EP0383053A1 - Liquid detergents - Google Patents

Abstract

In detergents for manual dishwashing characterized by high detergency and improved protection of the skin, composed of dialkylsulphosuccinates, anionic and non-ionic tensides and hydroxysulphonates of unsaturated fatty alcohols, the hydroxysulphonates used correspond to unsaturated fatty alcohols of formulae (I) or (II) or their alkaline, alkaline earth and ammonium salts, where y and z = 0 to 18; p = 0, 1 or 2; (y + z + p) = 4 to 18; x = 1 to 20; n = 2 to 4. The dialkylsulphosuccinates (Na salts) contain identical branched or preferably straightchain C8 alkyl residues, such as di-n-octylsulphosuccinate. These compositions contain as additional anionic tenside C10 to C18 alkylethersulphates, preferably C12 to C16 alkylethersulphates with 1 to 5 mol of ethylene oxide.

Description

Liquid washing, rinsing and cleaning agents are usually aqueous solutions of anionic and / or nonionic surfactants and conventional additives. They are used for washing textiles, for cleaning hard surfaces, for example glasses or ceramic materials, plastics, lacquered and polished Surfaces, which can also be metallic in nature, are used. A preferred area of application for such agents is the manual washing of dining utensils and other related equipment. The respective cleaning processes are usually carried out at slightly elevated temperatures. There is always an increased impact on human skin.

The present invention therefore relates to cleaning agents with strong cleaning performance and improved skin protection.

The commercially available dishwashing agents which are to be used manually are aqueous solutions of alkyl ether sulfates, that is to say sulfated adducts of ethylene oxide with fatty alcohols, preferably n-alkylbenzenesulfonates and / or alkanesulfonates, optionally also olefin sulfonates or alkyl sulfates, and also nonionic surfactants, solubilizers, colorants and fragrances.

From DE 23 17 076, however, liquid dishwashing detergents are also known which, in addition to alkyl sulfates or alkyl ether sulfates, contain alkyl sulfosuccinates in the form of dialkyl (C₇-C₉) esters of sulfosuccinic acid. The agents can additionally contain other detergents, hydrotropes, solvents, opaque agents, phosphates, silicates, dyes, fragrances and skin-friendly additives.

EP 71 411 discloses a detergent composition comprising a mixture of di- (C₈-alkyl) - and di- (C₆-alkyl) sulfosuccinate in combination with other anionic and / or nonionic surfactants.

European patent specification 112 044 describes dishwashing detergents which contain water-soluble salts of a dialkyl ester of sulfosuccinic acid with identical or different, straight-chain or branched-chain C₃ to C₁₂ alkyl radicals and special alkyl ether sulfates. According to European patent 112 045, similar agents should also be added to electrolytes containing magnesium ions.

From European patent 112 046 it is known to add foaming liquid detergent compositions of C₃- to C₁₂-dialkyl esters of sulfosuccinic acid, alkyl ether sulfates and / or polyethoxylated nonionic detergents or carboxylic acid di- (C₂-C₃) alkanolamides.

The aqueous mixture of alkyl sulfosuccinates and alkyl ether sulfates is also known from European patent 124 367. It also describes aqueous solutions of alkyl sulfosuccinates alone and of alkyl sulfosuccinates in a mixture with alkyl benzene sulfonates.

Many of the commercially available dishwashing detergents contain, as an anionic surfactant component, salts of alkylbenzenesulfonic acid, which have excellent cleaning effects, but because of their petrochemical origin are to be gradually replaced by other, but at least equally effective, surfactants.

It has now been found that this goal could be achieved by using surface-active hydroxysulfonates from unsaturated fatty alcohols with 16 to 22 carbon atoms in the alkyl radical.

The present invention therefore relates to liquid detergents for the manual washing of dishes based on an aqueous solution of dialkyl sulfosuccinates, optionally together with other anionic and / or nonionic surfactants and other conventional constituents such as solvents, solubilizers, corrosion inhibitors, foam stabilizers, preservatives, electrolytes, thickeners , Dyes and fragrances, which is characterized in that they contain surface-active hydroxysulfonates from unsaturated fatty alcohols having 16 to 22 carbon atoms in the alkyl radical.

oder deren Alkali-, Erdalkali- und Ammoniumsalzen, wobei y und z = 0 oder Zahlen von 1 bis 18, p = 0,1 oder 2 und die Summe (y + z + p) eine Zahl von 4 bis 18, x = 1 oder eine Zahl bis 20, vorzugsweise 3 bis 15, und n eine ganze Zahl von 2 bis 4 sein kön­nen.The hydroxysulfonates used according to the invention correspond to formulas I or II

or their alkali, alkaline earth and ammonium salts, where y and z = 0 or numbers from 1 to 18, p = 0.1 or 2 and the sum (y + z + p) a number from 4 to 18, x = 1 or a number up to 20, preferably 3 to 15, and n can be an integer from 2 to 4.

-R²,      (III)
in welcher
R¹ eine lineare Alkenylgruppe mit 16 bis 22 C-Atomen oder eine überwiegend aus Oleyl-, Palmitoleyl-, Linoleyl-, Gadoleyl- und/oder Erucylgruppen bestehende Fettalkyl­gruppen,
n eine ganze Zahl von 2 bis 4,
x = 0 oder eine Zahl bis 30 und
R²CO eine Acylgruppe mit 1 bis 4 C-Atomen darstellt,
mit Schwefeltrioxid umsetzt, das Umsetzungsprodukt in eine wäßrige Lösung von 1 bis 2,5 Mol Alkali-, Erdalkali- oder Ammoniumhydroxid pro Mol angelagertes SO₃ einträgt und die Lösung bei 90 bis 100 °C 0,5 bis 240 Minuten lang hydrolyiert, wobei cyclische Sulfonie­rungsprodukte in offenkettige Verbindungen übergehen und gleich­zeitig die Esterschutzgruppe unter Rückgewinnung einer terminalen OH-Funktion quantitativ verseift wird. Je nach Aufarbeitungsart können die Endprodukte als Nebenprodukte noch Verbindungen enthal­ten, die sich aus den Formeln (I) und (II) formal jeweils durch den Verlust eines Moleküls Wasser ableiten. Das alkalische Hydro­lyseprodukt kann, falls dies gewünscht wird, in an sich bekannter Weise, z.B. mit Wasserstoffperoxid oder Natriumhypochlorit ge­bleicht werden und und wird in jedem Fall mit Hilfe wäßriger Mi­neralsäuren, z. B. Salzsäure, auf einen pH-Wert um 7 eingestellt.The hydroxysulfonates are described in detail in the older German patent application P 37 25 030.2. They are obtained, for example, by using an unsaturated fatty alkyl or fatty alkyl polyoxyalkyl ester of the general formula III

R¹-O- (C _n H _2n O) _x -

-R², (III)
in which
R¹ is a linear alkenyl group with 16 to 22 C atoms or a fatty alkyl group consisting predominantly of oleyl, palmitoleyl, linoleyl, gadoleyl and / or erucyl groups,
n is an integer from 2 to 4,
x = 0 or a number up to 30 and
R²CO represents an acyl group with 1 to 4 carbon atoms,
reacted with sulfur trioxide, the reaction product in an aqueous solution of 1 to 2.5 moles of alkali, alkaline earth or ammonium hydroxide per mole of SO₃ added and the solution is hydrolyzed at 90 to 100 ° C for 0.5 to 240 minutes, cyclic sulfonation products merge into open-chain compounds and at the same time the ester protecting group is saponified quantitatively to recover a terminal OH function. Depending on the type of workup, the end products may also contain compounds as by-products which are formally derived from formulas (I) and (II) in each case by the loss of a molecule of water. The alkaline hydrolysis product can, if desired, be bleached in a manner known per se, for example with hydrogen peroxide or sodium hypochlorite and is in any case with the aid of aqueous mineral acids, e.g. B. hydrochloric acid, adjusted to a pH around 7.

Preferred hydroxysulfonates as a component in the cleaning agents according to the invention are obtained when an unsaturated C₁₀ to C₂₂, preferably C₁₆ to C₁₈ fatty alcohol or fatty alkyl polyoxyalkyl ester of the formula III in which n = 2 and x = 0 or a number up to 20, is preferably 1 to 10, i. H. an ester of an unsaturated fatty alcohol and an adduct of up to 20 moles of ethylene oxide, preferably up to 10 moles of ethylene oxide, is used on an unsaturated fatty alcohol. The group R²-CO can be a formyl, acetyl, propionyl or butyryl group; the acetyl group is preferred. The group R 1 is preferably an oleyl group or a fatty alkyl radical consisting predominantly of oleyl groups.

Preferred values for the sum (y + z + p) in the compounds I and II are consequently 12 to 18, preferably 12 to 14.

The dialkyl sulfosuccinates used are preferably those with the same straight-chain or branched-chain C₈-alkyl radicals, that is to say di-n-octyl or di-iso-octylsulfosuccinates, in the form of their alkali metal salts, in particular their sodium salts. The di-n-octyl sulfosuccinates are particularly preferred.

The cleaning agents according to the invention show a significantly better skin tolerance in the epidermal swelling test compared to those which contain alkyl ether sulfates, as will be shown below.

Suitable other common constituents of such agents for the purposes of this invention are solvents, solubilizers, electrolytes, thickeners, corrosion inhibitors, preservatives, foam stabilizers, dyes, fragrances, complexing agents, etc.

Other anionic and / or nonionic and / or amphoteric surfactants can also be added to the mixture, provided that they do not interfere with the synergistic effect of the detergent mixture according to the invention.

The composition of the aqueous cleaning agent solution according to the invention is as follows:
10 to 40, preferably 10 to 35% by weight of a surfactant mixture consisting of 1 to 50, preferably 2 to 25 parts by weight of a hydroxysulfonate and 50 to 99, preferably 75 to 98 parts by weight of a dialkyl sulfosuccinate,
0 to 50, preferably 0 to 30% by weight of a further anionic surfactant,
0 to 10, preferably 0 to 5% by weight of a nonionic surfactant,
0 to 10, preferably 0 to 5% by weight of an amphoteric surfactant,
0 to 20, preferably 2 to 10% by weight of a solvent,
0 to 20, preferably 0.2 to 5% by weight of a solubilizer,
0 to 10, preferably 0.2 to 5% by weight of an electrolyte,
0 to 10, preferably 0.5 to 8% by weight of a thickener, 0 to 5, preferably 0.1 to 2% by weight of corrosion inhibitors and preservatives,
0 to 10, preferably 0 to 5 wt .-% foam stabilizers
0 to 0.1% by weight of dye,
0 to 0.5% by weight of fragrances and
Balance up to 100% by weight: complexing agents, enzymes, bactericides, fungicides, water.

Other anionic surfactants that can be used are especially C₁₀- to C₁₈-, especially C₁₂- to C₁₆-alkyl ether sulfates with 3 to 5, preferably 2 to 4 moles of ethylene oxide in the molecule, but also n-alkylbenzenesulfonates with 9 to 16, preferably 12 carbon atoms in the alkyl radical, alkanesulfonates with 10 to 20, preferably 12 to 18 carbon atoms in the alkyl radical, olefin sulfonates with 12 to 16, preferably 12 to 14 carbon atoms in the n-alkyl radical and alkyl sulfates with 8 to 18, preferably 8 to 14 carbon atoms in the alkyl radical, and other sulfates or sulfonates . However, formulations free of alkylbenzenesulfonate are of particular interest.

eingesetzt werden, in der R₁ einen gegebenenfalls durch Hetero­atome oder Heteroatomgruppen unterbrochenen Alkylrest mit 8 bis 20, vorzugsweise 10 bis 18 Kohlenstoffatomen und R₂ und R₃ gleich­artige oder verschiedene Alkylreste mit 1 bis 3 Kohlenstoffatomen bedeuten. Bevorzugt werden C₁₀-C₁₈-Alkyl-dimethylcarboxymethyl-­betain und C₁₁-C₁₇-Alkylamidopropyl-dimethylcarboxymethyl-betain.Surface-active betaines of the formula can be used as amphoteric surfactants

are used in which R₁ is an alkyl radical with 8 to 20, preferably 10 to 18 carbon atoms and R₂ and R₃ which may be interrupted by heteroatoms or heteroatom groups and mean identical or different alkyl radicals having 1 to 3 carbon atoms. C₁₀-C₁₈-alkyl-dimethylcarboxymethyl-betaine and C₁₁-C₁₇-alkylamidopropyl-dimethylcarboxymethyl-betaine are preferred.

If nonionic surfactants are used, inter alia, alkyl glycosides, preferably alkyl glucosides, having 8 to 18, preferably 12 to 16 carbon atoms in the alkyl radical and 1 to 10, preferably 1, 2 to 4, glycose units in the molecule are addition products of 4 to 20, preferably 6 to 15 Mol alkylene oxide, preferably ethylene oxide on C₈-C₁₂-alkylbenzenes, C₁₀-C₂₀-, preferably C₁₂-C₁₈-alkanols, C₁₀-C₁₈-, carboxylic acid alkanolamides, but also the addition products of ethylene oxide with polypropylene glycols, which have become known under the name Pluronics ^(R) are, as well as addition products of 1 to 7 moles of ethylene oxide with 1 to 5 moles of propylene oxide reacted with C₁₂-C₁₈ alkanols.

The solvents to be added if necessary are low molecular weight alkanols with 1 to 4 carbon atoms in the molecule, preferably ethanol and isopropanol.

Alkanolamines, polyols such as ethylene glycol, 1,2-propylene glycol, glycerol and alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical, for example, can serve as solubilizers, for example for small amounts of colorants and fragrances. Higher molecular weight ethylene glycols with MG 200 to 600 are also suitable as solubilizers. Also suitable are C₈-C₁₂-, preferably C₈-C₁₀-fatty alcohol sulfates as well as unsaturated C₁₆-C₂₂-, preferably C₁₆-C₁₈-fatty acid sulfonates.

The preferred thickeners include urea or electrolytes such as sodium chloride, ammonium chloride and magnesium chloride, which can also be used in combination.

The totality of solvents, solubilizers, thickeners and electrolytes, which can be used individually or in any mixtures with one another, is also referred to as a viscosity regulator.

Examples of corrosion inhibitors and preservatives are sodium benzoate and sodium sulfite.

Known fatty acid alkanolamides can be used as foam stabilizers.

The liquid cleaning agents according to the invention can also contain conventional disinfectants such as bactericides or fungicides, provided that they have no effect on the skin-protecting effect of the surfactant mixture according to the invention.

The liquid cleaning agents according to the invention of the following examples were obtained by stirring the individual components together in any order and let the mixture stand until there are no bubbles. Sodium salts were used as anionic surfactants.

The application concentration of liquid, manually usable dishwashing detergents is generally 0.1 to 0.5, preferably 0.15 to 0.45 g of active substance (AS) per liter of water.

Examples Substances used:

i-OAS = i-oleyl alcohol sulfonate Na salt based on Ocenol 90/95 (oleyl alcohol, technical)

i-OES3 = i-oleyl ether sulfonate Na salt based on Ocenol 90/95 with an average of 3 moles of EO

i-OES5 = i-oleyl ether sulfonate Na salt based on Ocenol 90/95 with an average of 5 moles of EO ethoxylated

i-OES10 = i-oleyl ether sulfonate Na salt based on Ocenol 90/95 with an average of 10 moles of EO ethoxylated

i-OES15 = i-oleyl ether sulfonate Na salt based on Ocenol 90/95 with an average of 15 moles of EO ethoxylated

EO = ethylene oxide

ABS = dodecylbenzenesulfonate Na salt

FAS = C₁₂-C₁₄ fatty alcohol sulfate Na salt

FAES = C₁₂-C₁₄ fatty alcohol ether sulfate Na salt with an average of 2 moles of EO ethoxylated

Di-n-O = di-n-octylsulfosuccinate Na salt

Di-iO = di-iso-octylsulfosuccinate Na salt

Comperlan KD = coconut diethanolamide

Texapon 842 = C₈ fatty alcohol sulfate Na salt

Texapon NSO = C _12/14 -2EO sulfate Na salt (FAES)

AS - active substance

Skin tolerance in the epidermal swelling test

To determine the skin tolerance of the surfactant mixtures, the in vitro method used by Zeidler and Reese was used, which is described in detail in the journal "Medical Cosmetology" 13 (1983) 39-45.

The swelling of the pig epidermis served as a measure of the skin tolerance of the surfactant mixtures. The required epidermis was obtained immediately after young pigs were slaughtered and stored frozen.

For the measurement, punched-out epidermis strips measuring 1 cm × 6 cm were immersed for 30 minutes in the surfactant solutions, each containing 2% by weight of active substance, heated to 39 ° C. and adjusted to pH 6.5. Then, after briefly rinsing and removing the adhering water, the weight of the swollen strips was determined by gentle pressing under defined conditions. The strips were then dewatered over CaCl₂ and dried again. A standard measurement was carried out in order to eliminate influences that can be traced back to specific properties of the respective animal or the place of removal (back, side). An immediately adjacent strip of epidermis is treated in the same way with water instead of with surfactant solution. The measurement number t for the surfactant treatment and w for the treatment with water result from the relationship:

The standardized, relative swelling change Q is finally defined as

The Q value of the water-treated skin is therefore by definition 0%, negative values indicate swelling-inhibiting properties. The fact that the less swelling of the epitermis is, the more skin-compatible the surfactant is. Experience has shown that the swelling factors for anionic surfactants and systems containing anionic surfactants found using this method correlate very well with measurements of skin tolerance in vivo (cf. J. Soc. Cosmet. Chem. Jap. 20 (1986) 17). Surfactant A Surfactant B A % B % Epidermal swelling % i-OES10 Di-nO 100 0 20 ± 5 80 20th -10 ± 8 60 40 24 ± 6 40 60 26 ± 7 20th 80 28 ± 5 0 100 32 ± 8 i-OES5 Di-nO 100 0 28 ± 6 80 20th 20 ± 5 60 40 17 ± 4 40 60 16 ± 3 20th 80 19 ± 4 0 100 32 ± 6 i-OES3 Di-nO 100 0 37 ± 6 80 20th 33 ± 5 60 40 12 ± 3 40 60 25 ± 6 20th 80 26 ± 6 0 100 32 ± 6 FAES Di-nO 100 0 36 ± 7 80 20th 34 ± 6 60 40 32 ± 4 (Comparison) 40 60 29 ± 3 20th 80 30 ± 6 0 100 32 ± 6

It can thus be seen that the skin compatibility with surfactant mixtures according to the prior art according to EP 124 367 is in some cases still significantly better.

Plate test

The so-called plate test was carried out to demonstrate the cleaning performance. The methodology is described in the journal "Fette, Seifen, Anstrichmittel", 74 (1972), pages 163 to 165. It was worked with water of 45 ° C at 3 ° d and 16 ° d and the use of 0.15 g of product per liter of water as well as beef tallow contamination. The talgan soiling was used with 2 g / plate (saucer 14 cm in diameter, distributed in the cup recess); the soiled plates were rinsed after storage for 24 hours at room temperature under the conditions specified above.

Cleaning performance of individual surfactants (0.15 g / l) by the number of plates rinsed at 45 ° C and 3 ° d or 16 ° d: i-OES5 EO (42% AS) iOES10 EO (47% AS) iOES15 EO (49.7 AS) Di-nO 3 ° d 1 0 1 25th 16 ° d 1 0 1 20th

Cleaning performance of surfactant mixtures according to the invention (0.15 g / l) in number of plates rinsed at 45 ° C. and 3 ° d or 16 ° d: i-OES3 EO: Di-nO 100: 0 75: 25 50: 50 25: 75 10:90 0: 100 3 ° d 0 1 7 15 26 25th 16 ° d 0 1 6 12 14 20th i-OES10 EO: Di-nO 100: 0 75: 25 50: 50 25: 75 10:90 0: 100 3 ° d 0 10th 24th 27-28 26 25th 16 ° d 0 12 22 24th 22-23 20th i-OES.5 EO: Di-nO 100: 0 75: 25 50: 50 25: 75 10:90 0: 100 3 ° d 1 2nd 8th 17th > 30 25th 16 ° d 1 2nd 7 14 17th 20th

It can clearly be seen that the surfactant combination according to the invention is superior to the prior art.

A number of ready-made dishwashing detergents according to the invention are shown in the table below. They are ideal for use in both hard and soft water. The ternary blends with FAES are particularly suitable for obtaining clear, cold-stable formulations.

Claims (4)

1. Liquid cleaning agents for the manual washing of dishes based on an aqueous solution of dialkyl sulfosuccinates, if appropriate together with other anionic and / or nonionic and / or amphoteric surfactants and other usual constituents such as solvents, solubilizers, corrosion inhibitors, preservatives, electrolytes, thickeners, paint - and fragrances, characterized in that they contain surface-active hydroxysulfonates from unsaturated fatty alcohols with 16 to 22 carbon atoms in the alkyl radical. 2. Liquid cleaning agent according to claim 1, characterized in that they are compounds of the formulas I or II as hydroxysulfonates

or their alkali, alkaline earth and ammonium salts, where y and z = 0 or numbers from 1 to 18, p = 0.1 or 2 and the sum (y + z + p) a number from 4 to 18, x = 1 or a number up to 20, preferably 3 to 15, and n can be an integer from 2 to 4. 3. Cleaning agent according to one of claims 1 and 2, characterized in that they contain as dialkyl sulfosuccinates those with the same branched and / or preferably straight-chain C₈-alkyl radicals in the form of their sodium salts. 4. Detergent according to one of claims 1 to 3, characterized in that they contain as a further anionic surfactant C₁₀- to C₁₈-, preferably C₁₂- C₁₆-alkyl ether sulfates with 1 to 5, preferably 2 to 4, moles of ethylene oxide in the molecule.