US 2560839 A
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Patented July 17, 1951 DETERGENT COMPOSITION Jackson J. Ayo, Elizabeth, and Ferdinand J. Gajewski, Linden, N. J and Herbert L. Sanders, Easton, Pa., assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application July 24, 1947, Serial No. 763,442
This invention relates to detergents, and more particularly to detergent compositions for use in mechanical washing operations and the like.
Recent developments have resulted in improved synthetic detergents for use in novel types of washing machines, for dishwashing or laundering purposes, for example. While advances in both fields have been marked, chemical investigations and mechanical design have frequently progressed along separate lines so that the ultimate results failed to combine the best features of the chemical and mechanical developments. Thus detergents were developed which were superior to others in manual operation yet could not be used in washing machines because of mechanical problems. Conversely, improved machines had to be operated with detergents which, though low in detergent properties, were satisfactory from a mechanical standpoint.
It is an object of the present invention to eliminate this drawback and to provide detergent compositions combining latest chemical advances with performance characteristics which render them available for use in the most modern types of washing machines.
Research involving a large number of the new synthetic detergents, and a great variety of dishwashing and laundering machines, show that the property of the detergents mainly responsible for impeding the performance of the machines, frequently to the point of complete mechanical breakdown, is the excessive foaming of the synthetic detergents.
Accordingly, a specific objective of the present invention is to provide detergent compositions which have a materially reduced foaming capacity without any sacrifice of their overall detergent characteristics.
A large number of agents which we tried for the purpose of eliminating excessive foaming of the detergents were incompatible with the detergents employed. Some agents proved effective in cutting down the foaming but affected other properties of the detergents, for example, their solubllity,,so that the ultimate utility of the compositions was nil. Still other agents showed promise because of their compatibility with the detergents, yet failed to reduce the foaming sufflciently.
Another object of this invention, therefore, is to provide detergent compositions wherein detergents are combined with foam reducing agents compatible with the detergent components.
Detergent compositions for use in mechanical washing operations usually have been marketed come into contact.
in non-liquid and generally in powder form. However, there is a widespread demand for detergent compositions for use in washing machines which can be marketed in liquid form. One of the principal reasons for this demand is that a washing machine handles a liquid composition with much greater ease than a dry material where the necessary dissolving action creates problems of time loss and non-uniformity of dissolution. Liquid compositions involve further advantages of manufacture, storage, transportation, and sales appeal, provided the liquid compositions are stable, homogenous and present an unclouded appearance.
Accordingly, a primary objective of this invention is to provide detergent compositions for use in washing machines which can be marketed in liquid form.
Detergent compositions intended for use in washing machines should contain corrosion inhibiting agents Which prevent the detergent ingredients of the compositions from attacking the metal parts of the machines with which they Specific ingredients call for different types of corrosion inhibiting agents. Diiierent metals also require different corrosion inhibitors.
A further object of the invention, therefore, is to provide suitable corrosion inhibiting agents for use in our detergent compositions and particularly an agent which prevents aluminum from being tarnished.
Detergent compositions, in order to be effective in removing different kinds of soils, must contain several detergent components, each designed for a specific purpose within the composition. Thus, detergent compositions for use in dishwashing machines, for example, should contain detergent components which act specifically on proteins, for example, or lipstick, to give another example. A further ingredient of a detergent composition designed for all-around .efiiciency is an ion sequestering agent which, by softening any hard water used in the washingoperation, prevents the precipitation of insoluble calcium salts which would interfere with the washing operation.
Consequently, still another object of the invention is to provide detergent compositions for use in mechanical washing operations which contain several detergent ingredients with different specific functions within the compositions, as well as sequestering agents, these ingredients and agents to be so selected as to be compatible with the primary detergent, foam reducing and corrosion inhibiting components of the compositions.
- fication proceeds.
One of the basic components of the detergent compositions according to the invention is a hydroxy polyalkyleneoxy ether, or a polyalkyleneoxy thio-ether, of an alcohol or a phenol, said alcohol or phenol having at least one hydrocarbon radical, the hydrocarbon chain of which contains at least 4 carbon atoms and the polyalkyleneoxy ether radical containing at least 6 alkyleneoxy groups. Compounds of this classilcation are depicted by the following formula:
R.Z (CH2.CH2.0) 1H wherein R means at least one aliphatic hydrocarbon radical with at least 4 carbon atoms, such as lauryl, myristyl. oleyl, stearyl or abietyl, etc., radicals, or an aromatic ring system which is substituted by at least one hydrocarbon radical with at least 4 carbon atoms, i. e., butyl, is-- butyl, amyl, hexyl, heptyl, octyl, isooctyl, decyl, dodecyl, benzyl or phenyl, etc., radicals, Z stands for O or S, :1: stands for a number varying from 6 to 100, the number 9: increasing with the number of carbon atoms in R, the number in any event being sufficiently great to render the products soluble in water.
Compounds of this type and suitable for our purpose are disclosed in U. S. Patents 1,970,578, 2,213,477 and 2,205,021. These compounds may be obtained by introducing alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc., into organic compounds containing at least one hydroxyl or SH group. Compounds corresponding to the above formula include, for example, lauryl alcohol polyglycol ether (containing 15 mols of ethylene oxide), myristyl alcohol polyglycol ether (containing 25 mols of propylene oxide), oleyl alcohol polyglycol ether (containing 40 mols of ethylene oxide), stearyl alcohol polyglycol ether. (containing 60 mols of propylene oxide), abietyl alcohol polyglycol ether (containing 80 mols of ethylene oxide), tri-isobutyl phenyl polyglycol ether (containing 6 mols of ethylene oxide), isooctyl phenyl polyglycol ether (containing 10 mols of propylene oxide), isooctyl orthocresyl polyglycol ether (containing 10 mols of of butylene oxide) isododecyl phenyl polyglycol ether (containing 14 mols of propylene oxide), isododecyl cyclohexyl polyglycol ether (containing 15 mols of ethylene oxide), decyl polyglycol thio-ether (prepared according to Example 4 of U. S. P. 2,205,021 and containing 6 mols of ethylene oxide), dodecyl polyglycol thio-ether (prepared according to Example 1 of U. S. P. 2,205,021 and containing about 6 mols of ethylene oxide). and the like.
The above mentioned ingredient has as its principal function the dispersion and emulsification of the soil, for example, the soil on dishes to be cleaned in a mechanical dish-washing operation. Apart from excellent emulsifying and dispersing characteristics, these compounds have surface active and wetting properties which enhance their utility in washing methods.
Said compounds. however, when used per se, have the one drawback that they foam far too ,much in mechanical washing operations. Their foaming capacity under mechanical agitation is such that the flow of water in the machines is impeded to the point of complete breakdown.
The foaming power of such compounds. however, is materially reduced by the addition of a small amount of a soap. Any soap is suitable for our purposes but best results ensue when employing water soluble metal soaps. and particularly water soluble soaps of the alkali metals.
Potassium cocate has been found particularlyeifective as the foam reducing agent of our compositions, but potassium, sodium and other water soluble soaps obtained from palm oil, cottonseed oil, etc., or organic base soaps such as ethanolamine oleate, are also highly emcient.
The amount of soap present in our compositions is far too small to add to the detergent properties thereof and is employed solely for the purpose of reducing the foaming of the above detergent component to the point where the flow of water is no longer impeded.
An important ingredient for employment with the above components of our detergent composition is an alkali pyrophosphate. This component has a number of functions within the composition. First, it has a specific detergent effect on proteins, an essential property, particularly when utilized in dishwashing operations. Second, it is a good sequestering agent and, therefore, supplies water softenin characteristics to our compositions. Third, we have found that compared with other alkaline ingredients of detergent compositions, alkali pyrophosphates assist more effectively in removing lipstick, which is an important propertly in dishwashing operations. for example.
Tetrapotassium pyrophosphate has been found particularly effective but other pyrophosphates such as tetrasodium pyrophosphate may also be employed. We have found that advantages of compatibility and homogenuity result if the alkali components of the soap and sequestering agent correspond. Accordingly, if a potassium soap is used, tetrapotasslum pyrophosphate is preferred for use as the sequesterin agent in the composition.
Another important component of our compositions, is a corrosion and stain inhibiting agent for preventing the compositions from attacking and tarnishing the metal parts of any washing machine in which they are employed. Silicates, and particularly metasilicates. have been found useful for this purpose. Alkali metasilicates such as the sodium and potassium compounds. and ammonium compounds display detergent properties in addition to their corrosion and stain inhibiting characteristics. Sodium metasilicate is a particularly effective agent.
Another outstanding stain andcorrosion inhibiting agent which, when incorporated into our detergent compositions, prevents the same from tarnishing aluminum even to the slightest extent, is N,N'-tetracarboxymethyl-ethylene diamine, described in U. S. P. 2,130,505.
In addition to the important ingredients described above, the compositions of the invention may contain very small additions of alkali metal hydroxides and/or carbonates, which serve the purpose of clarifying the solutions. In the paste or cream-like compositions, a small amount of carboxy methyl cellulose may be added, if desired, as a stabilizer. The balance of the compositions is water.
As previously stated, the present compositions are preferably compounded and sold in the form of liquids, but they may also'be marketed in the form of pastes or creams.-
The relative proportions in which the several ingredients may be present in our compositions,
vary within fairly wide limits, depending upon the form in which the products are to be sold.
In the preferred case of the liqug compositions, the main detergent ingredient, i. e., the hydroxy polyalkyleneoxy ether, or polyalkyleneoxy thioether, may be present in amounts varying from about 3 to about 12% by weight of the composition; the soap or foam reducing component may be used in amounts from about 2 to about 5% by weight of the composition; the amount of the pyrophosphate or sequestering agent varies between about 3 and 8% by weight of the composition, and the corrosion or stain inhibiting agent is present in amounts varying from about 1 to about 5% by weight of the composition. Alkali metal hydroxides and/or carbonates, if added at all, total at most about .4%. This leaves a balance of water from about 69.6 to about 91% by weight for the liquid compositions.
When the compositions are prepared in paste or cream-like form, the amount of the main detergent ingredient may vary from about 10 to about 30% by weight of the paste or cream; the soap or foam reducing component may be used in amounts from about 3.3 to about 10% by weight of the product; the amount of pyrophosphate or sequestering agent varies between about 10 and about 30% by weight of the cream, and the corrosion or stain inhibiting agent is present in amounts varying from about 3.3 to about 10% by weight of the composition. Carboxy methyl cellulose, if added at all, does not exceed about 1 by weight, and alkali metal hydroxides and/or carbonates, if added at all, total at most about .4% by weight, leaving a balance of water from about 18.6 to about 73.4% of the paste or creamlike products.
The compositions according to the prersent invention areprepared by mixing the ingredients in the desired proportions. While it is preferred to start with the bulk of the water to be incorporated into the composition, and while stirring to add thereto the other ingredients, the sequence of mixing operations is not a material factor in the manufacture of these compositions. The entire mixing operation takes place at normal temperature and is continued until a uniform. homogenous product, either liquid or creamy, is obtained. Mechanical agitation for homogenizing purposes is particularly important for the paste or cream-like product.
The following examples illustrate a number of detergent compositions according to the invention, all parts being by weight of the composition, and the highly foaming hydroxy polyalkyleneoxy ether, or polyalkyleneoxy thio-ether, of the de-' finition and formula stated above being referred to in the examples for the sake of convenience, as the "Primary detergent component.
Example 1 Percent Primary detergent component 10.0 Potassium Cocate" (coconut oil fatty acid soap) 3.3 Tetrapotassium pyrophosphate 5.5 Sodium metasilicate 2.0 Water 79.2
Example 2 Per cent Primary detergent component 4.5 Potassium soap from palm kernel oil 2.0 Tetrapotassium pyrophosphate 3.0
N, N-tetracarboxymethyl-ethylene diamine 1.2
Potassium hydroxide .1 Water 89.2
Example 3 Per cent Primary detergent component 11.5 Sodium soap from castor oil 4.0 Tetrapotassium pyrophosphate 6.0 Sodium metasilicate 2.5 Potassium hydroxide .1 Potassium carbonate .1 Water 75.8
Example 4 Per cent Primary detergent component 17.8
Potassium Cocate" (coconut oil fatty acid soap) 6.3 Tetrapotassium pyrophosphate 17.8 Sodium metasilicate 4.3 Water 53.8
Example 5 Per cent Primary detergent component 16.1 Potassium soap from olive oil 5.6 Tetrapotassium pyrophosphate 16.1 Sodium metasilicate 4.0 Carboxy methyl cellulose .5 Water 57.7
Example 6 Per cent Primary detergent component 27.5 Sodium soap from olive oil -1 8.5 Tetrasodium pyrophosphate 25.0 N,N-tetracarboxymethyl-ethylene diamine 6.5 Sodium hydroxide .1 Sodium carbonate .1 later 32.3
We wish it to be understood that we do not desire to be limited to the exact details of the invention as described for purposes of illustration as various modifications within the scope of the claims may be made without departure from the invention or sacrifice of any of the advantages thereof.
1. A detergent composition particularly adapted for use in mechanical washing operations. comprising from about 3 to about 30% by weight of a highly foaming compound selected from the class consisting of hydroxy polyaklyleneoxy ethers and polyalkyleneoxy thio-ethers of a compound selected from the class consisting of allphatic alcohols and phenols, said alcohols and phenols having at least one hydrocarbon radical containing at least 4 carbon atoms, and the alkyleneoxy groups in said hydroxy polyalkyleneoxy ether and polyalkyleneoxy thio-ether radical numbering at least 6, from about 2 to about 10% by weight of a water-soluble alkali metal soap, from about 3 to about 30% by weight of an alkali metal pyrophosphate, with water being substantially the balance.
2. A detergent composition according to claim 1, in liquid form, which comprises from about 3 to about 12% by weight of the said highly foaming compound, from about 2 to about 5% by weight of the water-soluble alkali metal soap, from about 3 to about 8% by weight of the alkali metal pyrophosphate, from about 1 to about 5% by weight of a suitable corrosion inhibiting agent,
and from 0 to .4% by weight of an alkali metal hydroxide and alkali metal carbonate, the balance being water.
3. A detergent composition according to claim 1 in paste-like form, which comprises from about 10 to about 30% by weight of the said hi hly foaming compound, from about 3.3 to about 10% by weight of the water-soluble alkali metal soul). from about 10 to about 30% by weight o! the alkali metal pyrophosphate, from about 3.8 to about 10% by weight of a suitable corrosion inhibiting agent, and from 0 to 1% by weight ,0! carboxy methyl cellulose, with water being substantially the balance.
4. A detergent composition according to, claim 1, wherein the soap is a potassium soap.
5. A detergent composition according to claim 1, wherein the pyrophosphate is tetrapotassium pyrophosphate.
6. A detergent composition according to claim 2, wherein the corrosion inhibiting agent is N,N'-tetracarboxymethyl-ethylene diamine.
7. A detergent composition according to claim 1, containing not more than .4% by weight of an alkali metal hydroxide and alkali metal carbonate.
8. A detergent composition according to claim 1, containing an amount not exceeding 1% by weight of the composition, of carboxy methyl cellulose, as a stabilizer.
8 9. A detergent composition according to claim 1, in liquid soap, about 5.5% of tetrapotassium pyrophosphate, and about 2% of a suitable corrosion inhibiting agent, with water being substantially the balance.
JACKSON J. AYO. FERDINAND J. GAJEWSKI. HERBERT L. SANDERS.
REFERENCES CITED The following references are of record in th form, which comprises by weight" about 10% 01 the said highly foaming compound. about 3.3% of potassium coconut oil fatty acid