EP0763591B1 - Aqueous manual dishwashing composition - Google Patents

Description

Field of the Invention

The invention relates to aqueous hand dishwashing detergents with improved emulsifying power. containing defined amounts of low ethoxylated fatty alcohol ether sulfates in the form of their Magnesium salts.

State of the art

Hand dishwashing detergents (HGSM) are usually dilute aqueous detergent mixtures represents, in addition to anionic surfactants, especially non-ionic and amphoteric Contain surfactants. In addition to cleaning the dishes, these agents also have to meet the requirements a strong and stable foam, which does not even with considerable fat load collapses - even if this property does not directly affect the cleaning performance related. However, one particular problem is the detached one to emulsify lipophilic dirt, i.e. to prevent redeposition on the dishes. Products of the state of the art also show deficits here.

A number of hand dishwashing detergents are already known from the prior art, which are formulated with the use of magnesium salts. For example, European Patent Application EP-A 0 616 028 (Procter & Gamble) HGSM based on fatty alcohol ether sulfate sodium salts, enzymes and magnesium ions are proposed. HGSM are known from international patent applications WO 92/06156, WO 94/05769 and WO 94/24241 (Procter & Gamble), which contain combinations of anionic surfactants and glucamides, ether carboxylic acids or secondary alkyl sulfates with magnesium ions. The international patent application WO 94/04644 (Unilever) describes liquid cleaning agents containing fatty alcohol sulfates, nonionic surfactants and magnesium ions. US Pat. Nos. 5,269,974 and 5,338,491 (Procter & Gamble) relate to the use of betaines or glucamides together with magnesium salts in hand dishwashing detergents. Finally, the use of higher ethoxylated fatty alcohol ether sulfate magnesium salts in HGSM is known from British patent application GB-A 20 78 246 (Procter & Gamble). However, all of these publications do not provide a satisfactory solution for improving the emulsifying power of hand dishwashing detergents.

The complex object of the invention was therefore to provide aqueous hand dishwashing detergents to make available that at the same time have a good dishwashing capacity, a high base foam, good fat resistance and in particular an excellent emulsifying power feature.

Description of the invention

The invention relates to aqueous hand dishwashing detergents containing fatty alcohol ether sulfates of the formula ( I ), R ¹ O (CH ₂ CH ₂ O) _n SO ₃ Mg (I) in which R ^{1 is} an alkyl and / or alkenyl radical having 8 to 18 carbon atoms and n is a number from 0.5 to 1.5, in amounts of 40 to 90% by weight, based on the proportion of detergent substance and as further surfactants alkyl and alkenyl oligoglycosides of the formula (II) , R ² O- [G] _p (II) in which R ^{2 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. The fatty alcohol ether sulfates are present in amounts of preferably 45 to 90 and in particular 45 to 80% by weight, based on the proportion of detergent substance.

Surprisingly, it was found that the alkyl and / or Alkenyl oligoglycosides in combination with low ethoxylated fatty alcohol ether sulfates in Form their magnesium salts not only through an excellent dishwashing ability and also have a high base foam when exposed to fat, but also a special one have advantageous emulsifying power, which allows a redeposition of the To avoid plates detached lipophilic soiling on the washed goods safely. However, the condition is that the proportion of the above-mentioned magnesium salts - based on the Share of active detergent, i.e. surfactant - is above a critical limit. In In a preferred embodiment of the invention, the agents can be used as further surfactants Betaines and / or fatty alcohol sulfates contain.

Fatty alcohol ether sulfates

The fatty alcohol sulfates to be used for the purposes of the invention are substances known per se which, by the addition of very little, namely an average of 0.5 to 1.5, preferably about 1 mol, of ethylene oxide to a technical coconut fatty alcohol containing 8 to 18 and preferably 12 up to 14 carbon atoms, sulfation of the polyglycol ether and neutralization with a basic magnesium salt. A recent overview of magnesium salt surfactants is from H.Plate in Parf. Cosm. 76 , 28 (1995) .

Alkyl and / or alkenyl oligoglycosides

Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula (II) R ² O- [G] _p (II) in which R ^{2 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1-0 301 298 and WO 90/03977 . The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligo glucosides .

The index number p in the general formula (II) indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer and here can assume the values p = 1 to 6 in particular, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.

The alkyl or alkenyl radical R ² can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C ₁₂ - Alcohol can be contaminated and alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3).

The alkyl or alkenyl radical R ² can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.

Betaine

Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds. The starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine. The addition of unsaturated carboxylic acids such as acrylic acid is also possible. Regarding the nomenclature and in particular the distinction between betaines and "real" amphoteric surfactants, reference is made to the contribution by U.Ploog in Seifen-Öle-Fette-Wwachs, 198, 373 (1982) . Further overviews on this topic can be found for example by A. O'Lennick et al. in HAPPI, Nov. 70 (1986) , S. Holzman et al. in tens. Det. 23: 309 (1986) , R.Bibo et al. in Soap Cosm. Chem. Spec. Apr. 46 (1990) and P.Ellis et al. in Euro Cosm. 1 , 14 (1994). In addition, reference is made to the German patent application DE-A1 42 34 487 (Henkel), from which hand dishwashing detergents containing alkyl glucosides, betaines and fatty alcohol polyglycol ethers are known.

in der R³ für Alkyl- und/oder Alkenylreste mit 6 bis 22 Kohlenstoffatomen, R⁴ für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R⁵ für Alkylreste mit 1 bis 4 Kohlenstoffatomen, n für Zahlen von 1 bis 6 und X für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht.Examples of suitable betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (III)

in which R ³ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ⁴ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ⁵ for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and X for a Alkali and / or alkaline earth metal or ammonium.

Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C _12/14 -Kokosalkyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearyl, oleyl, C _16/18 tallow alkyl dimethyl amine and technical mixtures thereof.

in der R⁶CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 oder 1 bis 3 Doppelbindungen, m für Zahlen von 1 bis 3 steht und R⁴, R⁵, n und X die oben angegebenen Bedeutungen haben.Also suitable are carboxyalkylation products of amidoamines which follow the formula (IV)

in which R ⁶ CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m represents numbers from 1 to 3 and R ⁴ , R ⁵ , n and X have the meanings given above.

Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.

in der R⁷ für einen Alkylrest mit 5 bis 21 Kohlenstoffatomen, R⁸ für eine Hydroxylgruppe, einen OCOR⁷- oder NHCOR⁷-Rest und m für 2 oder 3 steht. Auch bei diesen Substanzen handelt es sich um bekannte Stoffe, die beispielsweise durch cyclisierende Kondensation von 1 oder 2 Mol Fettsäure mit mehrwertigen Aminen wie beispielsweise Aminoethylethanolamin (AEEA) oder Diethylentriamin erhalten werden können. Die entsprechenden Carboxyalkylierungsprodukte stellen Gemische unterschiedlicher offenkettiger Betaine dar.Furthermore, suitable starting materials for the betaines to be used in accordance with the invention are also imidazolines which follow the formula (V)

in which R ^{7 is} an alkyl radical having 5 to 21 carbon atoms, R ^{8 is} a hydroxyl group, an OCOR ⁷ or NHCOR ⁷ radical and m is 2 or 3. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as, for example, aminoethylethanolamine (AEEA) or diethylene triamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines.

Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C _12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

Alkyl and / or alkenyl sulfates

Alkyl and / or alkenyl sulfates, which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary alcohols which follow the formula ( VI ) R ⁹ O-SO ₃ Z (VI) in which R ^{9 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and Z is an alkali metal and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.

Typical examples of alkyl sulfates which can be used for the purposes of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arachelyl alcohol, aridyl alcohol, ela-elyl alcohol, ela-alcohol alcohol, and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali metal salts, and especially their sodium salts. Alkyl sulfates based on C _16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium, ammonium and / or magnesium salts are particularly preferred.

Hand dishwashing liquid

In a preferred embodiment of the invention, the aqueous hand dishwashing detergents contain the following ingredients: 40 to 100 (45 to 80)% by weight coconut fatty alcohol + 1EO sulfate magnesium salt, 0 to 35 (20 to 30)% by weight of alkyl sulfates (for example lauryl sulfate ammonium salt), 5 to 15 % By weight alkyl glucosides (eg coconut alkyl oligoglucoside) and 0 to 15 (5 to 15)% by weight betaines (e.g. coconut fatty acid amidobetaine).

The percentages relate to the proportion of detergent and complement each other 100% by weight. The preferred ranges are given in brackets. The means point a water content of preferably 75 to 85% by weight.

Industrial applicability

The agents according to the invention usually have a proportion of wash-active substance in the range of 5 to 40 and preferably 15 to 25% by weight. They are characterized by excellent dishwashing ability, high base foam, fat resistance and a particularly advantageous emulsifying power. Furthermore, they can be conventional components of dishwashing detergents such as builders (polycarboxylates, EDTA, NTA, Citric acid), alkalis, solubilizers (ethanol, propylene glycol, toluenesulfonate, cumene sulfonate), Dyes and fragrances included. In addition to the surfactants mentioned, still fatty alcohol ether sulfate sodium or ammonium salts, sulfosuccinates, monoglyceride sulfates, Fatty alcohol polyglycol ethers, fatty acid N-alkyl glucamides, protein hydrolyzates, protein fatty acid condensates and / or amine oxides may be included.

The following examples are intended to explain the subject matter of the invention without referring to it restrict.

Examples

• Die Ermittlung des Tellerspülvermögens wurde mit Hilfe des Tellertestes [Fette, Seifen, Anstrichmitt., 74, 163 (1972)] durchgeführt. Hierzu wurden Teller mit einem Durchmesser von 14 cm mit je 2 g Rindertalg ("RiTa", Säurezahl 9-10) bzw. einer Mischanschmutzung angeschmutzt und 24 h bei Raumtemperatur gelagert. Anschließend wurden die Teller bei 50°C bzw. 45°C mit 5 l Leitungswasser der Härte 16°d gespült. Die Prüfmischung wurde mit einer Dosierung von 0,5 g/l Aktivsubstanz/l eingesetzt. Der Spülversuch wurde abgebrochen, sobald der Schaum an der Oberfläche völlig verschwunden war.
• Die Ermittlung des Schaumvermögens erfolgte gemäß DIN 53 902, Teil 2 gemäß dem Ross-Miles Test. Die Testtemperatur betrug 20°C, die Wasserhärte 16°d und die Aktivsubstanzmenge 25 g/l. Bestimmt wurde der Basisschaum in ml mit und ohne Fettbelastung (Olivenöl).
• Das Emulgiervermögen wurde schließlich bei einer Temperatur von 25°C bei einer Wasserhärte von 16°d bestimmt. Hierzu wurden Emulsionen aus jeweils 10 g der Rezepturen R1 bis R10, 40 ml Wasser und 50 g Olivenöl hergestellt. Angegeben ist die Menge des aus der Emulsion abgeschiedenen Wassers nach 1 bzw. 4 h in %.

The test formulations R1 to R10 represent mixtures of various anionic surfactants (fatty alcohol ether sulfates or fatty alcohol sulfates), nonionic and amphoteric surfactants which contain polycarboxylic acid salts, sodium hydroxide and ethanol as further constituents. The content of detergent substance was 19% by weight in all cases. The formulas R1 to R3 are according to the invention, the formulas R4 to R10 are used for comparison. The composition of the recipes is summarized in Table 1; all data are understood as% by weight based on 100% by weight of active substance. The following application properties were tested as part of the investigations (for the results see also Table 1):

• The determination of the dishwashing power was determined using the plate test [Fette, Seifen, Anstrichmittel Mitt., 74, 163 (1972)] is performed. For this purpose, plates with a diameter of 14 cm were soiled with 2 g of beef tallow ("RiTa", acid number 9-10) or mixed soiling and stored for 24 hours at room temperature. The plates were then rinsed at 50 ° C or 45 ° C with 5 l tap water with a hardness of 16 ° d. The test mixture was used at a dosage of 0.5 g / l active substance / l. The rinsing attempt was stopped as soon as the foam on the surface had completely disappeared.
• The foaming power was determined in accordance with DIN 53 902, part 2 in accordance with the Ross-Miles test. The test temperature was 20 ° C, the water hardness 16 ° d and the amount of active substance 25 g / l. The base foam was determined in ml with and without fat (olive oil).
• The emulsifying power was finally determined at a temperature of 25 ° C and a water hardness of 16 ° d. For this purpose, emulsions were prepared from 10 g of the formulations R1 to R10, 40 ml of water and 50 g of olive oil. The amount of water separated from the emulsion is given in% after 1 or 4 hours.

Discussion of the results . The examples and comparative examples show that optimum emulsifying power with high dishwashing power and satisfactory base foam is only achieved if a coconut oil alcohol + 1EO-sulfate magnesium salt is used as the anionic surfactant in a concentration of 50% by weight and more, based on the content of detergent Substance is present on average. Above the critical limit, the recipe tolerates the use of other, otherwise not necessarily advantageous, anionic surfactants, but if the content falls below this level, the emulsifying capacity immediately deteriorates significantly.

Claims (5)

1. Water-based manual dishwashing detergents containing fatty alcohol ether sulfates corresponding to formula (I): R¹O(CH₂CH₂O)_nSO₃Mg in which R¹ is an alkyl and/or alkenyl group containing 8 to 18 carbon atoms and n is an integer of 0.5 to 1.5,
   in quantities of 40 to 90% by weight, based on the percentage content of detersive substance, and - as further surfactants - alkyl and alkenyl ollgoglycosides corresponding to formula (II): R²O-[G]_p in which R² is an alkyl and/or alkenyl group containing 4 to 22 carbon atoms, G is a sugar unit containing 5 or 6 carbon atoms and p is a number of 1 to 10.
2. Detergents as claimed in claim 1, characterized in that they contain betaines corresponding to formula (III):

   

   In which R³ represents alkyl and/or alkenyl groups containing 6 to 22 carbon atoms, R⁴ represents hydrogen or alkyl groups containing 1 to 4 carbon atoms, R⁵ represents alkyl groups containing 1 to 4 carbon atoms, n Is a number of 1 to 6 and X is an alkali metal and/or alkaline earth metal or ammonium,
   as further surfactants.
3. Detergents as claimed in claims 1 and 2, characterized in that they contain betalnes corresponding to formula (IV):

   

   in which R⁶CO is an aliphatic acyl group containing 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m is a number of 1 to 3 and R⁴, R⁵, n and X are as defined above,
   as further surfactants.
4. Detergents as claimed In claims 1 to 3, characterized in that they contain alkyl and/or alkenyl sulfates corresponding to formula (VI): R⁹O-SO₃Z in which R⁹ is an linear or branched aliphatic alkyl and/or alkenyl group containing 6 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and Z is an alkali metal and/or alkaline earth metal, ammonium, alkyl ammonium, alkanolammonium or glucammonium,
   as further surfactants.
5. Detergents as claimed in claims 1 to 4, characterized in that they contain 5 to 40% by weight of detersive substance.