NO123580B - - Google Patents

Description

Liquid, synthetic detergent mixture.

The invention relates to a liquid, synthetic detergent mixture.

It has been discovered that a liquid synthetic detergent containing at least 4% of a nonionic detergent and at least 8% of a phosphate builder salt can be obtained with excellent bactericidal properties and in which phase separation is reduced to a minimum if a quaternary ammonium-containing bactericidal agent is included in the product and if the phosphate building salt is sodium tripolyphos fat.

Phase separation is usually a serious problem with liquid products containing at least 4% of a nonionic detergent and at least 8% of a phosphate building salt. It has surprisingly been found that a quaternary ammonium-containing bactericide acts as a hydrotrope. Surprisingly enough, it has also been found that the bactericidal properties of such a mixture are

IN

marked"

The invention therefore provides a liquid, synthetic detergent containing by weight at least 4% of a non-ionic detergent, at least 8% sodium tripolyphosphate and a quaternary ammonium-containing bactericide.

Suitable non-ionic detergents for use in liquid products are well known" Usually they are condensates of ethylene oxide with lipophilic residues, e.g. fatty acids» fatty acid amides, fatty alcohols, alkylphenols, but there are also many other types.

Schwarz, Perry and Berch, Volume II, Chapter 4, Interscience Publishers, 1958, gives numerous examples" and more

is published later. As indicated, one feature they have in common is "a balance between hydrophilic and lipophilic properties" This is usually expressed quantitatively as the HLB value for a particular non-ionic detergent. For non-ionic detergents which are simple condensates of ethylene oxide with a lipophilic residue, the HL3° value is usually given as E/5", where E is the percentage by weight of the ethylene oxide part of the molecule. For non-ionic detergents which are not simple condensates of ethylene oxide with a lipophilic residue', such a simple formula as E/5 will give a result which is a source of misunderstanding. In order to determine the HLB value, a more basic approach is needed in such cases by means of experimentation. Polypropylene oxide/ethylene oxide condensates are examples of compounds where this is necessary. Here, the polypropylene oxide cannot be considered completely lipophilic.

It has been found that a non-ionic detergent for use

in a product according to the invention preferably has an HLB value of from 12 to 17. The lipophilic residue preferably contains from 12 to 18 carbon atoms. Particularly preferred are alkylphenol/ethylene oxide condensates.

The various classes of quaternary ammonium compounds useful as water-soluble bactericidal agents are well known. For example, Schwarz, Perry and Berch, Volume II, Chapter 7, Interscience Publishers, 1958, give numerous examples, and others have been subsequently published" In general, suitable quaternary ammonium compounds usually comprise at least one long-chain ^<C>8-22^ alkyl or substituted alkyl group. The other substitutes may vary, e.g. hydrogen, lower alkyl benzyl, phenyl.

The weight ratio of non-ionic detergent to quaternary aramonium-containing bactericide is preferably not less than 3ti, but not more than 20:1, particularly preferably not more than 10:1, although larger amounts of the quaternary aramonium-containing bactericide may be used. Typical

amounts of quaternary ammonium-containing bactericides in products according to the invention are 0.25 to 3 percent by weight, although larger amounts may be used. The total amount of non-ionic detergent and sodium tripolyphosphate is preferably not more than 25%, particularly preferably 20%, by weight of the product. The total amount of non-ionic detergent is not more than 10% by weight of the product, although if the HLB value is above 15, approx. 15 7. of the non-ionic detergent can be incorporated. The total amount of sodium tripolyphosphate is preferably not more than 15 7. particularly preferably no more than 12 7." in weight of the product.

The liquid products according to the invention can be used as detergents for sanitary purposes. For example, they can be used in the food industry and in hospitals. They are particularly useful as cleaning agents for hard surfaces in the household. The products may contain other compatible components, e.g. opacifying agents.

In all the examples, the percentages indicate weight.

EXAMPLE 1

The following standard recipe was used:

A solution of the non-ionic was added to the phosphate dish, which had previously been dissolved in water. The mixture was then adjusted to the final, predetermined volume.

An oily layer separated on top of the liquid which, on agitation, assumed a hazy, semi-opaque appearance. The temperature of the mixture was then changed to between 35 and 37°C and, with stirring, small amounts of quaternary ammonium compounds were added until the liquid became clear. The temperature was then raised and kept at 40°C. The product then became cloudy again due to the excretion of small amounts of the non-ionic agent. More of the quaternary ammonium compound was added until the mixture became clear. The total amount of quaternary ammonium compound used to solidify the system at 40°C was equivalent to the amount needed to obtain a homogeneous product

during storage at 37°C.

The following results were obtained for a range of non-ionic detergents. The non-ionic agents had the general formula:

where R is an alkyl group and n is an integer. In practice, n indicates an average, i.e. the average number of ethylene oxide units per alkylbenzene that is present.

The quaternary ammonium compound used was technical grade cetyltrimethylammonium chloride (CTAC) and is expressed as 100% active. Results are reproduced in table I.

EXAMPLE 2

3 mixtures were made, A, B and C, and the amounts of CTAC necessary to obtain a homogeneous, clear product were found as in Example 1. The results obtained are reproduced together with the compositions in Table II»

The viscosity numbers indicate a direct relationship between the viscosity and the amount of CTAC used» The viscosity increases with the amount of CTAC. This is the reverse of what happens when using conventional hydrotropes, e.g. sodium xylene sulfonates (SXS).

EXAMPLE 3

The loosening ability of CTAC was compared with sodium xylene sulphonate. A mixture of 10% STPP, 5% octylphenol-8~-E0 and 85 7. water required 2»82 7. sodium xylene sulfonate but only 0.84 7. CTAC to become clear.

EXAMPLE 4

Clear solutions were made as in Example 1, but with different quaternary ammonium compounds

EXAMPLE 5

Rideal-Walker coefficients were determined by standard methods Table IV shows the results. Non-ionic detergents normally have a predominantly reducing effect on the anti-bacterial properties of quaternary ammonium compounds. The results presented in this example show a surprising activity with respect to a quaternary ammonium bactericide in a liquid product containing a nonionic detergent and sodium tripolyphosphate.

Similar high Rideal-Walker coefficients were obtained using octylphenol condensates with less than 8 ethoxyl groups. Increasing the ethoxyl groups above this number caused a rapid drop in the Rideal-Walker values which leveled off at 13 ethoxyl groups. The values obtained from the nonyl derivatives were lower, but also dropped off sharply after 8 ethoxy groups.

It was found that increasing octyl enol-8~-EO from 5 to 10%, in the presence of 10 7 " sodium tripolyphosphate, produced a surprisingly smaller decrease in the Rideal-Walker coefficient than expected.

As Rideal-Walker coefficients or possibly another test showing total killing ability, relative to a control release of phenol, are not always reliable with respect to quaternary ammonium compounds, the remarkably high values were determined twice, but this did not change the up* running results.

EXAMPLE 6

The following recipe, see table V, was tested against several organisms.

The method used was that laid down by

British Standards Institute, BS.3286: 1960, The following conditions were used;

The tested sample concentrations were 0.25, 0.5" 1

and 2 7a" This was the final concentration in the contact bottles after the addition of organisms and dirt"

The test organisms were 18-hour-old cultures of Staphylococcus aureus, Escherichia coli, Salmonella cholera suis, Proteus vulgaris and Pseudomonas" The viable numbers of these cultures were approximately 5 x 10 g. These organisms were chosen, as they represent both food poisoning and spoilage organisms.

Temperature

Test solutions of the liquid detergent, organisms and dirt were brought into equilibrium by staying for 30 minutes in a water bath at the two test temperatures, 20°C and 40°G, before the test was continued.

Organic dirt

Whole milk lfission prepared from skimmed dry milk was used. It was added with the organisms to the liquid detergent, so that there was a final concentration of 1% milk in the contact bottle.

Suppressant

The suppressant used, see Table VI, was tested in a standard manner against both products to verify that it both neutralized the bactericide and that it did not stop the growth of the test organisms.

Diluting agent

10.1% peptone-water solution was used to prepare solutions of the suppressant. Deionized water was used for the preparation of solutions according to the prescriptions.

The culture substrate used was "Yeastrel" glucose agar + 10% horse serum to complete the suppression.

Incubation

Plates were incubated at the organisms' optimal growth temperature, either 30 or 37°C, for 43 hours.

The results are reproduced in tables VII and VIII.

Used in a concentration of 1 7." gave the product a reduction of between 99.9 and 99.99 7..

Used in a concentration of 2 7." gave the product a reduction of 99.99 7. without dirt, and of at least 99.9 7. in the presence of 1% milk against all the test organisms, including Proteus vulgaris which is normally resistant to most bactericides.

EXAMPLE 7

Two types of good, conventional products (A and B) were compared with a liquid product according to the invention

(C) with regard to ability to clean a linoleum surface. The recipes for the products are listed in Table IX.

To avoid accidental masking of differences,

the highly effective rengjorlhgad mechanical way reduced. The products were evaluated in a flow machine, where mechanical impact is minimal, since it is only due to the solution flowing over the objects to be examined. An artificial dirt was created to represent natural dirt from the kitchen miljci. The dirt contained 45 7" clay, 45% carbon, 9.5% triglycerides and 0.5% free fatty acids. The dirt was applied to an uncoated, uniform linoleum substrate of uniform color to an extent that resulted in a 40% reduction in reflection. The linoleum substrate was in the form of test pieces, 7 cm square. Washing was carried out by flowing the solution at 45°C over objects to be examined for 1 minute, the flow rate being 15 liters per minute. minute. The results obtained are reproduced in table X.

C, the liquid according to the invention, is an excellent cleaning liquid and is at least as good as A, although not as good as B.

EXAMPLE 8

Recipes according to the invention were compared with recipes where sodium tripolyphosphate was replaced with tetrapotassium pyrophosphate. The Rideal-Walker values obtained, as well as the compositions, are given in Table XI.

The Rtdeal-Walker values were averaged for 3 individual samples of A and B and for 2 individual samples of C and D„

EXAMPLE 9

Clear mixtures were made according to the invention, which contained 10 7. sodium tripolyphosphate, 1 70 cetyl-trimethylammonium chloride and 5% of respectively C-^ - straight chain alcohol-5-E0, coconut-ethanolamide-2T-H0 and polypropylene oxide (molecular weight I700)-Io"-E0.

Claims (2)

1. Liquid detergent mixture containing a non-ionic detergent, a phosphate building salt and a quaternary ammonium-containing bactericide, characterized in that it contains by weight at least 4 7. of the non-ionic detergent and at least 8 70 of the phosphate building salt , further that the non-ionic detergent has an HLB value of from 12 to 17, that the phosphate building salt is sodium tripolyphosphate, that the total amount of the non-ionic detergent and the sodium tripolyphosphate is not more than 25 percent by weight of the product, and that the weight ratio between the non-ionic detergent and the quaternary ammonium compound is greater than 3 Sl and not more than 20:1. 2. Liquid detergent mixture as stated in claim 1, characterized in that the non-ionic detergent contains a lipophilic residue with from 12 to 18 carbon atoms.