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WO1993018127A1 - Procede d'epaississement de produits de lavage et de nettoyage liquides non-aqueux - Google Patents

Procede d'epaississement de produits de lavage et de nettoyage liquides non-aqueux Download PDF

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Publication number
WO1993018127A1
WO1993018127A1 PCT/EP1993/000483 EP9300483W WO9318127A1 WO 1993018127 A1 WO1993018127 A1 WO 1993018127A1 EP 9300483 W EP9300483 W EP 9300483W WO 9318127 A1 WO9318127 A1 WO 9318127A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrotalcite
fatty acid
prepared
reacting
hydrophobicized
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.)
Ceased
Application number
PCT/EP1993/000483
Other languages
German (de)
English (en)
Inventor
Wolfgang Breuer
Helmut Endres
Thomas Förster
Michael Schaaf
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1993018127A1 publication Critical patent/WO1993018127A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1233—Carbonates, e.g. calcite or dolomite

Definitions

  • the present invention relates to a process for thickening non-aqueous liquid detergents and cleaning agents, in which hydrophobicized hydrotalcite, which can be prepared by certain different processes, is used as the thickener.
  • Liquid detergents are often preferred to powdery products for various reasons, for example because they are easier to dose, because they do not dust during handling and because they often take up less space during storage.
  • a disadvantage of liquid detergents containing solids is their tendency to sediment during storage. Difficulties in redispersing are often associated with this. It is therefore important that such suspensions are stabilized by suitable organic or inorganic thickeners.
  • suitable organic or inorganic thickeners Depending on whether the suspensions are aqueous or non-aqueous, different agents are used for stabilization.
  • non-aqueous liquid detergents for example, DE-A-38 20 631 cellulose ethers, acrylic and acrylamide polymers or colloidal clays or bentonites or montmorillonites treated with quaternary ammonium compounds have been proposed.
  • thermostable gels for cosmetic and pharmaceutical use (DE-A-39 32 377). It was not apparent from this prior art that hydrophobized hydrotalcites are suitable for thickening non-aqueous liquid washing and cleaning agents.
  • the present invention therefore relates to a process for thickening non-aqueous liquid detergents and cleaning agents, which is characterized in that hydrophobicized hydrotalcite can be prepared by one of the following processes
  • hydrophobicized hydrocatalysts which can be prepared by the abovementioned processes are all equally suitable for the process according to the invention for thickening non-aqueous liquid detergents and cleaning agents.
  • the hydrophobicized hydrotalcites which can be prepared in this way have the following idealized general formula I.
  • A represents an equivalent of an aliphatic monocarboxylic acid having 2 to 34 carbon atoms and the conditions 0, 1 ⁇ x 0, 5 0 ⁇ a ⁇ 0, 5 0 b ⁇ 0, 5 0 ⁇ (a + b) ⁇ 0, 5 0 ⁇ z ⁇ 10
  • hydrophobized hydrotalcites that can be used for the process according to the invention correspond to the products described in more detail in DE-A-4010606.
  • Hydrotalcite is a natural mineral with the ideal molecular formula M 96 A 12 ( 0H ) 16 C0 3 • 4H 2 ° 'whose structure is derived from that of brucite (Mg (0H) 2). Hydrotalcites continuously release water when heated or calcined. The drainage is complete at 200 ° C., it being possible to prove by X-ray diffraction that the structure of the hydrotalcite has been preserved.
  • a preferred embodiment of the process according to the invention is characterized in that hydrophobicized hydrotalcite, which is obtained by reacting 1 mol of hydrotalcite of the idealized su formula, suspended in organic solvents, with 0.5 to 4 mol of a fatty acid with 6 to 30 , preferably with 6 to 22 carbon atoms, dissolved in organic solvents at elevated temperature, separating off the solid, washing and drying at 90 to 120 ° C. under reduced pressure to constant weight.
  • Organic solvents which are sufficiently inert, for example isopropyl alcohol, are suitable for suspending the hydrotalcite.
  • Isopropyl alcohol is also a suitable solvent in many cases for dissolving the fatty acid with which hydrotalcite is made hydrophobic.
  • hydrotalcite for example with fatty acid
  • mixing units such as kneaders and mixers at elevated temperature.
  • hydrotalcite can be reacted with different amounts of fatty acid.
  • Hydrophobicized reaction products with less or more fatty acid, for example up to about 70% fatty acid, based on hydrotalcite, can also be prepared without difficulty.
  • the process according to the invention can also be carried out using hydrophobic hydrotalcite, the hydrotalcite of magnesium and aluminum salts in aqueous solution of alkali metal hydroxide which contains fatty acid alkali metal salt.
  • Suitable magnesium or aluminum salts are, for example, the nitrates, which are readily soluble in water.
  • Suitable fatty acid alkali salts are derived from fatty acids with 6 to 30 carbon atoms.
  • hydrophobicized hydrotalcite which is obtained by calcining hydrotalcite at 300 to 600 ° C., suspending the calcined hydrotalcite in water, reacting with a solution or a suspension of the alkali salt of a fatty acid or a fatty acid with 6 to 30 carbon atoms 60 to 90 ⁇ C, separating the solid has, washing and drying at 90 to 120 ° C under a pressure of 50 mbar to 200 prepared, the inventive method is suitable for implementation.
  • a temperature suitable for calcination is, for example, 500 ° C., which is left to act on the hydrotalcite for about 2 hours while losing water and CO2.
  • the fatty acid used to make the calcined hydrotalcite hydrophobic n organic solvents, isopropyl alcohol spielnag solved is either water or is.
  • Another object of the present invention is the use of hydrophobized hydrotalcite, produced by one of the previously described methods for thickening non-aqueous liquid detergents and cleaners in a concentration of 0.05 to 5, preferably 0.5 to 3 % By weight of hydrophobicized hydrotalcite, based on the washing and cleaning agent.
  • Non-aqueous liquid detergents or cleaning agents have the advantage over aqueous agents that they can be prepared with a higher active ingredient content than aqueous agents and that they can also contain, for example, the bleaching agents based on peroxide compounds which are unstable in aqueous agents.
  • the hydrophobized hydrotalcite is mixed with the liquid washing and cleaning agent by grinding, for example in a ball mill. A concentration-dependent increase in the yield point and viscosity, which have a particularly low temperature dependence, is observed in the products obtained in this way.
  • This example describes the hydrophobization of hydrotalcite in solvents.
  • a different solvent instead of isopropyl alcohol.
  • 50 g of hydrotalcite was reacted with 72.1 g of TMUL, Hoechst, (calculated as C27H55C00H), dissolved in 600 ml of tetrahydrofuran.
  • water can also be used.
  • lauric acid was dissolved in hot water. After heating to approx. 80 ° C, gas evolution started. The reaction mixture was kept at this temperature until the evolution of gas had ended. The solid portion was filtered off hot; it was washed with hot water and dried as described above. The analytical determination of the magnesium, aluminum, carbon and hydrogen content gave the expected values.
  • X-ray diffraction diagrams showed the layer structure of the compounds, infrared spectra the expected bands.
  • This example describes the hydrophopation of hydrotalcite without the use of solvents.
  • 50 g of hydrotalcite from Giulini were processed with 5 g of lauric acid or 5 g of behenic acid for one hour at 80 ° C. in a knee. After cooling, powdery products resulted.
  • hydrophobicized reaction products with less and with more fatty acid, for example up to about 70% fatty acid, based on hydrotalcite, can be produced.
  • This example describes the preparation of hydrophobic hydrotalcite by synthesis of the hydrotalcite.
  • this example describes the preparation of hydrophobic hydrotalcite by synthesis.
  • the solutions of 307.7 gg (N ⁇ 3) 2-6H2 ⁇ and 150.0 g Al (N ⁇ 3) 3.9H2 ⁇ in 8 l water were mixed with the solutions of 300 g 50% sodium hydroxide solution and a) 136.2 g behenic acid, b) 113.0 g of oleic acid, c) 80.1 g of lauric acid and d) 143.0 g of technical rapeseed oil-split fatty acid in 8 l of water each pumped through a Y-piece and reacted.
  • White suspensions were obtained, which were filtered off and washed. It was dried at 105 ° C and 100 mbar.
  • This example describes the preparation of hydrophobic hydrotalcite from caleined hydrotalcite.
  • Hydrotalcite was calcined at 500 ° C for two hours. A mass loss of water and CO2 of approx. 60% occurred.
  • This example also shows the preparation of hydrophobic hydrotalcite from calcined hydrotalcite.
  • the disperser was milled in different amounts together with the other solids in the ball mill and the theological properties were measured on the following day.
  • the hydrophobicized hydrotalcites which act as dispersants, were mixed into the detergent in different amounts.
  • the yield point and the viscosity of the detergents were given at 30s ⁇ l, measured with a Carri ed viscometer.
  • the hydrophobic hydrotalcite was ⁇ at 200 C and 100 mbar removed within 2 hours water of crystallization.
  • Dispersant I is hydrotalcite which has been hydrophobicized with oleic acid in isopropanol.
  • Dispersant II is hydrotalcite which has been hydrophobized in water with lauric acid.
  • Dispersant III is hydrotalcite, which was reacted with 40% lauric acid in a kneader.
  • Table 1 shows how viscosity and yield point are influenced by hydrophobic hydrotalcite, an increase in the yield point being associated with improved sedimentation stability.
  • An anhydrous mixture of the following composition was mixed with different amounts of hydrophobized hydrotalcite and the flow limit and viscosity were measured as described in Example 1:
  • Product II from Example 1 was used in various concentrations as the hydrophobicized hydrotalcite. The results listed in Table 2 were obtained.

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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)
  • Inorganic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

Les hydrotalcites rendus hydrophobes constituent des agents d'épaississement très efficaces de produits de lavage et de nettoyage liquides non-aqueux ayant une forte concentration en matière active.
PCT/EP1993/000483 1992-03-12 1993-03-03 Procede d'epaississement de produits de lavage et de nettoyage liquides non-aqueux Ceased WO1993018127A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4207802.4 1992-03-12
DE19924207802 DE4207802A1 (de) 1992-03-12 1992-03-12 Verfahren zum verdicken nichtwaessriger fluessiger wasch- und reinigungsmittel

Publications (1)

Publication Number Publication Date
WO1993018127A1 true WO1993018127A1 (fr) 1993-09-16

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Family Applications (1)

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PCT/EP1993/000483 Ceased WO1993018127A1 (fr) 1992-03-12 1993-03-03 Procede d'epaississement de produits de lavage et de nettoyage liquides non-aqueux

Country Status (2)

Country Link
DE (1) DE4207802A1 (fr)
WO (1) WO1993018127A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1247565A3 (fr) * 2001-04-06 2003-12-10 Mizusawa Industrial Chemicals Ltd. Agent d'onctuosité
EP3450530A1 (fr) * 2017-08-28 2019-03-06 Henkel AG & Co. KGaA Moyen de lavage ou de nettoyage structuré à limite d'écoulement

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4264466A (en) * 1980-02-14 1981-04-28 The Procter & Gamble Company Mulls containing chain structure clay suspension aids
US4340493A (en) * 1980-03-14 1982-07-20 Kyowa Chemical Industry Co. Ltd. Detergent-dispersant composition for lubricating or fuel oils
DE3820631A1 (de) * 1987-06-17 1989-01-19 Colgate Palmolive Co Nicht-waessrige, fluessige textil-waschmittelzusammensetzung zur faserbehandlung und verpackung dafuer
DE3732265A1 (de) * 1987-09-25 1989-04-06 Giulini Chemie Neuartige gelzusammensetzungen
WO1989008693A1 (fr) * 1988-03-11 1989-09-21 The Dow Chemical Company Modificateurs de viscosite pour produits fonctionnels aqueux
EP0345587A1 (fr) * 1988-06-06 1989-12-13 Henkel Kommanditgesellschaft auf Aktien Utilisation, dans les détergents, de composés cationiques stratifiés qui ne contiennent pas de silicates
US4931195A (en) * 1987-07-15 1990-06-05 Colgate-Palmolive Company Low viscosity stable non-aqueous suspension containing organophilic clay and low density filler
DE3932377A1 (de) * 1989-09-28 1991-04-11 Giulini Chemie Aluminium, magnesiumhydroxi-fettsaeure verbindungen und damit hergestellte thermostabile lipogele
DE4010606A1 (de) * 1990-04-02 1991-10-10 Henkel Kgaa Verwendung von hydrophobierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung
DE4110835A1 (de) * 1991-04-04 1992-10-08 Henkel Kgaa Verfahren zur herstellung hydrophobierter doppelschichthydroxid-verbindungen

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4264466A (en) * 1980-02-14 1981-04-28 The Procter & Gamble Company Mulls containing chain structure clay suspension aids
US4340493A (en) * 1980-03-14 1982-07-20 Kyowa Chemical Industry Co. Ltd. Detergent-dispersant composition for lubricating or fuel oils
DE3820631A1 (de) * 1987-06-17 1989-01-19 Colgate Palmolive Co Nicht-waessrige, fluessige textil-waschmittelzusammensetzung zur faserbehandlung und verpackung dafuer
US4931195A (en) * 1987-07-15 1990-06-05 Colgate-Palmolive Company Low viscosity stable non-aqueous suspension containing organophilic clay and low density filler
DE3732265A1 (de) * 1987-09-25 1989-04-06 Giulini Chemie Neuartige gelzusammensetzungen
WO1989008693A1 (fr) * 1988-03-11 1989-09-21 The Dow Chemical Company Modificateurs de viscosite pour produits fonctionnels aqueux
EP0345587A1 (fr) * 1988-06-06 1989-12-13 Henkel Kommanditgesellschaft auf Aktien Utilisation, dans les détergents, de composés cationiques stratifiés qui ne contiennent pas de silicates
DE3932377A1 (de) * 1989-09-28 1991-04-11 Giulini Chemie Aluminium, magnesiumhydroxi-fettsaeure verbindungen und damit hergestellte thermostabile lipogele
DE4010606A1 (de) * 1990-04-02 1991-10-10 Henkel Kgaa Verwendung von hydrophobierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung
DE4110835A1 (de) * 1991-04-04 1992-10-08 Henkel Kgaa Verfahren zur herstellung hydrophobierter doppelschichthydroxid-verbindungen

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1247565A3 (fr) * 2001-04-06 2003-12-10 Mizusawa Industrial Chemicals Ltd. Agent d'onctuosité
EP3450530A1 (fr) * 2017-08-28 2019-03-06 Henkel AG & Co. KGaA Moyen de lavage ou de nettoyage structuré à limite d'écoulement
US10781401B2 (en) 2017-08-28 2020-09-22 Henkel Ag & Co. Kgaa Structured washing agent or cleaning agent with a flow limit

Also Published As

Publication number Publication date
DE4207802A1 (de) 1993-09-16

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