized by addition of NaOH.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (14)

  1. Mélanges, contenant au moins deux substances tensioactives différentes, choisies dans les groupes a) et b), le composé tensioactif a) étant choisi parmi des composés de formule générale (Ia)
    Figure imgb0005
     dans laquelle M représente un radical CH2-CH2 ou CHR-CH2, R, R' ou R" représentent, chacun indépendamment, des radicaux alkyle ou alcényle saturés, insaturés, linéaires ou ramifiés ayant de 6 à 22 atomes de carbone, et les indices n et m peuvent prendre, indépendamment l'un de l'autre, des valeurs comprises entre 1 et 40,
    et/ou des composés de formule générale (Ib)
    Figure imgb0006
     dans laquelle R"' et R"" représentent, indépendamment l'un de l'autre, des radicaux alkyle ou alcényle saturés, insaturés, linéaires ou ramifiés ayant de 4 à 22 atomes de carbone, et les indices n et m peuvent prendre, indépendamment l'un de l'autre, des valeurs comprises entre 1 et 40, X' et X" représentent, indépendamment l'un de l'autre, H ou des radicaux alkyle ou alcényle saturés, insaturés, linéaires ou ramifiés, ayant de 1 à 18 atomes de carbone
    et les composés de type b) correspondant à la formule générale (II)

            R1O[CH2CH2O]xCH2CH(OM)R2     (II)

    dans laquelle R1 représente un radical alkyle et/ou alcényle linéaire ou ramifié ayant de 4 à 22 atomes de carbone, ou représente un radical R2-CH (OH) CH2, R2 représentant un radical alkyle et/ou alcényle linéaire ou ramifié ayant de 8 à 16 atomes de carbone, x représente un nombre valant de 20 à 80, de préférence de 40 à 80, et M représente un atome d'hydrogène ou un radical alkyle saturé ayant de 1 à 18 atomes de carbone et/ou de formule générale (III)

            R3O[CH2CHCH3O]z[CH2CH2O]yCH2CH(OH)R4 (     III)

    dans laquelle R3 représente un radical alkyle et/ou alcényle linéaire ou ramifié ayant de 8 à 22 atomes de carbone, R4 représente un radical alkyle et/ou alcényle linéaire ou ramifié ayant de 8 à 16 atomes de carbone, y représente un nombre valant de 10 à 35, z représente zéro ou doit être un nombre valant de 1 à 5.
  2. Mélanges selon la revendication 1, caractérisés en ce qu'ils contiennent un seul composé tensioactif a) en association avec un seul composé tensioactif b).
  3. Mélange selon les revendications 1 et 2, caractérisé en ce que dans la formule (Ia) R, R' et R" représentent chacun un radical alkyle linéaire, saturé, R représentant un radical alkyle ayant de 8 à 16 atomes de carbone, R' et R" représentant, indépendamment l'un de l'autre, un radical alkyle ayant de 10 à 16 atomes de carbone et n et m prenant, indépendamment l'un de l'autre, une valeur de 20 à 30.
  4. Mélanges selon les revendications 1 à 3, caractérisés en ce que dans la formule (Ib) les radicaux R"' et R"" représentent, indépendamment l'un de l'autre, des radicaux alkyle saturés ayant de 4 à 14 atomes de carbone, et les indices n et m prennent, indépendamment l'un de l'autre, des valeurs de 1 à 15 et en particulier de 1 à 12.
  5. Mélanges selon les revendications 1 à 4, caractérisés en ce que dans la formule (II) l'indice x représente un nombre valant de 40 à 70, de préférence de 40 à 60 et en particulier de 40 à 50.
  6. Mélange selon les revendications 1 à 5, caractérisé en ce que dans la formule (III) l'indice y représente un nombre valant de 20 à 30, de préférence de 20 à 25.
  7. Mélange selon les revendications 1 à 6, caractérisé en ce que les composés tensioactifs du type a) et du type b) sont présents en un rapport pondéral entre eux valant de 5:1 à 1:5, en particulier de 3:1 à 1:3 et de façon particulièrement préférée de 1:1.
  8. Mélange selon les revendications 1 à 7, caractérisé en ce qu'il contient en tant que composé tensioactif du type b1) un composé selon la formule générale (II), dans laquelle R1 représente un radical alkyle et/ou alcényle ayant de 8 à 10 atomes de carbone et R2 représente un radical alkyle ou alcényle ayant de 8 à 10 atomes de carbone et x représente un nombre valant de 40 à 50.
  9. Mélange selon les revendications 1 à 8, caractérisé en ce qu'il contient en tant que composé tensioactif du type b2) un composé selon la formule générale (III), dans laquelle R3 représente un radical alkyle et/ou alcényle ayant de 11 à 18 atomes de carbone et R4 représente un radical alkyle ou alcényle ayant de 8 à 10 atomes de carbone et y représente un nombre valant de 20 à 35.
  10. Mélange selon les revendications 1 à 9, caractérisé en ce qu'il contient en tant que composé tensioactif du type b2) un composé selon la formule générale (III), dans laquelle R3 représente un radical alkyle et/ou alcényle ayant de 8 à 12 atomes de carbone et R4 représente un radical alkyle ou alcényle ayant de 8 à 10 atomes de carbone et y représente un nombre valant de 20 à 35 et z représente un nombre valant de 1 à 3.
  11. Utilisation de mélanges selon les revendications 1 à 10 dans des produits de lavage et de nettoyage, de préférence dans des produits de nettoyage pour surfaces dures et en particulier dans des produits de nettoyage pour le lavage automatique de la vaisselle.
  12. Utilisation selon la revendication 11, caractérisée en ce que les mélanges sont utilisés en quantités de 0,1 à 15 % en poids, de préférence de 1 à 10 % en poids dans les produits de nettoyage.
  13. Utilisation de mélanges selon les revendications 1 à 10, pour l'amélioration du pouvoir de séchage de produits de nettoyage, de préférence de produits de nettoyage pour la vaisselle.
  14. Produit de nettoyage contenant de 0,1 à 15 % en poids de mélanges selon les revendications 1 à 10, ainsi que d'autres tensioactifs non ioniques, anioniques et/ou cationiques, ainsi qu'éventuellement des adjuvants actifs de détergence, des enzymes, des agents de rinçage et/ou d'autres additifs et adjuvants.
EP10187277A 2008-02-14 2009-02-06 Utilisation de substances tensioactives dans des nettoyants Active EP2267110B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008009366A DE102008009366A1 (de) 2008-02-14 2008-02-14 Verwendung oberflächenaktiver Substanzen in Reinigungsmitteln
EP09711301A EP2240562B1 (fr) 2008-02-14 2009-02-06 Utilisation de substances tensioactives dans des nettoyants

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EP2267110A2 EP2267110A2 (fr) 2010-12-29
EP2267110A3 EP2267110A3 (fr) 2011-04-27
EP2267110B1 true EP2267110B1 (fr) 2012-11-28

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US (1) US8148313B2 (fr)
EP (2) EP2267110B1 (fr)
CN (1) CN101945986B (fr)
AT (1) ATE523582T1 (fr)
AU (1) AU2009214382A1 (fr)
CA (1) CA2713335A1 (fr)
DE (1) DE102008009366A1 (fr)
ES (2) ES2373084T3 (fr)
PL (1) PL2240562T3 (fr)
WO (1) WO2009100855A2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201104244D0 (en) 2011-03-14 2011-04-27 Reckitt Benckiser Nv Detergent composition with improved drying performance
DE102011086639A1 (de) 2011-11-18 2013-05-23 Henkel Ag & Co. Kgaa Nichtionische Tenside als Soil-Release-Wirkstoffe
DE102012223339A1 (de) 2012-12-17 2014-06-18 Henkel Ag & Co. Kgaa Tensidkombination zur verbesserten Trocknung
US20190119606A1 (en) * 2016-04-18 2019-04-25 Basf Se Method for cleaning hard surfaces, and formulations useful for said method

Family Cites Families (15)

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Publication number Priority date Publication date Assignee Title
WO1995013260A1 (fr) * 1993-11-10 1995-05-18 Basf Aktiengesellschaft Procede de fabrication de melanges d'agents tensio-actifs non ioniques peu moussants a structure acetal
WO1996000253A1 (fr) * 1994-06-23 1996-01-04 The Dow Chemical Company Composition tensioactive contenant un produit d'addition acetal ou cetal
NZ285317A (en) 1994-09-12 1998-05-27 Ecolab Inc Rinse aid composition for use with plasticware
DE19738866A1 (de) 1997-09-05 1999-03-11 Henkel Kgaa Schaumarme Tensidmischungen mit Hydroxymischethern
CN1208296C (zh) * 2000-06-26 2005-06-29 巴斯福股份公司 含有13和15个碳原子的醇混合物及其在制备表面活性物质中的用途
DE10045289A1 (de) 2000-09-13 2002-03-28 Henkel Kgaa Schnell trocknendes Wasch- und Reinigungsmittel, insbesondere Handgeschirrspülmittel
DE10121724A1 (de) * 2001-05-04 2002-11-07 Cognis Deutschland Gmbh Geminitenside
DE10121723A1 (de) * 2001-05-04 2002-11-07 Cognis Deutschland Gmbh Geminitenside
DE10137925A1 (de) * 2001-08-07 2003-02-20 Cognis Deutschland Gmbh Geminitenside und Polyethylenglycol
DE10153047A1 (de) 2001-10-26 2003-05-08 Goldschmidt Ag Th Wässriges tensidhaltiges Reinigungsmittel mit verbessertem Trocknungsverhalten für die Reinigung harter Oberflächen, insbesondere von Geschirr
DE10162023A1 (de) * 2001-12-18 2003-07-03 Cognis Deutschland Gmbh Mischungen aus Geminitensiden und Fettalkoholalkoxylaten in Klarspülmitteln
EP1553160B1 (fr) 2003-12-29 2007-10-17 The Procter & Gamble Company Compositions de rinçage
DE102004048779A1 (de) 2004-10-07 2006-04-13 Cognis Ip Management Gmbh Reinigungsmittel, enthaltend Polyolhydroxyalkylether
DE102005044028A1 (de) * 2005-09-14 2007-03-15 Cognis Ip Management Gmbh Mischung oberflächenaktiver Substanzen zur Verwendung in Reinigungsmitteln
EP1897933A1 (fr) * 2006-09-05 2008-03-12 Cognis IP Management GmbH Utilisation des alcools gras alkoxylés à long chaîne comme additif au détergent pour le nettoyage de surfaces dures

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EP2267110A2 (fr) 2010-12-29
PL2240562T3 (pl) 2012-02-29
AU2009214382A1 (en) 2009-08-20
WO2009100855A2 (fr) 2009-08-20
US8148313B2 (en) 2012-04-03
WO2009100855A3 (fr) 2009-10-08
CA2713335A1 (fr) 2009-08-20
CN101945986B (zh) 2012-10-10
ES2373084T3 (es) 2012-01-31
US20100323948A1 (en) 2010-12-23
ES2400791T3 (es) 2013-04-12
EP2267110A3 (fr) 2011-04-27
CN101945986A (zh) 2011-01-12
DE102008009366A1 (de) 2009-08-20
ATE523582T1 (de) 2011-09-15
EP2240562A2 (fr) 2010-10-20
EP2240562B1 (fr) 2011-09-07

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