EP0814150A2 - Surfactant mixtures of acyloxyalkane suphonates and fatty acid esters - Google Patents
Surfactant mixtures of acyloxyalkane suphonates and fatty acid esters Download PDFInfo
- Publication number
- EP0814150A2 EP0814150A2 EP97108097A EP97108097A EP0814150A2 EP 0814150 A2 EP0814150 A2 EP 0814150A2 EP 97108097 A EP97108097 A EP 97108097A EP 97108097 A EP97108097 A EP 97108097A EP 0814150 A2 EP0814150 A2 EP 0814150A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- fatty acid
- alkyl ester
- acid
- acyloxyalkanesulfonate
- surfactant mixtures
- 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.)
- Withdrawn
Links
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
- C11D1/04—Carboxylic acids or 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
-
- 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
- C11D1/667—Neutral esters, e.g. sorbitan esters
Definitions
- Acyloxyalkanesulfonates are anionic surfactants, which are mainly used in solid cleaning agents such as bar soaps. These surfactants are usually prepared by the process of so-called direct esterification by reacting sodium isethionate with an excess of a free fatty acid. In this reaction, the viscosity of the reaction mixture increases sharply with increasing esterification. It has therefore proven necessary to add so-called consistency regulators so that the highly viscous reaction mass remains sufficiently stirrable. Paraffins (EP-A-0 246 471) and free fatty acids (WO 94/26866) are known as such consistency regulators.
- fatty acid esters as consistency regulators. According to the process described there, however, the consistency regulator is distilled as far as possible after the esterification reaction has ended and the end product is essentially free of fatty acid esters.
- EP-A-0 262 420 also describes the use of fatty acid esters as consistency regulators, but in this case they can remain in the end product. Only fatty acid esters that come from alcohols with at least three carbon atoms are suitable as fatty acid esters.
- the present invention relates to surfactant mixtures consisting essentially of acyloxyalkanesulfonate, fatty acid and fatty acid C 1 -C 2 alkyl ester, the content of fatty acid C 1 -C 2 alkyl ester in the surfactant mixture being 0.1 to 10% by weight, based on the content of acyloxyalkanesulfonate.
- the acyloxyalkanesulfonates contained in the surfactant mixtures according to the invention preferably have the formula R 1 COOR 2 SO 3 M wherein R 1 is C 5 -C 31 alkyl or C 5 -C 31 alkenyl, R 2 C 2 -C 4 alkylene or C 2 -C 4 alkenylene, preferably C 2 alkylene, and M is an alkali metal, alkaline earth metal -, Ammonium or substituted ammonium ion means.
- the alkyl and alkenyl groups R 1 can be straight-chain or branched.
- the group R 1 CO is derived from fatty acids such as, for example, caproic acid, capric acid, lauric acid, myristic acid, stearic acid, arachic acid, oleic acid, linoleic acid, linolenic acid, coconut fatty acid and tallow fatty acid and mixtures thereof.
- R 2 is preferably -CH 2 CH 2 -.
- acyloxyalkanesulfonates are prepared by processes known per se by esterification of at least one fatty acid with at least one hydroxyalkanesulfonate (direct esterification). Such a method is described for example in EP-A-0 585 071 (US-A-5 384 421). An excess of fatty acid and the salt of the hydroxyalkanesulfonic acid are reacted in the presence of an esterification catalyst at a temperature of 180 to 240 ° C. with the simultaneous removal of water present.
- the excess of free fatty acid is distilled off to a greater or lesser extent.
- the coconut fatty acid has an unpleasant smell, so that it is necessary to remove the coconut fatty acid completely. It is therefore preferred to work in such a way that a second fatty acid, such as stearic acid, which has a higher boiling point than coconut fatty acid, is added after the reaction has ended. and then distills off the lower boiling unwanted free coconut fatty acid.
- the presence of free fatty acid in the end product is desirable because the mixture of fatty acid and acyloxyalkanesulfonate has a better consistency and is easier to process than the acyloxyalkanesulfonate alone.
- the amount of remaining fatty acid is generally 1 to 50 wt .-%, based on the content of acyloxyalkanesulfonate.
- the addition of a second fatty acid can be dispensed with and the excess of free fatty acid is distilled practically completely from the reaction mixture in a thin-film evaporator at about 250 to 260 ° C. This is followed by the addition of the fatty acid C 1 -C 2 alkyl ester.
- the fatty acid C 1 -C 2 alkyl esters are primarily the methyl esters; the fatty acid residue is essentially derived from fatty acids with C 5 -C 31 , preferably C 8 -C 16 alkenyl groups.
- the amount of fatty acid alkyl ester is 0.1 to 10, preferably 0.5 to 5 wt .-%, based on the proportion of acyloxyalkanesulfonate.
- the fatty acid alkyl ester is added by mixing the solid reaction product with the fatty acid alkyl ester in suitable mixing devices, for example in a kneader, until the mixture is homogeneous.
- the fatty acid alkyl ester can also be added to the finished reaction product in the liquid melt, ie before cooling, or the already cooled product can be melted again and then mixed with the fatty acid alkyl ester. In the latter two cases, the final assembly is usually carried out using a scale roller or a cooling belt.
- the reaction product that is obtained in the reaction of fatty acid and isethionate contains, depending on the respective production conditions usually about 50 to 99% by weight of acyloxyalkanesulfonate.
- the rest consists essentially of free fatty acid.
- the free fatty acid can also be almost completely distilled off from the reaction mixture and thus products which are essentially free of fatty acid are obtained.
- the surfactant mixtures according to the invention obtained in this way are processed further in the customary manner to bar soaps.
- SCID I and SCID II sodium cocoyl isethionate
- basic soap 150 g of stearic acid
- water 150 g of water
- the same mixture of sodium cocoyl isethionate, basic soap, stearic acid and water was melted and the fatty acid alkyl ester was mixed in the melt, the percentage amounts of fatty acid alkyl ester given in the table below being based on the amount of sodium cocoyl isethionate (100%). In both cases the temperature was measured at which the melt could still be stirred.
Abstract
Description
Acyloxialkansulfonate sind anionische Tenside, die vor allem in festen Reinigungsmitteln wie beispielsweise in Stückseifen, eingesetzt werden. Die Herstellung dieser Tenside erfolgt üblicherweise nach dem Verfahren der sogenannten Direktveresterung durch Reaktion von Natrium-isethionat mit einem Überschuß einer freien Fettsäure. Bei dieser Reaktion steigt die Viskosität des Reaktionsgemisches mit zunehmender Veresterung stark an. Es hat sich daher als notwendig erwiesen, sogenannte Konsistenzregler zuzugeben, damit die hochviskose Reaktionsmasse noch ausreichend rührbar bleibt. Als derartige Konsistenzregler sind unter anderem Paraffine (EP-A-0 246 471) und freie Fettsäuren (WO 94/26866) bekannt.Acyloxyalkanesulfonates are anionic surfactants, which are mainly used in solid cleaning agents such as bar soaps. These surfactants are usually prepared by the process of so-called direct esterification by reacting sodium isethionate with an excess of a free fatty acid. In this reaction, the viscosity of the reaction mixture increases sharply with increasing esterification. It has therefore proven necessary to add so-called consistency regulators so that the highly viscous reaction mass remains sufficiently stirrable. Paraffins (EP-A-0 246 471) and free fatty acids (WO 94/26866) are known as such consistency regulators.
Auch die Verwendung von Fettsäureestern als Konsistenzregler ist bereits bekannt (EP-A-0 182 017). Gemäß dem dort beschriebenen Verfahren wird der Konsistenzregler jedoch nach Abschluß der Veresterungsreaktion so weit wie möglich abdestilliert und das Endprodukt ist im wesentlichen frei von Fettsäureestern. EP-A-0 262 420 beschreibt ebenfalls die Verwendung von Fettsäureestern als Konsistenzregler, die in diesem Fall jedoch im Endprodukt verbleiben können. Als Fettsäureester kommen hier nur solche in Frage, die sich von Alkoholen mit mindestens drei C-Atomen herleiten.The use of fatty acid esters as consistency regulators is already known (EP-A-0 182 017). According to the process described there, however, the consistency regulator is distilled as far as possible after the esterification reaction has ended and the end product is essentially free of fatty acid esters. EP-A-0 262 420 also describes the use of fatty acid esters as consistency regulators, but in this case they can remain in the end product. Only fatty acid esters that come from alcohols with at least three carbon atoms are suitable as fatty acid esters.
Gegenstand der vorliegenden Erfindung sind Tensidmischungen bestehend im wesentlichen aus Acyloxialkansulfonat, Fettsäure und Fettsäure-C1-C2-alkylester, wobei der Gehalt an Fettsäure-C1-C2-alkylester in der Tensidmischung 0,1 bis 10 Gew.-%, bezogen auf den Gehalt an Acyloxialkansulfonat, beträgt.The present invention relates to surfactant mixtures consisting essentially of acyloxyalkanesulfonate, fatty acid and fatty acid C 1 -C 2 alkyl ester, the content of fatty acid C 1 -C 2 alkyl ester in the surfactant mixture being 0.1 to 10% by weight, based on the content of acyloxyalkanesulfonate.
Die in den erfindungsgemäßen Tensidmischungen enthaltenen Acyloxialkansulfonate haben vorzugsweise die Formel
R1COOR2SO3M
worin R1 C5-C31-Alkyl oder C5-C31-Alkenyl, R2 C2-C4-Alkylen oder C2-C4-Alkenylen, vorzugsweise C2-Alkylen, und M ein Alkalimetall-, Erdalkalimetall-, Ammonium- oder substituiertes Ammonium-Ion bedeutet. Die Alkyl- und Alkenyl-Gruppen R1 können geradkettig oder verzweigt sein. Die Gruppe R1CO-leitet sich ab von Fettsäuren wie beispielsweise Capronsäure, Caprinsäure, Laurinsäure, Myristinsäure, Stearinsäure, Arachinsäure, Ölsäure, Linolsäure, Linolensäure, Cocosfettsäure und Talgfettsäure sowie Mischungen davon. R2 ist bevorzugt -CH2CH2-.The acyloxyalkanesulfonates contained in the surfactant mixtures according to the invention preferably have the formula
R 1 COOR 2 SO 3 M
wherein R 1 is C 5 -C 31 alkyl or C 5 -C 31 alkenyl, R 2 C 2 -C 4 alkylene or C 2 -C 4 alkenylene, preferably C 2 alkylene, and M is an alkali metal, alkaline earth metal -, Ammonium or substituted ammonium ion means. The alkyl and alkenyl groups R 1 can be straight-chain or branched. The group R 1 CO is derived from fatty acids such as, for example, caproic acid, capric acid, lauric acid, myristic acid, stearic acid, arachic acid, oleic acid, linoleic acid, linolenic acid, coconut fatty acid and tallow fatty acid and mixtures thereof. R 2 is preferably -CH 2 CH 2 -.
Die Herstellung dieser Acyloxialkansulfonate erfolgt nach an sich bekannten Verfahren durch Veresterung von mindestens einer Fettsäure mit mindestens einem Hydroxialkansulfonat (Direktveresterung). Ein solches Verfahren ist zum Beispiel in EP-A-0 585 071 (US-A-5 384 421) beschrieben. Dabei wird ein Überschuß an Fettsäure und das Salz der Hydroxialkansulfonsäure in Gegenwart eines Veresterungskatalysators bei einer Temperatur von 180 bis 240°C umgesetzt unter gleichzeitiger Entfernung von vorhandenem Wasser.These acyloxyalkanesulfonates are prepared by processes known per se by esterification of at least one fatty acid with at least one hydroxyalkanesulfonate (direct esterification). Such a method is described for example in EP-A-0 585 071 (US-A-5 384 421). An excess of fatty acid and the salt of the hydroxyalkanesulfonic acid are reacted in the presence of an esterification catalyst at a temperature of 180 to 240 ° C. with the simultaneous removal of water present.
Nach Beendigung der Veresterung wird der Überschuß an freier Fettsäure zu einem mehr oder weniger großen Teil abdestilliert. In der Praxis nimmt man bevorzugt Cocosfettsäure zur Veresterung und demzufolge verbleibt nach der Veresterung noch überschüssige freie Cocosfettsäure im Endprodukt. Bedingt durch den Anteil niederer Fettsäuren weist jedoch die Cocosfettsäure einen unangenehmen Geruch auf, so daß es notwendig ist, die Cocosfettsäure vollständig zu entfernen. Man arbeitet deshalb bevorzugt in der Weise, daß man nach Beendigung der Reaktion eine zweite Fettsäure zusetzt, wie z.B. Stearinsäure, die einen höheren Siedepunkt als die Cocosfettsäure aufweist, und destilliert dann die niedriger siedende unerwünschte freie Cocosfettsäure ab. Die Anwesenheit freier Fettsäure im Endprodukt ist deshalb erwünscht, weil das Gemisch aus Fettsäure und Acyloxialkansulfonat eine bessere Konsistenz hat und sich besser verarbeiten läßt als das Acyloxialkansulfonat allein. Die Menge an verbleibender Fettsäure beträgt im allgemeinen 1 bis 50 Gew.-%, bezogen auf den Gehalt an Acyloxialkansulfonat. Nach dem Abdestillierten der niedriger siedenden Fettsäure erfolgt dann die Zugabe des Fettsäure-C1-C2-alkylesters.After the esterification has ended, the excess of free fatty acid is distilled off to a greater or lesser extent. In practice, preference is given to using coconut fatty acid for the esterification, and consequently excess free coconut fatty acid remains in the end product after the esterification. However, due to the proportion of lower fatty acids, the coconut fatty acid has an unpleasant smell, so that it is necessary to remove the coconut fatty acid completely. It is therefore preferred to work in such a way that a second fatty acid, such as stearic acid, which has a higher boiling point than coconut fatty acid, is added after the reaction has ended. and then distills off the lower boiling unwanted free coconut fatty acid. The presence of free fatty acid in the end product is desirable because the mixture of fatty acid and acyloxyalkanesulfonate has a better consistency and is easier to process than the acyloxyalkanesulfonate alone. The amount of remaining fatty acid is generally 1 to 50 wt .-%, based on the content of acyloxyalkanesulfonate. After the lower-boiling fatty acid has been distilled off, the fatty acid C 1 -C 2 -alkyl ester is then added.
Nach einer Variante dieses Verfahrens kann man auf die Zugabe einer zweiten Fettsäure verzichten und destilliert den Überschuß an freier Fettsäure im Dünnschichtverdampfer bei ca. 250 bis 260°C praktisch vollkommen aus dem Reaktionsgemisch ab. Hieran anschließend erfolgt dann die Zugabe des Fettsäure-C1-C2-alkylesters.According to a variant of this process, the addition of a second fatty acid can be dispensed with and the excess of free fatty acid is distilled practically completely from the reaction mixture in a thin-film evaporator at about 250 to 260 ° C. This is followed by the addition of the fatty acid C 1 -C 2 alkyl ester.
Als Fettsäure-C1-C2-alkylester kommen vor allem die Methylester in Frage, der Fettsäurerest leitet sich im wesentlichen ab von Fettsäuren mit C5-C31-, vorzugsweise C8-C16-Alkenylgruppen. Die Menge an Fettsäurealkylester beträgt 0,1 bis 10, vorzugsweise 0,5 bis 5 Gew.-%, bezogen auf den Anteil an Acyloxialkansulfonat. Die Zugabe des Fettsäurealkylesters erfolgt, indem man das feste Reaktionsprodukt mit dem Fettsäurealkylester in geeigneten Mischvorrichtungen solange mischt, beispielsweise in einem Kneter, bis die Mischung homogen ist. Man kann den Fettsäurealkylester auch dem fertigen Reaktionsprodukt in der flüssigen Schmelze, d.h. vor dem Abkühlen zufügen oder das bereits abgekühlte Produkt wieder aufschmelzen und dann mit dem Fettsäurealkylester vermischen. In den beiden letzten Fällen erfolgt die endgültige Konfektionierung üblicherweise mit Hilfe einer Schuppenwalze oder eines Kühlbandes.The fatty acid C 1 -C 2 alkyl esters are primarily the methyl esters; the fatty acid residue is essentially derived from fatty acids with C 5 -C 31 , preferably C 8 -C 16 alkenyl groups. The amount of fatty acid alkyl ester is 0.1 to 10, preferably 0.5 to 5 wt .-%, based on the proportion of acyloxyalkanesulfonate. The fatty acid alkyl ester is added by mixing the solid reaction product with the fatty acid alkyl ester in suitable mixing devices, for example in a kneader, until the mixture is homogeneous. The fatty acid alkyl ester can also be added to the finished reaction product in the liquid melt, ie before cooling, or the already cooled product can be melted again and then mixed with the fatty acid alkyl ester. In the latter two cases, the final assembly is usually carried out using a scale roller or a cooling belt.
Das Reaktionsprodukt, das bei der Umsetzung von Fettsäure und Isethionat anfällt, enthält in Abhängigkeit von den jeweiligen Herstellbedingungen üblicherweise ca. 50 bis 99 Gew.-% an Acyloxialkansulfonat. Der Rest besteht im wesentlichen aus freier Fettsäure. Wie oben dargelegt, kann man auch die freie Fettsäure praktisch vollständig aus dem Reaktionsgmeisch abdestillieren und erhält somit Produkte, die im wesentlichen frei von Fettsäure sind. Die so erhaltenen erfindungsgemäßen Tensidmischungen werden in üblicher Weise zu Stückseifen weiterverarbeitet.The reaction product that is obtained in the reaction of fatty acid and isethionate contains, depending on the respective production conditions usually about 50 to 99% by weight of acyloxyalkanesulfonate. The rest consists essentially of free fatty acid. As stated above, the free fatty acid can also be almost completely distilled off from the reaction mixture and thus products which are essentially free of fatty acid are obtained. The surfactant mixtures according to the invention obtained in this way are processed further in the customary manner to bar soaps.
Ein Gemisch aus 2,1 kg Natriumcocoylisethionat (SCID I und SCID II), 600 g Grundseife, 150 g Stearinsäure und 150 g Wasser wurde in einem Kneter mit unterschiedlichen Mengen eines Fettsäurealkylesters vermischt. Gemäß einer Variante wurde das gleiche Gemisch aus Natriumcocoylisethionat, Grundseife, Stearinsäure und Wasser aufgeschmolzen und der Fettsäurealkylester in der Schmelze zugemischt, wobei die in der folgenden Tabelle angegebenen prozentualen Mengen an Fettsäurealkylester auf die Menge an Natriumcocoylisethionat (100 %ig) bezogen sind. In beiden Fällen wurde die Temperatur gemessen, bei der die Schmelze noch gerührt werden konnte. Die Grenzwerte für diese Temperaturen sind in der folgenden Tabelle zusammengefaßt:
SCID II: hochkonzentrierte Ware mit einem Gehalt von 90 % Natriumcocoylisethionat. Der Rest besteht im wesentlichen aus Polyvinylsulfonat, Na-isethionat und Fettsäure.
Grundseife: handelsübliches Gemisch aus 87-89 Gew.-% Fettsäure-Na-Salz (25 % Cocosfettsäure und 75 % Talgfettsäure) und Rest Wasser.
SCID II: highly concentrated product with a content of 90% sodium cocoyl isethionate. The rest consists essentially of polyvinyl sulfonate, Na isethionate and fatty acid.
Basic soap: commercially available mixture of 87-89% by weight fatty acid Na salt (25% coconut fatty acid and 75% tallow fatty acid) and the rest water.
Claims (4)
R1COOR2SO3M
hat, worin R1 C5-C31-Alkyl oder C5-C31-Alkenyl, R2 C2-C4-Alkylen oder C2-C4-Alkenyl, und M ein Alkalimetall-, Erdalkalimetall-, Ammonium- oder substituiertes Ammonium-Ion bedeutet.Surfactant mixture according to claim 1, characterized in that the acyloxyalkanesulfonate has the formula
R 1 COOR 2 SO 3 M
in which R 1 is C 5 -C 31 alkyl or C 5 -C 31 alkenyl, R 2 C 2 -C 4 alkylene or C 2 -C 4 alkenyl, and M is an alkali metal, alkaline earth metal, ammonium or substituted ammonium ion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1996120748 DE19620748A1 (en) | 1996-05-23 | 1996-05-23 | Mixtures of surfactants made from acyloxyalkanesulfonates and fatty acid esters |
| DE19620748 | 1996-05-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0814150A2 true EP0814150A2 (en) | 1997-12-29 |
| EP0814150A3 EP0814150A3 (en) | 1999-02-10 |
Family
ID=7795105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97108097A Withdrawn EP0814150A3 (en) | 1996-05-23 | 1997-05-20 | Surfactant mixtures of acyloxyalkane suphonates and fatty acid esters |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0814150A3 (en) |
| JP (1) | JPH1053793A (en) |
| BR (1) | BR9703374A (en) |
| DE (1) | DE19620748A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7659235B2 (en) * | 2006-12-20 | 2010-02-09 | Conopco, Inc. | Stable liquid cleansing compositions which may be prepared using fatty acyl isethionate surfactants |
| US7674759B2 (en) * | 2007-09-05 | 2010-03-09 | Conopco, Inc. | Stable liquid cleansing compositions containing high level of fatty acid isethionate surfactant products having more than 10 wt. % of fatty acid/fatty soap content |
| US7807612B2 (en) * | 2007-12-18 | 2010-10-05 | Conopco, Inc. | Fatty acyl isethionate product-containing liquid cleansing compositions stabilized with mixture of long chain and short chain fatty acids/fatty soaps |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2415141A1 (en) * | 1978-01-19 | 1979-08-17 | Unilever Nv | DETERGENT BARS WITH IMPROVED PROPERTIES |
| EP0182017A2 (en) * | 1984-11-22 | 1986-05-28 | Akzo Patente GmbH | Surface-active condensation products |
| US5185101A (en) * | 1991-08-15 | 1993-02-09 | Dr. Gene, Inc. | Compositions containing salts of acyloxyalkanesulfonates |
| WO1994026866A1 (en) * | 1993-05-19 | 1994-11-24 | Unilever Plc | Improvememts relating to soap bars |
-
1996
- 1996-05-23 DE DE1996120748 patent/DE19620748A1/en not_active Withdrawn
-
1997
- 1997-05-20 EP EP97108097A patent/EP0814150A3/en not_active Withdrawn
- 1997-05-21 JP JP13093797A patent/JPH1053793A/en not_active Withdrawn
- 1997-05-23 BR BR9703374A patent/BR9703374A/en not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2415141A1 (en) * | 1978-01-19 | 1979-08-17 | Unilever Nv | DETERGENT BARS WITH IMPROVED PROPERTIES |
| EP0182017A2 (en) * | 1984-11-22 | 1986-05-28 | Akzo Patente GmbH | Surface-active condensation products |
| US5185101A (en) * | 1991-08-15 | 1993-02-09 | Dr. Gene, Inc. | Compositions containing salts of acyloxyalkanesulfonates |
| WO1994026866A1 (en) * | 1993-05-19 | 1994-11-24 | Unilever Plc | Improvememts relating to soap bars |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19620748A1 (en) | 1997-11-27 |
| BR9703374A (en) | 1998-09-15 |
| EP0814150A3 (en) | 1999-02-10 |
| JPH1053793A (en) | 1998-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0302329B1 (en) | Process for the preparation of concentrated fluid aqueous solutions of betaines | |
| DE2546716A1 (en) | PROCESS FOR MANUFACTURING A SURFACE-ACTIVE PRODUCT | |
| EP0613457B1 (en) | Esters of fatty acids with ethoxylated polyols | |
| EP0182017B1 (en) | Surface-active condensation products | |
| DE1493370A1 (en) | Process for the production of surface-active substances | |
| EP0391392B1 (en) | Low-foam, cold-stable aqueous detergents containing nonionic, anionic and cationic surface active agents and their utilization | |
| EP0452349B1 (en) | Process for producing amphoteric surface-active imidazoline derivatives | |
| EP0814150A2 (en) | Surfactant mixtures of acyloxyalkane suphonates and fatty acid esters | |
| DE2820035C3 (en) | Mild detergent | |
| EP0739878B2 (en) | Process for the preparation of concentrated fluid aqueous betaine solutions | |
| EP0370273A1 (en) | Fatty alcohol mixtures and their ethoxylates having low temperature characteristics | |
| DE2225793C3 (en) | Process for the continuous production of a mixture of primary and secondary phosphate esters of organic hydroxy compounds | |
| EP0518881B1 (en) | Method for sulphonation of mixtures containing alkyl glycosides | |
| EP0674701B1 (en) | Aqueous textile softener dispersions | |
| DE2817626C2 (en) | ||
| DE3722186A1 (en) | METHOD FOR PRODUCING 1- (ACYLAMINOALKYL) -2-IMIDAZOLINES SUBSTITUTED IN THE 2-POSITION | |
| DE19622981A1 (en) | Acid adducts of fatty acid polyhydroxyalkylamides | |
| DE60002657T2 (en) | Process for producing soap from neutral fats | |
| EP0834547A2 (en) | Surfactant mixture containing acyloxyalkanesulphonates | |
| DE69914228T2 (en) | METHOD FOR PRODUCING SALT-FREE AMPHOTHERES WITH HIGH MONO-AMPHOPROPIONATE CONTENT | |
| EP0735021A2 (en) | Process for the preparation of acyloxyalkanesulfonates | |
| EP0834545A2 (en) | Surfactant mixtures containing acyloxysulphonates | |
| EP0262420A2 (en) | Surfactant condensation products | |
| DD207142A5 (en) | MEANS OF INCREASING THE QUANTITY OF SUGAR EFFICIENT FROM SUGAR BEET | |
| DE19640571A1 (en) | Surfactant mixtures containing acyloxyalkanesulfonates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL PT SE |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL PT SE |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
| 18W | Application withdrawn |
Withdrawal date: 19990309 |