EP0079105B1 - Foam-controlled washing agents - Google Patents

Abstract

1. Controlled-foaming detergent composition, based on an anionic detergent or a combination of an anionic detergent and a nonionic detergent, having a mono- and/or dialkyl orthophosphate content, of which the alkyl group has 12-22 carbon atoms or of which the alkyl group is separated from the P-atom by up to 6 alkylene oxide groups, characterized in that it further has a metal soap content originating from di- or trivalent metal cations.

Description

The present application relates to foam-controlled detergents.

Detergents that are to be suitable for use in (household) washing machines, in particular in drum machines, must not develop so much foam under all conditions that occur in practice that overexposure from the washing machine could occur.

In the prior art, numerous proposals have already been made for the production of such foam-controlled detergents, which are satisfactory in terms of their effect, but which are based on other parameters, such as, for. B. Solubility and foaming behavior in hand washing, washing-in behavior in the washing machine, consumer acceptance etc. may not have fully satisfactory effects or may lose their effectiveness during storage. As a result, the choice of the optimal detergent active substance (WAS) or of WAS combinations is restricted.

The present invention now allows the use of WAS substances or their combinations which are optimal in terms of their technical behavior and their cost, without being severely restricted in their choice by their foaming behavior. In the case of heavy-duty detergents that should be able to be used at all temperatures, different foaming behavior is also desirable at different temperatures. It has now been found that the intended purpose can be achieved by adding a mixture of metal soaps and alkyl phosphates to a detergent. The desired foam profile can be set by a suitable selection of the components, which have different individual characteristics over the entire temperature range of approx. 20-100 ° C., by the interaction of their mutually influencing properties.

It is already known from DE-B-1 089 905 to use a mixture of metal soaps and nonionic surfactants as a non-foaming detergent.

Alkyl phosphates have also already been proposed in low-foaming detergents, mostly together with nonionic surfactants (DE-A-2701 663; DE-A-2 532 804; DE-A-2 537 570). The use of mixtures of metal soaps and alkyl phosphates cannot be deduced from this prior art. Metal soaps are to be understood as meaning soaps with divalent or trivalent metal cations.

The metal soaps which can be used according to the invention are those metal soaps which, up to the maximum temperature at which they are said to be effective, are not in solution in the washing process by sufficiently long C chains and avoidance of reversion into their Na salt can go. Examples of suitable metal cations include Ca, Mg, Al, Zn; Examples of suitable fatty acids from which the metal soaps are produced are the higher molecular weight (C ₁₂ -C ₂₂ or higher) fatty acids or mixtures thereof, such as stearic acid, palmitic acid and higher fatty acids. A preferred metal soap is calcium stearate. The alkyl phosphates that can be used according to the invention. are mono- and / or dialkyl orthophosphates whose alkyl group contains 12-22 carbon atoms or whose alkyl group is separated from the P atom by a number of alkylene oxide groups (up to 6). The alkyl phosphates are present as alkali metal salts. Suitable examples are C ₁₆ -C ₁₈ monoalkyl phosphate (sodium salt), such as stearyl monophosphate, mixtures of mono- and distearyl phosphate, mono- and dilauryl ether phosphate etc. In general, the metal soaps are used in an amount of 0.1 to 3, preferably 0.1 5 to 1.5 wt .-% of the detergent, and the alkyl phosphates in an amount of 0.05 to 2, preferably 0.2 to 1 wt .-%.

The mixture of metal soaps and alkyl phosphates is preferably added to the detergent secondary. Examples of suitable processes are secondary spraying of metal soaps and alkyl phosphates dispersed in nonionic surfactant onto the detergent powder, homogeneous mixing being attempted by various measures (such as, for example, ultrasound); Granulation of metal soaps and alkyl phosphates and secondary addition of this granulated mixture to the detergent powder; Encapsulation of dispersions of metal soaps and alkyl phosphates and secondary addition of this encapsulated mixture to the detergent powder; Dusting the metal soaps and alkyl phosphates on the still sticky detergent powder etc.

Preferably, the metal soap and the alkyl phosphate are dispersed in a nonionic surfactant, and this dispersion is sprayed onto the detergent secondary.

As mentioned before, the invention allows the use of an optimal WAS in the detergent. Above all, these are purely anionogenic substances. Examples of such anionogenic substances are usually water-soluble alkali metal salts of organic sulfonates or sulfuric acid esters, which have alkyl radicals with about 8 to 22 carbon atoms. Examples of such synthetic anionic detergent compounds are sodium or potassium alkyl sulfuric acid esters, in particular those which can be prepared by sulfating Ca to C ₁₈ fatty alcohols, which are obtained by reducing fatty acids derived from tallow or coconut oil, or synthetic alcohols, e.g. . B. can be obtained by oxo synthesis or Ziegler syn thesis; Sodium or potassium alkyl (C _s -C ₂₀ ) benzene sulfonates; in particular sodium umlin.-sec.-alkyl (C ₁₀ ―C ₁₅ ) -benzenesulfonates; Sodium or potassium alkyl polyglycol ether sulfuric acid esters, in particular from ethers of higher alcohols which are obtained from tallow or coconut oil, or from synthetic higher alcohols; Sodium or potassium salts of fatty acid mono glyceride sulfates or sulfonates; Reaction products of fatty acids, e.g. B. tallow or coconut fatty acid, neutralized with isethionic acid and with sodium or potassium hydroxide; Sodium and potassium salts of fatty acid methyl taurides; Alkane monosulfonates, such as those obtained by reacting C _a - to C ₂₀ -alpha-olefins with sodium bisulfite or by reacting paraffin with S0 ₂ and C1 ₂ or 0 ₂ and subsequent hydrolysis with sodium or potassium hydroxide, and also olefin sulfonates, with this expression the material is to be referred to, which is obtained by reacting olefins, in particular alpha-olefins, with SO ₃ and subsequent hydrolysis and neutralization.

However, it has been shown that the invention is particularly suitable for binary WAS combinations, ie for combinations of an anionogenic and a nonionic surfactant. Such WAS combinations are well known per se and contain the usual anionogenic and nonionic surfactants in all possible mixing ratios and in a total amount of up to over 30% by weight. Examples of such nonionic surfactants are the reaction products of alkylene oxide, in particular ethylene oxide and / or propylene oxide, with alkyl (C ₆ -C ₁₂ ) phenols, C ₈ -C ₂₀ alkanols, fatty acid amides, with generally 5 to 30 ethylene oxide units per molecule are present, block polymers of propylene oxide and ethylene oxide, condensation products of ethylene oxide with reaction products of propylene oxide with ethylene diamine, etc. Other nonionic detergent compounds include long-chain tertiary amine or phosphine oxides and dialkyl sulfoxides. Examples of such combinations of anionogenic and nonionic surfactants are mixtures of sodium dodecylbenzenesulfonate and tallow fatty alcohol condensed with 5 mol EO, or sodium dodecylbenzenesulfonate and C ₁₂ ―C ₁₅ oxo alcohol condensed with 12-18 mol EO. The detergents can moreover contain the usual, further detergent constituents, such as organic and / or inorganic build-up salts, in the usual amounts. Examples of build-up salts are phosphates, citrates, oxidized starch and cellulose derivatives, in particular those with dicarboxyl radicals, sodium alkenyl- (C ₁₀ ―C ₂₀ ) -succinates, sodium sulfofatty acids, alkali metal carbonates, sodium aluminum silicates, carboxymethyloxysuccinates, nitrilotriacetates, etc., other conventional materials Detergent compositions according to the invention are present in the usual amounts, e.g. B. dirt suspending agents, hydrotropes, corrosion inhibitors, dyes, fragrances, fillers, optical brighteners, enzymes, foam boosters, foam suppressants, germicides, anti-tarnishing agents, fabric softeners, chlorine-releasing agents, oxygen-releasing bleaching agents such as sodium perborate or percarbonate with or without peracid precursor compounds, buffers and the like . The rest of the detergent compositions consist of water, e.g. B. in the range of about 5 to 15% in the powder detergent compositions.

The invention is further discussed using the following examples.

In the examples, the percentages relate to% by weight, based on the weight of the basic batch.

example 1

The following approach was produced by weighing single items:

0.6% stearyl monophosphate, 0.5% or 1.0% calcium stearate and 1.6% C ₁₂ -C ₁₅ oxo alcohol, condensed with 12 mol EO, were added to this mixture as a secondary mixture.

This mixture was made by dispersing the soap in the molten mixture of stearyl phosphate and nonionic surfactant. These batches A and B (with 0.5 and 1.0% calcium stearate) were tested for their foaming behavior in the dynamic foam. 6 g / l of the batch were used and the water hardness was 0.23 kg / m ³ , calculated as CaC (= 23 ° DH).

Figure 1 shows the foam behavior of these approaches; as can be seen, no foaming occurred over the entire temperature range.

Example 2

Diesem Grundsatz wurde 1% Na-Stearat zugesetzt, das in 0,25% C₁₂-C₁₅-Oxo-Alkohol, kondensiert mit 8 Mol E0, dispergiert war (Vergleichsansatz C). In Ansatz D wurde statt Na-Stearat 1% Ca-Stearat, ebenfalls in 0,25% des gleichen nichtionogenen Tensids dispergiert, zugesetzt. In Ansatz E wurde 1% AI-Stearat zugesetzt. Auch mit diesen Ansätzen wurden wie in Beispiel 1 Schaumversuche durchgeführt, wobei die Waschpulverdosierung 8 g/I betrug. Figur 2 zeigt wieder die Schaumverhalten der Ansätze C―E.The following batch was prepared as a finished powder:

1% Na stearate was added to this principle, which was dispersed in 0.25% C ₁₂ -C ₁₅ oxo alcohol, condensed with 8 mol E0 (comparative approach C). In batch D, 1% Ca stearate, likewise dispersed in 0.25% of the same nonionic surfactant, was added instead of Na stearate. In approach E 1% Al stearate was added. Foam tests were also carried out with these batches as in Example 1, the washing powder dosage being 8 g / l. Figure 2 again shows the foaming behavior of the approaches C ― E.

Example 3

The same additives were used as in Example 2, but with a different principle. This was of the following composition:

FIG. 3 shows the foaming behavior of these batches F (= comparative batch) (with Na stearate), G (with Ca stearate) and H (with Al stearate).

Claims (4)

1. Controlled-foaming detergent composition, based on an anionic detergent or a combination of an anionic detergent and a nonionic detergent, having a mono- and/or dialkyl orthophosphate content, of which the alkyl group has 12-22 carbon atoms or of which the alkyl group is separated from the P-atom by up to 6 alkylene oxide groups, characterized in that it further has a metal soap content originating from di- or trivalent metal cations.

2. Composition according to Claim 1, characterized in that it has a calcium stearate content.

3. Process for the preparation of a composition according to Claim 1 or 2, characterized in that the mono- and/or dialkyl orthophosphates and the metal soaps are added secondarily to the detergent composition.

4. Process for the preparation of a composition containing a combination of an anionic detergent and a nonionic detergent according to Claim 3, characterized in that the mono- and/or dialkyl orthos- phosphates and the metal soaps are dispersed in a nonionic detergent and the dispersion is sprayed on to the washing powder.

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