EP0084154B1 - Use of viscosity regulators in surface-active concentrates - Google Patents
Use of viscosity regulators in surface-active concentrates Download PDFInfo
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- EP0084154B1 EP0084154B1 EP82111846A EP82111846A EP0084154B1 EP 0084154 B1 EP0084154 B1 EP 0084154B1 EP 82111846 A EP82111846 A EP 82111846A EP 82111846 A EP82111846 A EP 82111846A EP 0084154 B1 EP0084154 B1 EP 0084154B1
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- viscosity
- ethylene oxide
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Classifications
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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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
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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
- C11D1/02—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
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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
- C11D1/02—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
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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
- C11D1/72—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
- C11D1/83—Mixtures of non-ionic with anionic compounds
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/03—Organic sulfoxy compound containing
Definitions
- aqueous slurries which contain a large part or all of the detergent constituents. From an economic point of view, it is important that the slurry be as rich in detergent components as possible. H. is as low in liquid fiber as possible. The lowest possible amount of water is therefore used to prepare the slurries. Concentration is limited by the highest possible viscosity at which the slurry is just processing, i.e. especially can be pumped and sprayed.
- An essential component of detergents and cleaning agents are surfactants.
- Anionic surfactants are mostly used in the production of detergent slurries as paste-like concentrates with a surfactant content of approx. 30 to approx. 60% by weight; a higher surfactant content would be desirable, but is problematic because the processability of the surfactant concentrates, which is then no longer guaranteed, due to the excess viscosity.
- a peculiarity in the rheological behavior of surfactant concentrates is that they do not react to the addition of water with a decrease in viscosity but first with a thickening to a gel-like state, from which further problems arise for the processor. For example, it is often not easy to dissolve gel clumps that have formed, or valves from pumps and containers become blocked,
- DE-A-22 51 405 describes the salts of certain carboxylic acids, in particular hydroxycarboxylic acids, as viscosity regulators.
- sulfonated aromatic compounds are suitable for this purpose.
- DE-A-123 28 006 mentions sulfates or sulfonates of aliphatic, optionally substituted hydrocarbons as viscosity reducers.
- the addition of lower alkanols is also mentioned as a possibility for reducing the viscosity in the publications mentioned.
- the addition of the well-known hydrotropes such.
- the invention aims to lower the viscosity of concentrates of alkyl sulfates, alkylarylsulfonates and a-sulforett acid esters.
- polyglycol ether-containing compounds from the group of the non-sulfated polyethylene glycols with a molecular weight of 600 to 6000, the non-sulfated polypropylene glycols with a molecular weight of 250 to 4000, the adducts of 20 to 80 moles of ethylene oxide with aliphatic Alcohols with 10 to 20 carbon atoms or from 20 to 60 moles of ethylene oxide with alkylphenols with 6 to 12 carbon atoms in the alkyl group, which are used in amounts of at most 10% by weight, based on the surfactant concentrates, of aqueous concentrates of the water-soluble salts of the anionic surfactants.
- Sulfofatty acid esters, alkylarylsulfonates, alkyl sulfates are added as viscosity regulators, which can reduce the viscosity of these concentrates to a value of at most 10,000 mPas at the usual processing temperature of the concentrates.
- inorganic salts e.g. B. trisodium phosphate (Na 3 P0 4 ) or sodium sulfate (Na 2 S0 4 ) or alkali metal hydroxide as a viscosity regulator acts as a viscosity-reducing agent, especially with alkyl sulfate concentrates.
- B. trisodium phosphate (Na 3 P0 4 ) or sodium sulfate (Na 2 S0 4 ) or alkali metal hydroxide acts as a viscosity-reducing agent, especially with alkyl sulfate concentrates.
- the surfactants are present in the concentrates in amounts of about 30% by weight of a-sulfofatty acid ester, alkyl sulfates) or, as in the case of the alkylarylsulfonates, in amounts of about 50 to 60 percent by weight.
- the viscosity reducer according to the invention, the viscosity of the concentrates at the respective processing temperature, ie at the temperature at which the surfactant concentrates are produced, pumped, mixed with other detergent constituents or sprayed, which is carried out between about 50 and 90 ° C. reduce a workable viscosity of at most 10000 mPas.
- surfactant content of the concentrates can be increased by 3 to 15% by weight without the viscosity exceeding the upper limit of about 10,000 mPas permissible for processability. which means that the surfactant concentrates contain less water, which is very important for the economy of production and the quality of the detergents.
- the viscosity regulators are added to the aqueous surfactant concentrates in amounts of preferably 0.1 to 5% by weight. Quantities of 0.5 to 3% by weight are particularly preferred. These figures relate to the aqueous surfactant concentrate. In particular, the amount of the viscosity regulator is determined by the desired lowering of the viscosity of the respective concentrate. In some cases, the maximum achievable viscosity reduction is achieved with an addition of 3% by weight.
- non-sulfated polyalkylene glycols suitable as viscosity regulators are derived from straight-chain or branched glycols having 2 or 3 carbon atoms.
- Particularly suitable polyethylene glycols have a molecular weight of 1000 to 4000, in particular 1500 to 2500.
- Such products are commercially available, for example, under the name Polywachs " ® (Chemische Werke Hüls, Marl, Federal Republic of Germany).
- Particularly suitable polypropylene glycols have a molecular weight of 400 to 2000, in particular 400 to 800.
- ethylene oxide with aliphatic alcohols suitable as viscosity regulators are derived in particular from fatty acids from natural fats, for example from coconut oil or tallow fat.
- fatty acids from natural fats, for example from coconut oil or tallow fat.
- corresponding Ziegler or oxo alcohol ethoxylates can also be used, a degree of ethoxylation of 30 to 80 moles of ethylene oxide per mole of alcohol, in particular 40 to 60 moles of ethylene oxide per mole of alcohol, giving particularly good results.
- a particularly effective viscosity regulator for ⁇ -sulfofatty acid esters and alkylarylsulfonate concentrates is, for example, the adduct of 50 moles of ethylene oxide with 1 mole of tallow alcohol.
- Suitable alkylphenol ethoxylates have in particular 8 to 12, for example predominantly 9 carbon atoms in the alkyl group and preferably 30 to 50 moles of ethylene oxide per mole of alkylphenol in the molecule.
- the adduct of 40 moles of ethylene oxide with 1 mole of nonylphenol is an example of a viscosity regulator that is particularly effective with concentrates of a-sulfofatty acid esters and alkylarylsulfonates.
- surfactants are derived in particular from fatty acids with 10 to 20, preferably 12 to 18 carbon atoms and from aliphatic alcohols with 1 to 10, preferably 1 to 2 carbon atoms in the molecule.
- the sulfo group is introduced either by sulfonation of the fatty acid and subsequent esterification of the carboxyl group with the alcohol or by sulfonation of a corresponding fatty acid ester. According to both methods, esters of sulfo fatty acids are obtained which contain the sulfo acid group in the a position.
- ⁇ -Sulfofatty acid esters which are particularly suitable as surfactants are the alkali metal or ammonium salts of the methyl and ethyl esters of tallow fatty acid with a sulfo group in the a position, the acid component of which essentially consists of saturated and unsaturated C 16 and C 18 fatty acids.
- Surfactants of this class are the sulfuric acid esters of fatty alcohols.
- the alcohol component can be saturated or unsaturated and generally has 8 to 24 carbon atoms, preferably 10 to 18 carbon atoms.
- the alcohol is derived, for example, from coconut oil or, in particular, from tallow fat.
- FAS are usually in the form of their alkali. or ammonium salts.
- ABS Alkylarylsulfonates
- ABS are the sulfonation products of alkylbenzene in particular.
- the alkyl group can be straight-chain or branched, saturated or unsaturated.
- the alkyl radical preferably has 4 to 16, in particular 6 to 14, carbons.
- the aqueous surfactant concentrates according to the invention can also contain other surface-active agents and inorganic salts such as sodium chloride and / or sodium sulfate, which in turn can likewise influence the viscosity of the concentrates.
- An aqueous concentrate of a-sulfotalg fatty acid methyl ester with approx. 29% by weight of active substance had a viscosity in the temperature range from 40 to 65 ° C without the addition of a viscosity reducer between approx. 31,000 mPas (40 ° C) and approx. 25,000 mPas (65 ° C).
- the concentrate After addition of 1.5% by weight, based on the concentrate, of nonylphenol + 20 moles of ethylene oxide, the concentrate had a viscosity between approximately 1,500 mPas (65 ° C.) and approximately 14,000 (40 ° C.).
- the ⁇ -sulph tallow fatty acid methyl ester concentrate from Example i was mixed with 1.5% by weight tallow alcohol + 25 mol ethylene oxide. The viscosity was then between approximately 1,500 mPas (65 ° C) and approximately 22,000 mPas (40 ° C). Equal additions of tallow alcohol + 50 moles of ethylene oxide or tallow alcohol + 80 moles of ethylene oxide gave comparable or better results, while typical detergent surfactants such as tallow alcohol + 14 moles of ethylene oxide and tallow alcohol + 5 moles of ethylene oxide gave poorer results.
- the same concentrate as in the previous examples was mixed with 1.5% by weight of polypropylene glycol, molecular weight 2000.
- the viscosity decreased in the range from 40 to 65 ° C to 3000 mPas (65 ° C) to 10,000 mPas (40 ° C).
- the viscosity at 40 ° C was below 6000 mPas.
- the same surfactant concentrate as in the previous examples was mixed with 1.5% by weight of polyethylene glycol, molecular weight 2000.
- the viscosity dropped to approx. 9000 mPas (40 ° C) or approx. 1000 mPas (65 ° C). Similar results were obtained with other polyethylene glycols with molecular weights between approximately 1000 and approximately 4000, while the viscosity-reducing effect of polyethylene glycols with molecular weights below 1000 was significantly lower.
- a tallow alcohol sulfate paste with 31.2% by weight of active substance had a viscosity between about 35,000 mPas (55 ° C) and about 13,000 mPas (80 ° C) without addition. After the addition of 1.5% by weight of polyethylene glycol molecular weight 2000, the viscosity dropped to approximately 10,000 mPas (55 ° C) or approximately 8000 (80 ° C).
- a tallow alcohol sulfate paste with 30.1% by weight of active substance had a viscosity between about 35,000 mPas (55 ° C) and about 10,000 mPas (80 ° C) without the addition of a viscosity reducer.
- the addition of 3% by weight of nonylphenol + 20 moles of ethylene oxide resulted in a viscosity of 9500 mPas (55 ° C) or 3100 mPas (80 ° C).
- the addition of 3% by weight tallow alcohol + 25 moles of ethylene oxide caused the viscosity to drop to 21000 mPas (55 ° C) or 2100 mPas (80 ° C).
- the active substance of the surfactant concentrates can be increased by about 3 to 5 percent by weight, depending on the type of surfactant, without the viscosity increasing to a value of about 10,000 mPas; this viscosity represents approximately the upper limit for the pumpability and processability of surfactant concentrates in the detergent slurry.
- the water content of the surfactant concentrates can be reduced by the same amount; this means considerable progress in the industrial production of detergents.
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- Detergent Compositions (AREA)
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Abstract
Description
Bei der Herstellung von pulverförmigen oder körnigen Wasch- und Reinigungsmitteln nach dem im großtechnischen Maßstab gebräuchlichen Heißsprühverfahren geht man von wäßrigen Aufschlämmungen ("Slurry" genannt) aus, die einen großen Teil oder auch alle Waschmittelbestandteile enthalten. Unter wirtschaftlichen Gesichtspunkten ist es wichtig, daß der Slurry möglichst reich an Waschmittelbestandteilen, d. h. möglichst arm an flüssigen Ballaststoffen ist. Man verwendet zum Ansetzen des Slurries daher die geringstmögliche Wassermenge. Der Konzentrierung sind aber Grenzen gesetzt durch die höchstmögliche Viskosität, bei der der Slurry gerade noch verarbeitet, d.h. vor allem gepumpt und versprüht werden kann.In the production of powdery or granular detergents and cleaning agents by the hot spray process customary on an industrial scale, aqueous slurries (called "slurry") are used which contain a large part or all of the detergent constituents. From an economic point of view, it is important that the slurry be as rich in detergent components as possible. H. is as low in liquid fiber as possible. The lowest possible amount of water is therefore used to prepare the slurries. Concentration is limited by the highest possible viscosity at which the slurry is just processing, i.e. especially can be pumped and sprayed.
Wesentlicher Bestandteil von Wasch- und Reinigungsmitteln sind Tenside. Anionische Tenside werden bei der Herstellung des Waschmittelslurries meist als pastenförmige Konzentrate mit einem Tensidgehalt von ca. 30 bis ca. 60 Gew.-% eingesetzt; ein höherer Tensidgehalt wäre zwar wünschenswert, ist aber wegen der dann nicht mehr gewährleisteten Verarbeitbarkeit der Tensidkonzentrate infolge zu hoher Viskosität problematisch. Eine Besonderheit im rheologischen Verhalten von Tensidkonzentraten besteht darin, daß diese auf die Zugabe von Wasser nicht mit einer Viskositätsverminderung sondern zunächst mit einer Verdickung zu einem gelartigen Zustand reagieren, woraus für den Verarbeiter weitere Probleme erwachsen. Beispielsweise ist es häufig nicht einfach, gebildete Gelklumpen wieder in Lösung zu bringen, oder es verstopfen Ventile von Pumpen und Behältern,An essential component of detergents and cleaning agents are surfactants. Anionic surfactants are mostly used in the production of detergent slurries as paste-like concentrates with a surfactant content of approx. 30 to approx. 60% by weight; a higher surfactant content would be desirable, but is problematic because the processability of the surfactant concentrates, which is then no longer guaranteed, due to the excess viscosity. A peculiarity in the rheological behavior of surfactant concentrates is that they do not react to the addition of water with a decrease in viscosity but first with a thickening to a gel-like state, from which further problems arise for the processor. For example, it is often not easy to dissolve gel clumps that have formed, or valves from pumps and containers become blocked,
Zur Lösung dieser Probleme sind verschiedene Vorschläge bekannt geworden. In der DE-A- 22 51 405 beispielsweise werden die Salze bestimmter Carbonsäuren, insbesondere Hydroxycarbonsäuren als Viskositätsregulatoren beschrieben. Nach der Lehre der DE-A- 23 05 554 sind sulfonierte aromatische Verbindungen für diesen Zweck geeignet. Die DE-A- 123 28 006 nennt Sulfate oder Sulfonate von aliphatischen, gegebenenfalls substituierten Kohlenwasserstoffen als Viskositätsverminderer. Auch der Zusätz von niederen Alkanolen wird als Möglichkeit zur Viskositätsverminderung in den genannten Druckschriften aufgeführt. Ferner wird der Zusatz der altbekannten Hydrotrope wie z. B. Cumolsulfonat, oder von sauren Phosphorsäureestern (DE-B- 16 17 160) oder von mehrwertigen Alkoholen, bestimmten Carbonsäuren und/oder Estern dieser Verbindungen beschrieben (EP-A- 8060). Aus der EP-A-24 711 ist bekannt, zur Verbesserung des Fließverhaltens von anionischen Tensidkonzentraten Sulfate von bestimmten Polyalkylenetherglykolen zuzusetzen. Gewünschtenfalls können zusätzlich zusammen mit den Sulfaten niedere Polyalkylenetherglykole eines Molekulargewichts von mindestens 1 500 verwendet werden.Various proposals have been made to solve these problems. DE-A-22 51 405, for example, describes the salts of certain carboxylic acids, in particular hydroxycarboxylic acids, as viscosity regulators. According to the teaching of DE-A-23 05 554, sulfonated aromatic compounds are suitable for this purpose. DE-A-123 28 006 mentions sulfates or sulfonates of aliphatic, optionally substituted hydrocarbons as viscosity reducers. The addition of lower alkanols is also mentioned as a possibility for reducing the viscosity in the publications mentioned. Furthermore, the addition of the well-known hydrotropes such. B. cumene sulfonate, or of acidic phosphoric acid esters (DE-B-16 17 160) or of polyhydric alcohols, certain carboxylic acids and / or esters of these compounds (EP-A-8060). From EP-A-24 711 it is known to add sulfates of certain polyalkylene ether glycols to improve the flow behavior of anionic surfactant concentrates. If desired, lower polyalkylene ether glycols with a molecular weight of at least 1,500 can additionally be used together with the sulfates.
Manche der in der Literatur genannten Zusätze wirken nur bei bestimmten Tensiden, andere verdünnen die Konzentrate zu sehr mit waschunwirksamen Zusätzen, da sie nur in größeren Mengen wirksam sind, wieder andere, wie niedere Alkanole, erniedrigen den Flammpunkt.Some of the additives mentioned in the literature only work with certain surfactants, others dilute the concentrates too much with additives that are not effective in washing, since they are only effective in larger amounts, while others, such as lower alkanols, lower the flash point.
Aufgabe der vorliegenden Erfindung ist daher die Verwendung vin Viskositätsverminderern für wäßrige Konzentrate anionischer Tenside, so daß sie in höheren Konzentrationen als bisher verarbeitbar sind bzw. beim Verdünnen mit Wasser kein Ansteigen der Viskosität aufweisen.It is therefore an object of the present invention to use vin viscosity reducers for aqueous concentrates of anionic surfactants, so that they can be processed in higher concentrations than previously or have no increase in viscosity when diluted with water.
Die Erfindung will die Viskosität von Konzentraten von Alkylsulfaten, Alkylarylsulfonaten und a-Sulforettsäureestern erniedrigen.The invention aims to lower the viscosity of concentrates of alkyl sulfates, alkylarylsulfonates and a-sulforett acid esters.
Es wurde nun gefunden, daß man durch die Verwendung von Polyglykolethergruppen enthaltenden Verbindungen aus der Gruppe der nichtsulfatierten Polyethylenglykole mit einem Molekular gewicht von 600 bis 6000, der nichtsulfatierten Polypropylenglykole mit einem Molekulargewicht von 250 bis 4000, der Anlagerungsprodukte von 20 bis 80 Mol Ethylenoxid an aliphatische Alkohole mit 10 bis 20 Kohlenstoffatomen oder von 20 bis 60 Mol Ethylenoxid an Alkylphenole mit 6 bis 12 Kohlenstoffatomen in der Alkylgruppe, die man in Mengen von maximal 10 Gew.-%, bezogen auf die Tensidkonzentrate, wäßrigen Konzentraten der wasserlöslichen Salze der anionischen Tensidea-Sulfofettsäureester, Alkylarylsulfonate, Alkylsulfate als Viskositätsregler zusetzt, die Viskosität dieser Konzentrate bei der üblichen Verarbeitungstemperatur der Konzentrate auf einen Wert von höchstens 10 000 mPas vermindern kann.It has now been found that by using polyglycol ether-containing compounds from the group of the non-sulfated polyethylene glycols with a molecular weight of 600 to 6000, the non-sulfated polypropylene glycols with a molecular weight of 250 to 4000, the adducts of 20 to 80 moles of ethylene oxide with aliphatic Alcohols with 10 to 20 carbon atoms or from 20 to 60 moles of ethylene oxide with alkylphenols with 6 to 12 carbon atoms in the alkyl group, which are used in amounts of at most 10% by weight, based on the surfactant concentrates, of aqueous concentrates of the water-soluble salts of the anionic surfactants. Sulfofatty acid esters, alkylarylsulfonates, alkyl sulfates are added as viscosity regulators, which can reduce the viscosity of these concentrates to a value of at most 10,000 mPas at the usual processing temperature of the concentrates.
Auch der Zusatz bestimmter anorganischer Salze, z. B. Trinatriumphosphat (Na3P04) oder Natriumsulfat (Na2S04) oder Alkalihydroxid als Viskositätsregler wirkt viskositätsvermindemd, insbesondere bei Alkylsulfatkonzentraten.The addition of certain inorganic salts, e.g. B. trisodium phosphate (Na 3 P0 4 ) or sodium sulfate (Na 2 S0 4 ) or alkali metal hydroxide as a viscosity regulator acts as a viscosity-reducing agent, especially with alkyl sulfate concentrates.
Die Tenside liegen in den Konzentraten je nach Art der Tenside in Mengen von etwa 30 Gew.-% a-Sulfofettsäureester, Alkylsulfate) oder, wie im Fall der Alkylarylsulfonate in Mengen von ca. 50 bis 60 Gewichtsprozent. Durch die erfindungsgemäße Verwendung der Viskositätsverminderer kann man die Viskosität der Konzentrate bei der jeweiligen Verarbeitungstemperatur, d. h. bei der Temperatur, bei der die Tensidkonzentrate hergestellt, gepumpt, mit anderen Waschmittelbestandteilen vermischt oder versprüht werden, was man zwischen etwa 50 und 90°C vornimmt, auf eine noch verarbeitbare Viskosität von höchstens 10000 mPas vermindern. Ein weiterer, sehr wesentlicher Vorteil der erfindungsgemäßen Verwendung besteht darin, daß man den Tensidgehalt der Konzentrate um 3 bis 15 Gew.-% erhöhen kann, ohne daß die Viskosität, die für die Verarbeitbarkeit zulässige Obergrenze von etwa 10000 mPas übersteigt, wodurch die Tensidkonzentrate entsprechend weniger Wasser enthalten, was für die Ökonomie der Herstellung und die Qualität der Waschmittel sehr wichtig ist.Depending on the type of surfactant, the surfactants are present in the concentrates in amounts of about 30% by weight of a-sulfofatty acid ester, alkyl sulfates) or, as in the case of the alkylarylsulfonates, in amounts of about 50 to 60 percent by weight. Through the use of the viscosity reducer according to the invention, the viscosity of the concentrates at the respective processing temperature, ie at the temperature at which the surfactant concentrates are produced, pumped, mixed with other detergent constituents or sprayed, which is carried out between about 50 and 90 ° C. reduce a workable viscosity of at most 10000 mPas. Another very important advantage of the use according to the invention is that the surfactant content of the concentrates can be increased by 3 to 15% by weight without the viscosity exceeding the upper limit of about 10,000 mPas permissible for processability. which means that the surfactant concentrates contain less water, which is very important for the economy of production and the quality of the detergents.
Die Viskositätregler setzt man den wäßrigen Tensidkonzentraten in Mengen von vorzugsweise 0,1 bis 5 Gew.-% zu. Besonders bevorzugt sind Mengen von 0,5 bis 3 Gew.-% Diese Angaben bezeihen sich auf das wäßrige Tensidkonzentrat. Im einzelnen wird die Menge des Viskositätsreglers durch die erwünschte Viskositätserniedrigung des jeweiligen Konzentrats bestimmt. In machen Fällen ist bereits bei einem Zuzatz von 3 Gew.-% die maximal erreichbare Viskositätssenkung erreicht.The viscosity regulators are added to the aqueous surfactant concentrates in amounts of preferably 0.1 to 5% by weight. Quantities of 0.5 to 3% by weight are particularly preferred. These figures relate to the aqueous surfactant concentrate. In particular, the amount of the viscosity regulator is determined by the desired lowering of the viscosity of the respective concentrate. In some cases, the maximum achievable viscosity reduction is achieved with an addition of 3% by weight.
Die als Viskositätsregler geeigneten nichtsulfatierten Polyalkylenglykole leiten sich von geradkettigen oder verzweigten Glykolen mit 2 oder 3 Kohlenstoffatomen ab. Besonders geeignete Polyethylenglykole weisen ein Molekulargewicht von 1000 bis 4000, insbesondere 1500 bis 2500 auf. Derartige Produkte sind beispielsweise im Handel unter der Bezeichnung Polywachs"® (Chemische Werke Hüls, Marl, Bundesrepublik Deutschland) erhältlich.The non-sulfated polyalkylene glycols suitable as viscosity regulators are derived from straight-chain or branched glycols having 2 or 3 carbon atoms. Particularly suitable polyethylene glycols have a molecular weight of 1000 to 4000, in particular 1500 to 2500. Such products are commercially available, for example, under the name Polywachs " ® (Chemische Werke Hüls, Marl, Federal Republic of Germany).
Besonders geeignete Polypropylenglykole weisen ein Molekulargewicht von 400 bis 2000 auf, insbesondere 400 bis 800.Particularly suitable polypropylene glycols have a molecular weight of 400 to 2000, in particular 400 to 800.
Die als Viskositätsregler geeignete Anlagerungsprodukte von Ethylenoxid an aliphatische Alkohole leiten sich insbesondere von Fettsäuren natürlicher Fette, beispielsweise von Kokosöl oder Talgfett ab. Es können aber auch entsprechende Ziegler- oder Oxoalkoholethoxylate verwendet werden, wobei ein Ethoxylierungsgrad von 30 bis 80 Mol Ethylenoxid pro Mol Alkohol, insbesondere 40 bis 60 Mol Ethylenoxid pro Mol Alkohol besonders gute Ergebnisse liefert. Ein besonders wirksamer Viskositätsregler für a-Sulfofettsäureester und Alkylarylsulfonat-Konzentrate ist beispielsweise das Anlagerungsprodukt von 50 Mol Ethylenoxid an 1 Mol Talgalkohol.The addition products of ethylene oxide with aliphatic alcohols suitable as viscosity regulators are derived in particular from fatty acids from natural fats, for example from coconut oil or tallow fat. However, corresponding Ziegler or oxo alcohol ethoxylates can also be used, a degree of ethoxylation of 30 to 80 moles of ethylene oxide per mole of alcohol, in particular 40 to 60 moles of ethylene oxide per mole of alcohol, giving particularly good results. A particularly effective viscosity regulator for α-sulfofatty acid esters and alkylarylsulfonate concentrates is, for example, the adduct of 50 moles of ethylene oxide with 1 mole of tallow alcohol.
Geeignete Alkylphenolethoxylate haben insbesondere 8 bis 12, beispielsweise überwiegend 9 Kohlenstoffatome in der Alkylgruppe und vorzugsweise 30 bis 50 Mol Ethylenoxid pro Mol Alkylphenol im Molekül. Das Anlagerungsprodukt von 40 Mol Ethylenoxid an 1 Mol Nonylphenol ist ein Beispiel für einen Viskositätsregler, der besonders wirksam bei Konzentraten von a-Sulfofettsäureestern und Alkylarylsulfonaten ist.Suitable alkylphenol ethoxylates have in particular 8 to 12, for example predominantly 9 carbon atoms in the alkyl group and preferably 30 to 50 moles of ethylene oxide per mole of alkylphenol in the molecule. The adduct of 40 moles of ethylene oxide with 1 mole of nonylphenol is an example of a viscosity regulator that is particularly effective with concentrates of a-sulfofatty acid esters and alkylarylsulfonates.
Die Tensidkonzentraten, deren Viskosität durch die vorgenannten Viskositätsregler beeinflußt werden kann, enthalten insbesondere die folgenden Tenside:
- 1. a-Sulfofettsäureester (SFE)
- 1. a-sulfofatty acid ester (SFE)
Diese Tenside leiten sich insbesondere von Fettsäuren mit 10 bis 20, vorzugsweise 12 bis 18 Kohlenstoffatomen und von aliphatischen Alkoholen mit 1 bis 10, vorzugsweise 1 bis 2 Kohlenstoffatomen im Molekül ab. Die Einführung der Sulfogruppe erfolgt entweder durch Sulfonierung der Fettsäure und anschließende Veresterung der Carboxylgruppe mit dem Alkohol oder durch Sulfonierung eines entsprechenden Fettsäureesters. Nach beiden Verfahren werden Ester von Sulfofettsäuren erhalten, die die Sulfosäuregruppe in a-Stellung enthalten. Als Tenside besonders geeignete a-Sulfofettsäureester sind die Alkali- oder Ammoniumsalze der Methyl- und Ethylester von Talgfettsäure mit einer Sulfogruppe in a -Stellung, deren Säurekomponente also im wesentlichen aus gesättigten und ungesättigten C16- und C18-Fettsäuren besteht.These surfactants are derived in particular from fatty acids with 10 to 20, preferably 12 to 18 carbon atoms and from aliphatic alcohols with 1 to 10, preferably 1 to 2 carbon atoms in the molecule. The sulfo group is introduced either by sulfonation of the fatty acid and subsequent esterification of the carboxyl group with the alcohol or by sulfonation of a corresponding fatty acid ester. According to both methods, esters of sulfo fatty acids are obtained which contain the sulfo acid group in the a position. Α-Sulfofatty acid esters which are particularly suitable as surfactants are the alkali metal or ammonium salts of the methyl and ethyl esters of tallow fatty acid with a sulfo group in the a position, the acid component of which essentially consists of saturated and unsaturated C 16 and C 18 fatty acids.
Tenside dieser Klasse sind die Schwefelsäureester von Fettalkoholen. Die Alkoholkomponente kann dabei gesättigt oder ungesättigt sein und weist in der Regel 8 bis 24 Kohlenstoffatome, vorzugsweise 10 bis 18 Kohlenstoffatome auf. Der Alkohol leitet sich beispielsweise von Kokosöl oder insbesondere von Talgfett ab. FAS liegen üblicherweise in Form ihrer Alkali. oder Ammoniumsalze vor.Surfactants of this class are the sulfuric acid esters of fatty alcohols. The alcohol component can be saturated or unsaturated and generally has 8 to 24 carbon atoms, preferably 10 to 18 carbon atoms. The alcohol is derived, for example, from coconut oil or, in particular, from tallow fat. FAS are usually in the form of their alkali. or ammonium salts.
ABS sind die Sulfonierungsprodukte von insbesondere Alkylbenzol. Die Alkylgruppe kann geradkettig oder verzweigt, dabei gesättigt oder ungesättigt sein. Vorzugsweise besitzt der Alkylrest 4 bis 16, insbesondere 6 bis 14 Kohlenstoffe. Besondere Bedeutung besitzen ABS, deren Alkylreste 8 bis 12 Kohlenstoffatome aufweisen und als Alkali- oder Ammoniumsalze vorliegen.ABS are the sulfonation products of alkylbenzene in particular. The alkyl group can be straight-chain or branched, saturated or unsaturated. The alkyl radical preferably has 4 to 16, in particular 6 to 14, carbons. ABS, whose alkyl radicals have 8 to 12 carbon atoms and are present as alkali or ammonium salts, are of particular importance.
Neben diesen anionischen Tensiden können die erfindungsgemäßen wäßrigen Tensidkonzentrate auch andere oberflächenaktive Mittel sowie anorganische Salze wie Natriumchlorid und/oder Natriumsulfat enthalten, die ihrerseits ebenfalls einen Einfluß auf die Viskosität der Konzentrate ausüben können.In addition to these anionic surfactants, the aqueous surfactant concentrates according to the invention can also contain other surface-active agents and inorganic salts such as sodium chloride and / or sodium sulfate, which in turn can likewise influence the viscosity of the concentrates.
Ein wäßriges Konzentrat von a-Sulfotalgfettsäuremethylester mit ca. 29 Gew.-% Aktivsubstanz hatte im Temperaturbereich von 40 bis 65 °C ohne Zusatz eines Viskositätsverminderers eine Viskosität zwischen ca. 31 000 mPas (40 °C) und ca. 25 000 mPas (65 °C). Nach Zusatz von 1,5 Gew.-%, bezogen auf das Konzentrat, Nonylphenol + 20 Mol Ethylenoxid hatte das Konzentrat eine Viskosität zwischen ca. 1 500 mPas (65 °C) und ca. 14 000 (40 °C). Ähnliche oder bessere Ergebnisse wurden erhalten, wenn man als Viskositätsregler die gleiche Menge Nonylphenol mit 40 bzw. 60 Mol Ethylenoxid verwendete. Eine wesentlich geringere Wirkung wurde dagegen mit Nonylphenol + 10 und Nonylphenol + 6,5 Mol Ethylenoxid, also typischen Waschmitteltensiden, erhalten.An aqueous concentrate of a-sulfotalg fatty acid methyl ester with approx. 29% by weight of active substance had a viscosity in the temperature range from 40 to 65 ° C without the addition of a viscosity reducer between approx. 31,000 mPas (40 ° C) and approx. 25,000 mPas (65 ° C). After addition of 1.5% by weight, based on the concentrate, of nonylphenol + 20 moles of ethylene oxide, the concentrate had a viscosity between approximately 1,500 mPas (65 ° C.) and approximately 14,000 (40 ° C.). Similar or better results were obtained if the same amount of nonylphenol with 40 or 60 moles of ethylene oxide was used as the viscosity regulator. On the other hand, a significantly lower effect was obtained with nonylphenol + 10 and nonylphenol + 6.5 mol ethylene oxide, i.e. typical detergent surfactants.
Das a-Sulfotalgfettsäuremethylester-Konzentrat von Beispiel i wurde mit 1,5 Gew.-% Talgalkohol + 25 Mol Ethylenoxid versetzt. Die Viskosität lag dann zwischen ca. 1 500 mPas (65 °C) und ca. 22 000 mPas (40 °C). Gleichgroße Zusätze von Talgalkohol + 50 Mol Ethylenoxid oder Talgalkohol + 80 Mol Ethylenoxid ergaben vergleichbare oder bessere Ergebnisse, während typische Waschmitteltenside wie Talgalkohol + 14 Mol Ethylenoxid und Talgalkohol + 5 Mol Ethylenoxid schlechtere Ergebnisse lieferten.The α-sulph tallow fatty acid methyl ester concentrate from Example i was mixed with 1.5% by weight tallow alcohol + 25 mol ethylene oxide. The viscosity was then between approximately 1,500 mPas (65 ° C) and approximately 22,000 mPas (40 ° C). Equal additions of tallow alcohol + 50 moles of ethylene oxide or tallow alcohol + 80 moles of ethylene oxide gave comparable or better results, while typical detergent surfactants such as tallow alcohol + 14 moles of ethylene oxide and tallow alcohol + 5 moles of ethylene oxide gave poorer results.
Das gleiche Konzentrat wie in den vorangegangenen Beispielen wurde mit 1,5 Gew.- % Polypropylenglykol, Molekulargewicht 2000, vermischt. Die Viskosität ging im Bereich 40 bis 65 °C auf 3000 mPas (65 °C) bis 10 000 mPas (40 °C) zurück. Bei Verwendung der gleichen Menge Polypropylenglykol, Molekulargewicht 400 und 600 lag die Viskosität bei 40 °C unter 6000 mPas.The same concentrate as in the previous examples was mixed with 1.5% by weight of polypropylene glycol, molecular weight 2000. The viscosity decreased in the range from 40 to 65 ° C to 3000 mPas (65 ° C) to 10,000 mPas (40 ° C). When using the same amount of polypropylene glycol, molecular weight 400 and 600, the viscosity at 40 ° C was below 6000 mPas.
Das gleiche Tensidkonzentrat wie in den vorangegangenen Beispielen wurde mit 1,5 Gew.- % Polyethylenglykol, Molekulargewicht 2000, vermischt. Die Viskosität sank auf ca. 9000 mPas (40 °C) bzw. auf ca. 1000 mPas (65 °C). Mit anderen Polyethylenglykolen mit Molekulargewichten zwischen etwa 1000 und etwa 4000 wurden ähnliche Ergebnisse erhalten, während die viskositätsvermindernde Wirkung von Polyethylenglykolen mit Molekulargewichten unter 1000 deutlich geringer war.The same surfactant concentrate as in the previous examples was mixed with 1.5% by weight of polyethylene glycol, molecular weight 2000. The viscosity dropped to approx. 9000 mPas (40 ° C) or approx. 1000 mPas (65 ° C). Similar results were obtained with other polyethylene glycols with molecular weights between approximately 1000 and approximately 4000, while the viscosity-reducing effect of polyethylene glycols with molecular weights below 1000 was significantly lower.
Eine Alkylbenzolsulfonat-Paste mit 59 Gew-% Aktivsubstanz wies ohne Zusatz eines Viskositätsverminderers eine Viskosität von ca. 17 000 mPas (40 °C) bzw. von ca. 13 000 mPas (55 °C) auf. Nach Zusatz von 1,5 Gew.-% Polyethylenglykol, Molekulargewicht 2000 betrug die Viskosität nur noch ca. 2800 mPas (40-55 ° C). Vergleichbare Ergebnisse erhielt man, wenn man der ABS-Paste die gleiche Menge Talg-Menge talgalkohol + 50 Mol Ethylenoxid oder Nonylphenol + 40 Mol Ethylenoxid zusetzte, während Talgalkohol + 14 Mol Ethylenoxid eine deutlich geringere Viskositätsverminderung bewirkte.An alkylbenzenesulfonate paste with 59% by weight of active substance had, without the addition of a viscosity reducer, a viscosity of approx. 17,000 mPas (40 ° C.) or approx. 13,000 mPas (55 ° C.). After adding 1.5% by weight of polyethylene glycol, molecular weight 2000, the viscosity was only approx. 2800 mPas (40-55 ° C). Comparable results were obtained if the same amount of tallow tallow alcohol + 50 mol ethylene oxide or nonylphenol + 40 mol ethylene oxide was added to the ABS paste, while tallow alcohol + 14 mol ethylene oxide caused a significantly lower viscosity reduction.
Eine Talgalkoholsulfat-Paste mit 31,2 Gew.-% Aktivsubstanz wies ohne Zusatz eine Viskosität zwischen ca. 35 000 mPas (55 °C) und ca. 13 000 mPas (80 °C) auf. Nach Zusatz von 1,5 Gew.-% Polyethylenglykol Molekulargewicht 2000 sank die Viskosität auf ca. 10 000 mPas (55 °C) bzw. ca. 8000 (80 ° C).A tallow alcohol sulfate paste with 31.2% by weight of active substance had a viscosity between about 35,000 mPas (55 ° C) and about 13,000 mPas (80 ° C) without addition. After the addition of 1.5% by weight of polyethylene glycol molecular weight 2000, the viscosity dropped to approximately 10,000 mPas (55 ° C) or approximately 8000 (80 ° C).
Eine Talgalkoholsulfat-Paste mit 30,1 Gew.-% Aktivsubstanz wies ohne Zusatz eines Viskositätsverminderers eine Viskosität zwischen ca. 35 000 mPas (55 °C) und ca. 10 000 mPas (80 °C) auf. Ein Zusatz von 2,0 Gew.-% Polyethylenglykol, Molekulargewicht 2000, bewirkte eine Senkung der Viskosität auf Werte zwischen ca. 22 000 mPas (55 °C) und ca. 6000 (80 °C). Der Zusatz von 3 Gew.-% Nonylphenol + 20 Mol Ethylenoxid führte zu einer Viskosität von 9500 mPas (55 ° C) bzw. 3100 mPas (80 °C). Ein Zusatz von 3 Gew.-% Talgalkohol + 25 Mol Ethylenoxid bewirkte eine Viskositätssenkung auf 21000 mPas (55 °C) bzw. 2100 mPas (80 °C).A tallow alcohol sulfate paste with 30.1% by weight of active substance had a viscosity between about 35,000 mPas (55 ° C) and about 10,000 mPas (80 ° C) without the addition of a viscosity reducer. The addition of 2.0% by weight of polyethylene glycol, molecular weight 2000, brought about a reduction in the viscosity to values between approximately 22,000 mPas (55 ° C) and approximately 6000 (80 ° C). The addition of 3% by weight of nonylphenol + 20 moles of ethylene oxide resulted in a viscosity of 9500 mPas (55 ° C) or 3100 mPas (80 ° C). The addition of 3% by weight tallow alcohol + 25 moles of ethylene oxide caused the viscosity to drop to 21000 mPas (55 ° C) or 2100 mPas (80 ° C).
Durch die erfindungsgemäße Verwendung der viskositätssenkenden Zusätze läßt sich die Aktivsubstanz der Tensid-Konzentrate je nach Tensid-Typ um etwa 3 bis 5 Gewichtsprozent anheben, ohne daß die Viskosität auf einen Wert von über etwa 10 000 mPas ansteigt; diese Viskosität stellt etwa die Obergrenze für die Pumpbarkeit und Verarbeitbarkeit von Tensidkonzentraten im Waschmittel-Slurry dar. Entsprechend der höheren Aktivsubstanz-Konzentration kann man den Wassergehalt der Tensid-Konzentrate um den gleichen Betrag verringern; dies bedeutet bei der großtechnischen Waschmittel-Herstellung einen erheblichen Fortschritt.Through the use according to the invention of the viscosity-reducing additives, the active substance of the surfactant concentrates can be increased by about 3 to 5 percent by weight, depending on the type of surfactant, without the viscosity increasing to a value of about 10,000 mPas; this viscosity represents approximately the upper limit for the pumpability and processability of surfactant concentrates in the detergent slurry. According to the higher active substance concentration, the water content of the surfactant concentrates can be reduced by the same amount; this means considerable progress in the industrial production of detergents.
Claims (6)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AT82111846T ATE20357T1 (en) | 1981-12-28 | 1982-12-20 | USE OF VISCOSITY REGULATORS FOR TENSIDE CONCENTRATES. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19813151679 DE3151679A1 (en) | 1981-12-28 | 1981-12-28 | "USE OF VISCOSITY REGULATORS FOR SURFACTANT CONCENTRATES" |
DE3151679 | 1981-12-28 |
Publications (3)
Publication Number | Publication Date |
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EP0084154A1 EP0084154A1 (en) | 1983-07-27 |
EP0084154B1 true EP0084154B1 (en) | 1986-06-11 |
EP0084154B2 EP0084154B2 (en) | 1990-02-21 |
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ID=6149903
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EP82111846A Expired - Lifetime EP0084154B2 (en) | 1981-12-28 | 1982-12-20 | Use of viscosity regulators in surface-active concentrates |
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US (1) | US4482470A (en) |
EP (1) | EP0084154B2 (en) |
JP (1) | JPS58118899A (en) |
AT (1) | ATE20357T1 (en) |
BR (1) | BR8207499A (en) |
CA (1) | CA1200733A (en) |
DE (2) | DE3151679A1 (en) |
MX (1) | MX7401E (en) |
ZA (1) | ZA829512B (en) |
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DE3240403A1 (en) * | 1982-11-02 | 1984-05-03 | Henkel KGaA, 4000 Düsseldorf | USE OF LOW MOLECULAR ORGANIC COMPOUNDS AS A VISCOSITY REGULATOR FOR HIGH VISCOSE TECHNICAL TENSIDE CONCENTRATES |
DE3305430A1 (en) * | 1983-02-17 | 1984-08-23 | Henkel KGaA, 4000 Düsseldorf | USE OF ALCOHOLS AND THEIR DERIVATIVES AS VISCOSITY REGULATORS FOR HIGH VISCOSE TECHNICAL TENSIDE CONCENTRATES |
US4675127A (en) * | 1985-09-26 | 1987-06-23 | A. E. Staley Manufacturing Company | Process for preparing particulate detergent compositions |
JPS62116698A (en) * | 1985-11-15 | 1987-05-28 | 花王株式会社 | High concentration aqueous solution of alpha-sulfo-fatty acid ester |
DE3603580A1 (en) * | 1986-02-06 | 1987-08-13 | Henkel Kgaa | ESTERSULPHONATE CONTAINING TENSIDE CONCENTRATES AND THEIR USE |
CA1323280C (en) * | 1987-07-31 | 1993-10-19 | Mario Bulfari | Liquid detergent compositions |
GB8718217D0 (en) * | 1987-07-31 | 1987-09-09 | Unilever Plc | Liquid detergent compositions |
FR2630454B1 (en) * | 1988-04-22 | 1990-08-10 | Air Liquide | STORAGE-STABLE AQUEOUS AQUEOUS LIQUID LIQUIDS AND WASHING METHOD |
GB2223611A (en) * | 1988-10-07 | 1990-04-11 | Nigel Anthony Collier | Electronic bark suppressor |
US5152932A (en) * | 1989-06-09 | 1992-10-06 | The Procter & Gamble Company | Formation of high active detergent granules using a continuous neutralization system |
US5045238A (en) * | 1989-06-09 | 1991-09-03 | The Procter & Gamble Company | High active detergent particles which are dispersible in cold water |
US6087320A (en) * | 1989-09-14 | 2000-07-11 | Henkel Corp. | Viscosity-adjusted surfactant concentrate compositions |
DE4024657A1 (en) * | 1990-08-03 | 1992-02-06 | Henkel Kgaa | METHOD FOR DRYING AND GRANULATING WAESS-RATED PASTE WASH ACTIVE AGGREGATE MIXTURES |
DE4105851A1 (en) * | 1991-02-25 | 1992-08-27 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF ALKYL AND / OR ALKENYL SULPHATE PAST WITH IMPROVED FLOWING CAPACITY |
GB9105808D0 (en) * | 1991-03-19 | 1991-05-01 | Shell Int Research | A liquid aqueous concentrated alkylsulphate composition |
US5298195A (en) * | 1992-03-09 | 1994-03-29 | Amway Corporation | Liquid dishwashing detergent |
EP0647262A4 (en) * | 1992-06-16 | 1998-04-29 | Henkel Corp | Viscosity-adjusted surfactant concentrate compositions. |
DE4227210A1 (en) * | 1992-08-17 | 1994-02-24 | Huels Chemische Werke Ag | Process for the preparation of high bulk density alkyl sulfate powders |
LT3962B (en) | 1993-12-21 | 1996-05-27 | Albright & Wilson | Funcional fluids |
WO1996025482A1 (en) * | 1995-02-13 | 1996-08-22 | The Procter & Gamble Company | Process for producing detergent agglomerates in which particle size is controlled |
US5574005A (en) * | 1995-03-07 | 1996-11-12 | The Procter & Gamble Company | Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties |
WO2016160407A1 (en) * | 2015-03-31 | 2016-10-06 | Stepan Company | Detergents based on alpha-sulfonated fatty ester surfactants |
US20180216038A1 (en) | 2017-01-27 | 2018-08-02 | The Procter & Gamble Company | Detergent particle comprising polymer and surfactant |
CN110691839B (en) | 2017-05-30 | 2021-09-24 | 联合利华知识产权控股有限公司 | Liquid detergent composition |
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DE1225799B (en) * | 1964-01-10 | 1966-09-29 | Henkel & Cie Gmbh | Liquid or paste-like, soap-containing washing active substance concentrates |
BE790362A (en) * | 1971-10-20 | 1973-02-15 | Albright & Wilson | DETERGENT COMPONENTS |
PH14451A (en) * | 1972-10-31 | 1981-07-23 | Procter & Gamble | Detergent compositions |
US4198308A (en) * | 1973-07-23 | 1980-04-15 | Colgate Palmolive Company | Manufacture of free-flowing fabric softening detergent |
US4000080A (en) * | 1974-10-11 | 1976-12-28 | The Procter & Gamble Company | Low phosphate content detergent composition |
JPS5159909A (en) * | 1974-11-20 | 1976-05-25 | Kao Corp | Ryujomataha funjosenjozaisoseibutsu |
JPS5335711A (en) * | 1976-09-14 | 1978-04-03 | Kao Corp | Neutral liquid detergent composition |
US4261941A (en) * | 1979-06-26 | 1981-04-14 | Union Carbide Corporation | Process for preparing zeolite-containing detergent agglomerates |
EP0024711B2 (en) * | 1979-09-01 | 1989-02-08 | Henkel Kommanditgesellschaft auf Aktien | Watery tenside concentrates and process for the improvement of the flowing property of difficultly movable watery tenside concentrates |
DE3002993A1 (en) * | 1980-01-29 | 1981-07-30 | Henkel KGaA, 4000 Düsseldorf | Aq. tenside salt concentrate - contg. added water-soluble lower poly:alkylene ether glycol mono:- and or di:sulphate salt as viscosity regulator |
JPS5665098A (en) * | 1979-10-31 | 1981-06-02 | Lion Corp | High concentration surfactant slurry |
EP0034039B1 (en) * | 1980-02-05 | 1984-09-26 | THE PROCTER & GAMBLE COMPANY | Liquid detergent composition |
US4316824A (en) * | 1980-06-26 | 1982-02-23 | The Procter & Gamble Company | Liquid detergent composition containing alkyl sulfate and alkyl ethoxylated sulfate |
JPS57187399A (en) * | 1981-05-12 | 1982-11-18 | Lion Corp | High concentration surfactant slurry |
-
1981
- 1981-12-28 DE DE19813151679 patent/DE3151679A1/en not_active Withdrawn
-
1982
- 1982-07-06 US US06/395,588 patent/US4482470A/en not_active Expired - Fee Related
- 1982-10-07 CA CA000413024A patent/CA1200733A/en not_active Expired
- 1982-12-16 MX MX8210418U patent/MX7401E/en unknown
- 1982-12-20 AT AT82111846T patent/ATE20357T1/en not_active IP Right Cessation
- 1982-12-20 DE DE8282111846T patent/DE3271700D1/en not_active Expired
- 1982-12-20 EP EP82111846A patent/EP0084154B2/en not_active Expired - Lifetime
- 1982-12-27 BR BR8207499A patent/BR8207499A/en not_active IP Right Cessation
- 1982-12-27 ZA ZA829512A patent/ZA829512B/en unknown
- 1982-12-28 JP JP57235094A patent/JPS58118899A/en active Pending
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DE3271700D1 (en) | 1986-07-17 |
JPS58118899A (en) | 1983-07-15 |
CA1200733A (en) | 1986-02-18 |
MX7401E (en) | 1988-09-23 |
ZA829512B (en) | 1983-09-28 |
DE3151679A1 (en) | 1983-07-07 |
EP0084154B2 (en) | 1990-02-21 |
EP0084154A1 (en) | 1983-07-27 |
US4482470A (en) | 1984-11-13 |
ATE20357T1 (en) | 1986-06-15 |
BR8207499A (en) | 1983-10-18 |
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