US 2898181 A
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FIP83 SR unuoo nttttttittit Stt'itf'fiit 09 xs 2,898,181 51 United States Patent PROCESS FOR WASHING AND BLEACHING COMPOSITIONS THEREFOR Karl Dithmar, Frankfurt am Main, and Ulrich Holfmann, Bad Homhurg (Taunus), Germany, assignors to Deutsche Goldund Silber-Scheideanstalt vormals Roessler, Frankfurt am Main, Germany No Drawing. Application October 23, 1957 Serial No. 691,802
Claims priority, application Germany May 20, 1953 4 Claims. (Cl. 8-137) The present invention relates to a novel washing process and compositions therefor, and more particularly to a washing process employing washing compositions containing perborate bleaching agents, preferably sodium perborate, and washing compositions particularly adapted therefor.
Textile fibers and textiles produced therefrom, especially when natural vegetable fibers such as cotton or linen are concerned, are often washed by a procedure in which the goods to be washed are introduced into a washing bath at room or slightly raised temperatures containing the normal surface active washing agents, such as soaps or synthetic detergents which also can contain inorganic builders and fillers, such as alkalies, water glass, phosphates, sulfates, peroxide compounds and the like, and slowly raising the temperature of the bath to about the boiling point and maintaining the bath at such temperature for some time. This customary boiling method is not only troublesome and expensive, but also, when goods are washed which are partly or completely produced from delicate fibers, such as artificial silk, regenerated cellulose staple fibers or fully synthetic fibers, there is a danger of fiber damage. Consequently, attempts have been made to provide washing procedures which could be carried out at lower temperatures than boiling temperatures, but they have not met with very satisfactory results. It was found that the optimum cleaning effect of the usual washing agents on cellulosic fibers is only attained at or near the boiling point of the washing fluid, so that when lower temperatures are employed insufficient cleaning efiects are obtained. When so-called self-actin or automatic washing compositions which normally contain perborates, such as sodium perborate, are employed at temperatures below those at or near the boiling point, for example, at 60-70 C., an insufficient bleaching effect is obtained, for the stability of commercial perborates is normally so adjusted that they only give oif their active oxygen to the fiber at high temperatures.
In accordance with the invention, it was unexpectedly discovered that the addition of certain carboxylic acid amides to washing compositions containing washing agents (organic surface active compounds which reduce the surface tension of water) and perborate bleaching agents improved such washing compositions so that they have a good cleaning action as well as a good bleaching action at temperatures lower than boiling temperatures, for example, at about 60-70 C. With such Washing compositions, the cleaning and bleaching effects obtained at temperatures of about 6070 C. were about the same as attainable with washing compositions not containing an amide activator at temperatures of about 95100 C. The amide activators employed according to the invention, it was found, have the property of increasing the oxygen liberated by the perborates. It was, for example, determined that a washing bath containing a perborate containing washing composition to which 0.5 g./l. of formamide had been added only contained 25% of its original 2,898,181 Patented Aug. 4, 1959 active oxygen content after two hours at 60 0., whereas in the absence of formamide such bath, otherwise under the same conditions, still contained of the original active oxygen content. Consequently, in the bath containing formarnide the quantity of oxygen given olf to the fibers is about three times that in a bath not containing the formamide.
The amides which have according to the invention been found particularly suitable as activators in peroxide containing washing agents are those of saturated or unsaturated carboxylic acids containing 1 to 4 carbon atoms, for example, amides of formic, acetic, proprionic, butyric, acrylic and methacrylic acids. Such amides can be produced in the usual way by reacting the fatty acids or functional derivatives thereof with ammonia or amines. The amides employed according to the invention must be soluble in water or washing solutions even if only to a slight extent. For this reason, it can be desirable to employ amides whose amido group carries solubilizing substitutents, for example, those derived from monoor diethanol amines.
The general formula of the amides suitable according to the invention is as follows:
in which R is selected from the group consisting of hydrogen and aliphatic hydro-carbon radicals containing 1 to 3 carbon atoms and R and R" are selected from the group consisting of hydrogen and C H OH.
The acrylamides and methacrylamides are especially suitable for the purposes of the invention as they are stable, non-hydroscopic products which render it possible to produce stable storable washing powders. The quantity of amide activator employed according to the invention can be between about 0.1 to 1.0 g. per liter of washing bath or in amounts of about 5 to 50%, preferably 10 to 25 of the organic surface active washing agents, that is, of the soaps or synthetic detergents in the washing bath or washing composition. 1
The organic surface active agents (washing agents), which form an essential part of the washing compositions and washing liquids according to the invention, as indicated can either be the commonly employed soaps, such as the alkali metal soaps of fatty acids, such as stearic and palmitic acids, or of rosin acids, such as abietic acid, or the so-called synthetic detergents which the art usually considers apart from the ordinary soaps. With regard to what the art considers as synthetic detergents, reference is made to the article concerning synthetic detergents by Donald Price, Chemical Week, October 22, 1955, pages 40-45, as well as the succeeding table of synthetic detergents available on the market (pages 46-82).
The organic surface active agents employed as washing agents contain a combination of a hydrophilic moiety and a hydrophobic moiety and are classified as being anionic, cationic or non-ionic. Both the anionic and cationic surface active agents are ionizable but differ in that in the anionic surface active agent the hydrophobic moiety is in the anion and that in the catonic surface active agent the hydrophobic moiety is in the cation. Ordinary soaps, such as sodium stearate and the like, as well as synthetic detergents of the sulfonated or sulfated types, are well known anionic surface active agents. Quaternary ammonium salts, such as cetyl pyridium chloride and the like, as well as salts of tertiary amines, such as, for example, compounds of the formula RCONHC HN C H .HC1
wherein RC0 is the acyl radical of a higher fatty acid, such as oleic acid, are typical cationic surface active agents. Polyoxyethylene esters of fatty acids, polyoxyethylene ethers of alkyl phenols, polyoxyethylene, fatty acid alkanol amine condensation products and the like are typical non-ionic surface active agents.
In general, the most important organic surface active agents belong to one of the following types of compounds:
Soaps Aminocarboxylic acids Acylation products of aminocarboxylic acids Salts of acid sulfuric acid esters Sulfated fatty acids and fatty acid derivatives Alkyl sulfates Salts of organic sulfonic acids Fatty acid sulfonates Alkyl sulfonic acids and their salts Alkyl aryl sulfonates Aliphatic-aromatic sulfonic acids Polyglycol ethers Polyglycol esters Polyalcohols Polyamines Alkylolamines The quantity of organic surface active agent (washing agent) contained in the perborate and carboxylic acid amide washing compositions and washing baths according to the invention can vary within wide limits. Experience has shown that only very small quantities of such organic surface active agents are required to effect the activation action of the carboxylic acid amides upon the perborate. Nevertheless, in general, the quantity of the organic surface active agent for practical purposes should be sufficient for efiicient soil removal when such washing compositions or washing baths are employed for washing. Consequently, the organic surface active agent content of the known generally employed perborate containing washing compositions more than suflices to provide the activation action on the carboxylic acid amides employed according to the invention. In the dry washing compositions, the organic surface active agent content can, for example, be between about and about 80% and in the washing baths it can, for example, be between about 0.1 and 1%.
The quantity of perborate in the compositions according to the invention preferably is such that 0.2 to 5 grams of active oxygen are provided per liter of washing bath.
The following examples will serve to illustrate several modifications of the process and products of the invention:
Example 1 A washing solution was prepared by dissolving grams per liter of a perborate containing washing powder of the following composition in water:
% sodium perborate 5% powder sodium water glass 40% soap 20% sodium sulfate 5% sodium carbonate 5% sodium pyrophosphate Three portions of this washing solution were taken, of which two contained no further addition, whereas 0.5 g./l. of formamide was added to the third. One of the first two solutions and the third solution were heated at 60 C. and the other of the first two solutions was heated at 95 C. for a number of hours. Samples were taken from time to time from each of the three solutions and titrated with a N/10 potassium permanganate solution to ascertain the decline in the peroxide content of such solutions.
The following table gives the results of such tests:
I II III no addition no addition 0.5 g./l. Time, Minutes at C. at 60 O. formamide g./l. act. 0 g./l. act. 0 addition 60 0.- g [1. act. 0
Example 2 Cotton goods which had been given a standard soiling with soot and oil were introduced into an aqueous washing liquid containing 15 g./l. of the washing powder disclosed in Example 1 and 0.5 g./l. of formamide at room temperature and the washing liquid heated in /z hour to 60 C. and heated at this temperature for /2 hour and then rinsed and dried. The ratio of cotton goods to bath was 1:30. A good washing and bleaching effect was achieved by such treatment. On the other hand, in a control test carried out under the same conditions, but with the omission of the formamide, it was found that a very noticably poorer washing and bleaching effect was obtained.
In a further comparative test, in which the soiled cotton goods were introduced into a washing liquid containing no formamide at room temperature and the temperature of the washing liquid raised to 95 C. in /2 hour and maintained at this temperature for /2 hour, it was found that the same washing and bleaching effects were obtained as were obtained with the 60 C. treatment with the formamide containing bath according to the invention.
Example 3 2.5% of acrylic acid amide was incorporated in a washing powder of the composition given in Example 1, and a washing bath was prepared containing 10 g./l. of such composition so that the bath contained 0.25 g./l. of acrylic acid amide.
When such a washing bath was used to wash soiled cottion goods at a temperature of 60 C., the same washing and bleaching effect was obtained as only could be in the absence of the acrylic acid amide addition at 9() C. The oxygen liberated in the acrylic acid amide containing washing liquid at 60 C. also corresponded to that which was attainable in the absence of the acrylic acid amide at 90100 C.
Similar results were obtained with washing baths in which the acrylic acid amide had been replaced by methacrylic acid amide. Perborate washing compositions containing about 2.5 to 5% of acrylic acid or methacrylic acid amide have been found admirably suited for washing purposes. Good results were also obtained when 2.5 to 5% of acrylic acid amido ethanol or methacrylic acid amido ethanol were employed in place of the acrylic or methacrylic acid amide. In each instance the incorpora tion of the amido compound rendered it possible to obtain good cleaning and bleaching effects at lower temperatures than were possible in the absence of such amido compounds.
Example 4 A washing powder of the following composition was prepared:
of lauryl al- Example 5 Washing baths were prepared by dissolving the following compositions in water at 60 C. The quantities of the components are given in grams per liter of finished washing bath.
7.5 grams Marseilles soap 1.5 grams formamide 2.0 grams sodium perborate Composition lb:
7.5 grams Marseilles soap 2.0 grams sodium perborate Composition 2a:
4.0 grams sodium lauryl sulfate 2.0 grams formamide 3.0 grams sodium perborate Composition 2b:
4.0 grams sodium lauryl sulfate 3.0 grams sodium perborate The active oxygen content was measured right after the washing baths were prepared and the percentage of active oxygen retained in such baths after varying periods of time was measured, giving the following result:
Time, Minutes Oompo- Oompo- Compo- Composition 1a sition 1b sitlon 2a sition 2b This is a continuation-impart of application Serial No. 429,969, filed May 14, 1954, and now abandoned.
1. In a process of washing textile materials with aqueous washing liquids containing an organic surface active washing agent and a perborate bleaching agent, the step which comprises incorporating an aliphatic carboxylic acid amide of the formula R.CO.NR'R" in which R is selected from the group consisting of hydrogen and aliphatic hydrocarbon radicals containing 1 to 3 carbon atoms and R and R" are selected from the group consisting of hydrogen and C H OH in the washing liquid employed to wash the textile, the quantity of such amide incorporated being between 0.1 and 1 gram per liter of washing liquid, the quantity of perborate in said washing liquid providing 0.2 to 5 grams of active oxygen per liter of washing liquid and the quantity of the organic surface active agent in said washing liquid being between about 1 and 10 grams per liter.
2. The process of washing textile materials according to claim 1 in which said washing liquid is maintained at a temperature between about and C.
3. In combination with an organic surface active agent and perborate bleaching agent containing washing composition for textiles, an aliphatic carboxylic acid amide of the formula R.CO.NR'R in which R is selected from the group consisting of hydrogen and aliphatic hydrocarbon radicals containing 1 to 3 carbon atoms and R and R" are selected from the group consisting of hydrogen and -C H OH, the quantity of said amide being 0.1 to 1 part by weight per 1 to 10 parts by Weight of organic surface active agent and the quantity of perborate providing 0.2 to 5 parts by weight of active oxygen per 0.1 to 1 part by weight of the amide.
4. In combination with an organic surface active washing agent and perborate containing aqueous bath, an aliphatic carboxylic acid amide of the formula in which R is selected from the group consisting of hydrogen and aliphatic hydro-carbon radicals containing 1 to 3 carbon atoms and R and R" are selected from the group consisting of hydrogen and -C H OH in a quantity of 0.1 to 1 g. per liter of such bath, the quantity of organic surface active agent in said bath being 1 to 10 grams per liter and the quantity of perborate providing 0.2 to 5 grams of active oxygen per liter of said bath.
References Cited in the file of this patent UNITED STATES PATENTS 1,006,798 Schmidt Oct. 24, 1911 1,101,449 Kemmerich June 23, 1914 2,120,430 Reiche June 14, 1938 2,254,434 Lind et al. Sept. 2, 1941 2,730,428 Lindner Jan. 10, 1956 OTHER REFERENCES Folgner: Monatsehrift fiir Textile Industrie, October 1937, p. 257.