NL8202294A - LIQUID PHOSPHATE-FREE DETERGENT. - Google Patents

Description

S 2158-28 • -, P & C "%

Liquid phosphate-free detergent.

The invention relates to a liquid phosphate-free detergent containing detergent compounds, enzymes, enzyme stabilizing agents. , water and, if desired, further customary additives.

Such a detergent is known from Dutch Patent Application 8103169 laid open to public inspection. Although the liquid detergent according to that patent application may contain phosphate, it is not necessary, as appears from Examples III and IV. However, the detergent of patent application 8103169 must contain a builder and, furthermore, as a stabilizing agent for the enzyme, a combination of polyol and boric acid 10 or an equivalent thereof in one. weight ratio of more than 1, in addition to a neutralized, cross-linked polyacrylate polymer.

The drawback of this is that the stabilizing system is relatively complicated and includes substances which do not normally contribute to the action of such a detergent, such as the borax used in all embodiments of patent application 810316.

As the detergent active component in such liquid detergents, combinations of anionic and nonionic materials are usually used. Obviously, it is a great advantage if a detergent can be used here, which itself has a stabilizing effect on the enzymes.

It has now been found that this may indeed exist and that the ether carboxylic acid class detergents exhibit such a stabilizing effect.

The invention therefore relates to a liquid phosphate-free wax-free agent of the type described in the preamble, characterized in that the enzyme stabilizing agent contains an ether carboxylic acid salt.

The ether carboxylic acid salts are a long-known class of surfactant compounds. They can generally be represented by the formula R- (OC_H.) OCH.COOM, wherein R is an aliphatic or aliphatic-2 4 n 2 aromatic, hydrophobic residue, n a number with an average value of about 0.5 -10 and m represents a suitable cation (usually alkali metal, ammonium or amine). Optionally, part of the oxyethylene groups can be replaced by oxypropylene groups. These compounds are generally prepared by reacting a compound ROH with epoxyethane (optionally also with epoxypropane) and reacting the resulting product in an alkaline medium with monochloroacetate. As is known, the first step results in a mixture of compounds with varying values for n and in general this whole mixture is further converted.

If alkaline catalysis is used in the first step, the value for n in the individual compounds varies over a relatively 8202 2 9 4 - 2 - wide range, while in catalysis with a Lewis acid a product with a narrow distribution of the values of n arises.

The ether carboxylic acids can be used in any amount that has a stabilizing effect on the enzymes. An exact limit for this cannot be indicated, because it depends on the chosen enzymes and on the other constituents of the liquid detergent, in particular the other detergent substances. For example, alkylarylsulfonic acid salts are sometimes found to have an unfavorable effect on the stability of the enzymes, while polyether alcohols, i.e. compounds of the formula RO (CIH.O) H

2 4: Xi 10 generally appear to have a beneficial effect. In general, it can be stated that the amount of ether carboxylic acid must in any case comprise at least 1% by weight of the total liquid detergent and preferably at least 3% by weight.

As already mentioned, the detergent composition of the invention may contain further conventional additives. For example, an alcohol or glycol is usually added as a solubilizing agent, and to improve overall performance, it may sometimes be preferable to add a non-sequestering agent that is not phosphate, for example, EDTA. A preservative is also often added.

Stability tests were performed with 2 NOVO "Esperase 8.0 Slurry" and "Savinase 8.0 Slurry" commercial products, see J. Am. Oil Chemists Soc., 55 (January 1978) pp. 109-113. According to the information on page 109, these commercial products have a standardized activity of 8.0 kg Novo proteinase units per gram (KNPU / g). The stability tests were performed in the manner described in the article, but at a temperature of 30 ° C. The residual activity was monitored for 8 weeks, from which a half-life was calculated.

A number of liquid detergents without an enzyme were prepared and the investigated enzyme preparation was added thereto. It should also be noted that generally an enzyme dose of 0.12 KNPU / l wash solution is considered sufficient. The table below summarizes the composition of the detergents and the half-lives obtained for the two enzyme preparations.

8202294 * - 3 -

A B C I D 'E

Alkylarysulfonic acid (1) 12.7-10.3

Caustic soda 50% 3.3 - 2.7 -

Palm kernel fatty acid - 5.8 18.0 1.15 1.15 5 Potassium hydroxide 50% - 2.3 7.0 0.45 0.45

Lauric acid diethanol amide 1.5

Lauryl ether sulfonate (28%} "18.6 16.2

Softened water 61.3 20.3 37.0 51.6 48.2 10 Preservative 0.1 0.1 0.1 E.D.T.A. 0.1 - 0.4 -

Hexylene glycol - - - 20.0 20.0

Ethanol 1.5 20.3 25.0

Lauryl myristyl 4.5 Ξ0 y. carboxylic acid, monoethanolamine salt (2) 2.6 - - -

Alkyl 3.8 EO carboxylic acid, sodium salt (3) - 12.7 - 4.8 15.0

Lauryl myristyl 7 EO

alcohol (4) - 22.3 - 21.6 15.0 20 ~ ”————————— pH 7.9 7.0 8.2 6.6 6.5

Half-life in days

Esperase 8.0 L 2 2 2 ca 26 ca 21

Savinase 8.0 SL 2 56, approx .: 25 56 ca 53 (1) Commercial product Marlon AS-3 Saure (Hüls) (2) 70% Lauryl, 30% Myristyl (3) Alkyl = C1 ~ C16 / close division of n 2Q Off the above table shows that better results are obtained with Savinase than with Esperase, but that Esperase also undergoes an important stability improvement in two of the three tests with ether carboxylic acid. It is not clear why test B with Esperase does not give a good result; this may be due to the use of lauryl ether sulfate.

In test A, a bad result is obtained with both enzymes despite the use of ether carboxylic acid. This is undoubtedly due to the simultaneous use of alkylarylsulfonic acid. Compared to this test, a considerably better result is obtained in test C with Savinase, possibly due to the use of fatty acid soap. (palm kernel fatty acid and caustic potash), although the result for Savinase lags far behind in tests B ~, D and E. In tests D and E it is furthermore worth noting that the results thereof are surprisingly good, 5 in particular because of the high water content.

It is known that anionic detergents exhibit various inhibitory effects on saccharase and that this inhibitory activity is associated with a physiological tolerability as determined in the skin tests, see American Perfumer and Cosmetics 78_ (September 1963), pp. 21-26. In this test the detergents of the ether carboxylic acid class appear to be very satisfactory and they are therefore physiologically well tolerated. This is further evidence of their general stabilizing effect on enzymes.

82 02 29 4

Claims (4)

1. Liquid phosphate-free detergent, containing detergent compounds, enzymes, enzyme stabilizing agent, water and, if desired, further customary additives, characterized in that the enzyme stabilizing agent contains an ether carboxylic acid salt. Liquid phosphate-free detergent according to claim 1, characterized in that it contains at least 1% by weight of ether carboxylic acid derivative. Liquid phosphate-free detergent according to claim 1 or 2, characterized in that the detergent active component contains a combination of anionic and non-ionic surfactants. Liquid phosphate-free detergent according to claim 3, characterized in that the non-ionic surfactant is at least partly formed by an oxyethylene alcohol of the formula RO- (C 1 H 3 O 1 H), wherein R is a hydrophobic alkyl or alkylaryl radical and n represents a number with an average value of 0.5-10