US3131991A - Washing and bleaching - Google Patents

Description

United States Patent Oficc 3,131,991 Patented May 5, 1964 3,131,991 WASHING AND BLEACHING Knrt miner and Elfriede Eiclrler, Berlin-Lichterfelde,

Germany, assignors to Henkel & Cie. G.|n.b.H., Duseldorf-Holtlrauaen, Germany, a German corporation No Drawing. Filed June 30, 1961, Ser. No. 120,913 Claims priority, application Germany July 7, 1960 19 Claims. (Cl. 8-137) I The present invention relates to improvements in washing and bleaching, and more particularly to a process and detergent preparation including liquid water-containing concentrates of washing active and active oxygencontaining components for washing and bleaching articles in a washing medium.

Recently many attempts have been made in the washing and cleaning industry to provide liquid water-containing washing and cleaning agent concentrates on account of the more versatile and convenient dosage form and the easier and more attractive packaging possibilities, as well as the rapid dissolution of such concentrates in use. Such attempts have been made in increasing measure, especially with respect to application in dish washing, household cleaning, car washing, hair care, general and specific disinfecting purposes, and the like. More and more, the formerly popular powder detergent and washing agent products are being replaced by liquid concentrates.

Nevertheless, heretofore it has not been possible to adapt the so-called self-acting washing and bleaching agents, in particular where used in household laundry application and commercial self-service laund-ries, to the liquid concentrate form. The reason for this is the instability of such compounds, which contain active oxygen and which are customarily employed for washing and bleaching processes, where these compounds are in the form of liquid water-containing washing and bleaching agents. The shelf-life or aorage of .these compounds is undesirably short. Moreover, since these active oxygencontaining compounds are often employed in combination with other necessary washing agents of a neutral or alkaline nature, the active oxygen-containing compounds are rapidly decomposed in the resulting alkaline environment. Therefore, a storage of these preparations in liquid concentrate form has not been possible up to the present.

It is known that hydrogen peroxide may be prepared in concentrated aqueous solutions such that the same are stable in storage by adding to these solutions acids or acid-acting materials, such as, for example, phosphoric acid, pyrophosphoric acid, sulfuric acid, acid alkali pyrophosphates, alkali hisulfa-tes, and similar compounds. However, these preparations are neither washing active nor bleaching active and, therefore, are not particularly suitable for household laundry purposes, especially since they are not provided in dosage forms for use by the housewife.

It is an object of the present invention to overcome the foregoing drawbacks and to provide improvements in the washing and bleaching of articles, such as laundry, by employing liquid water-containing concentrates of washing active and active oxygen-containing components.

Other and further objects of the invention will become apparent from a study of the within specification and accompanying examples.

it has been found, in accordance with thepresent invention, that a detergent preparation and process for washing and bleaching articles in a washing medium may be effectively provided. The preparation comprises liquid water-containing concentrates of washing active and active oxygen-containing components, including an acid component concentrate having an active oxygen-contain- 0 mm g ageni I ing compound and an acid-stable organic in an aqueous washing mediumfant; an alkaline compo- 5 containing the articles to be washed of suflicient pH for effecting the washing and bleaching treatment.

The acid-stable organic washing agent and the alkaline-stable organic washing agent may be either non-ionic or anionic in nature.

The acid component concentrate may be an acid-stabilized aqueous peroxide solution containing an alkylene oxide adduct of an organic compound having a saturated alkyl group containing an active hydrogen atom. The adducts may be alkylene oxide adducts of fatty alcohols, fatty acids, fiatty amines, fatty acid amides, fatty acid alkylol-amides, mercaptans, alkyl phenols and alkyl naphthols. Specifically, the adduct may be an ethylene oxide adduct, for example, of a higher molecular weight saturated fatty alcohol having from 5 to 16 ethoxyl groups in the molecule or of a higher molecular weight saturated alkyl-phenol having from S to 16 ethoxy groups in the alkyl moiety.

,The acid component concentrate may also be an acidstabikzed aqueous peroxide'solution which may contain, for example, condemation products of high molecular alkyl sulfonic acids with albumin hydrolysates, condensation products of high molecular alkaryl sulfonic acids with albumin hydrolysates, or acid-stable high molecular aliphatic sulfonic acids or acid-stable high molecular mixed aliphatic-aromatic sulfonic acids. The acid component concentrate may additionally contain a solution promotor, such as a low molecular alkyl-aromatic sulfonic acid or the alkali salt thereof.

On the other hand, the alkaline component concentrate alkaline-stable organic washing agent may be an alkylene oxide adduct of an organic compound having an active hydrogen atom. The adduct preferably may be an ethylene oxide adduct of a fatty alcohol or an alkyl phenol. The alkaline compound concentrate alkaline-stable organic washing agents in accordance with the invention may be fatty acids, acylated-hydroxy alkane sulfonates, acylated amino-alkane-sulfonates, soluble alkyl sulfates, alkyl ether sulfates, fatty acid-alkylol-amide-sulfates, alkyl benzene sulfonates, soaps, salts of nitrogen bases and mixtures thereof. Similarly, the alkaline component concentrate may additionally contain a solution promotor such as a low molecular alkyl-aromatic sulfonic acid or an alkali salt thereof.

The alkaline reacting compound of the alkaline component concentrate is suitably an alkali, such as caustic alkali, alkali carbonate, alkali orthophosphates, alkali meta-silicates, alkaline reacting organic nitrogen bases and alkali salts of weak organic acids.

The pH of the acid medium of the acid component concentrate is preferably between 3 and 5, while the pH of the over-all washing medium formed may be neutral to weakly alkaline, or moderately alkaline, i.e., contemplating pH values between 7.5 and ll.

The over-all washing medium formed may additionally contain inorganic washing agents, sequestration agents, solvents, thickening agents, disinfecting agents, dirt-carrying-eflect-compounds, fiber-protecting agents, skin-protecting agents, oxygen stabilizers, foam-stabilizers, foambreaking agents, corrosion protection agents, dye stuff- 5 optical brighteners, perfumes, and the like.

Preferably, the alkaline component liquid water-containing concentrate is added to the washing medium for the article to be treated prior to the adding of the acid component liquid water-containing concentrate. Moreover, the alkaline component liquid water-containing concentrate may be applied to the article to be treated in the washing medium, and after a suitable prewashing treatmerit, the acid component liquid water-containing concentrate may be added and the washing treatment comleted.

P The product of the invention represents a detergent preparation for applying to an article to be washed and bleached in a washing medium which comprises measured quantities of two separately maintained discrete liquid water-containing concentrates of washing-active and active oxygen-containing components, including an acid component concentrate having an active oxygeneontaining compound as well as an acid-stable organic washing agent in aqueous acid medium, and an alkaline component concentrate having an alkaline-stable organic washing agent and an alkaline reacting compound in aqueous alkaline medium, the amount of alkaline reacting compound being adjusted to render the combined concentrates of sufiicient pH for effecting overall the washing and bleaching treatment. The pH, in this regard, may suitably range between 7.5 and 11.

Specifically, it is possible to carry out washing and bleaching processes, with regard to household laundry and commercial self service laundry applications, in accordance with the invention, whereby two liquid watercontaining concentrates are separately employed. One of these concentrates is adjusted to within the acid range and contains the necessary compounds having active oxygen therein as well as non-oxidizable, acid-stable organic wash active agents of non-ionic and/or anionic nature. The other concentrate may also contain organic non-ionic and/or anionic wash active agents, and additionally alkaline reacting compounds in such amounts that the washing liquid formed after adding the two concentrates will possess the necessary pH value for carrying out the washing and bleaching procedure.

In this respect, the acid concentrate will preferably possess pH values between 2.5 and 5 whereas the alkaline concentrate will be maintained such that the acid constituent or constituents of the acid concentrate will be effectively neutralized. Furthermore, at least a neutral to weakly alkaline reaction of the washing and bleaching material will be attained, although it is often preferred to have a moderately alkaline reaction condition for washing purposes, i.e. wherein the pH ranges between 8 and 11, and preferably between 9 and 10.

The acid component concentrate which contains the active oxygen ingredient is made up of per-compounds, such as for example concentrated aqueous hydrogen peroxide solutions or adducts of hydrogen peroxide with alkali borates, alkali carbonates, alkali pyrophosphates, alkali polyphosphates, urea, and the like. These concentrates further contain non-oxidizable, saturated hydrocarbon acid-stable organic wash active agents of the nonionic and/or anionic type, such as ethylene oxide ad ducts to fatty compounds, such as fatty alcohols, fatty amines, fatty acids, fatty acid amides, fatty acid alkylolamides, alkylphenols, and the like, as well as condensation products of high molecular alkyl-sulfonic acids or alkyl-aryl-sulfonic acids with albumin hydrolysates. Furthermore, in the same connection, acid-stable high molecular sulfonic acids of the aliphatic or mixed aliphatic aromatic type may be used together with the per compounds.

Optionally, solution promoting low molecular aromatic sulfonic acids or their alkali salts may be employed in small quanities in the acid component concentrate. Among these are, for example, toluene sulfonic acid, xylene sulfonic acid, or their alkali salts, such as their potassium salts.

Suitable adjustments to the required acidity may be carried out with the use of acid acting materials, such as phosphoric acid, pyrophosphoric acid, sulfuric acid, alkali-acid pyrophosphates, alkali bisulfates, alkali-acidorthophosphates and the like, as well as other acids, such as hydrochloric acid, oxalic acid, benzoic acid, lactie acid, and the like. Nevertheless, such acids are employed in the form of the free acids or in the form of the acid salts, in such amounts that in the course of the washing and bleaching action, the same will be neutralized and converted into wash effective compounds. This is particularly true with respect to the phosphoric acid, pyrophosphoric acid, polyphosphoric acids, and the acid salts and acidified neutral salts of these acids. Significantly, the phosphoric acids and their salts may be used in the form of their hydrogen peroxide adducts, as well, whereby the presence of the active oxygen constituent and the acid constituent is satisfied in the same compound.

The above-mentioned non-oxidizable ethylene oxide adducts of fatty alcohols, alkyl phenols and the like increase and intensify the stabilizing effect of the acids or acid salts employed for stabilizing the active oxygen per compounds. Accordingly, the storability of the particular concentrates is intensely improved. While the anion active acid stable wash active materials also exert a stabilizing effect, such effect is less than that of the non-ionic type compounds.

Specifically, concerning the alkaline component concentrate, the same also contains an organic non-ionic and/or anionic wash active agent which, however, may be wholly or partly unsaturated in nature. This is true since a preferred oxidation of such wash active materials by the active oxygen constituent of the acid component concentrate, during the washing and bleaching action, is not detrimental nor to be avoided. Suitable wash active agents of the non ionic type, in this connection, include the already mentioned ethylene oxide adducts to fatty alcohols, alkyl phenols and the like. As anion active materials, in this regard, fatty acids, acylated hydroxyor amino-alkane sulfonates, easily soluble alkyl sulfates, alkyl ether sulfates, fatty acid alkylol-amide sulfates, alkyl benzene sulfonates, and the like, may be used. Moreover, soaps or soap-containing mixtures may also be used. In place of the alkali salts, i.e. preferably the potassium salts, the salts of nitrogen bases which are more easily convertible into liquid concentrate form may also be used. Among such salts are ethanol amines, morpholine, and the like. Mixtures of anionic and nonionic compounds and/or various anionic agents in admixture, and various non-ionic agents in admixture are frequently employed.

In order to improve the solubility properties of the concentrate, hydrotropic substances may be used, such as for example potassium, toluene sulfonate or potassium xylene sulfonate. These substances are suitably used in small quantities.

The necessary alkalinity of the alkaline component concentrate may be readily effected by adding caustic alkalis, alkali carbonates, alkali ortho-phosphates, alkali metasilicates, or other more strongly alkaline active inorganic and organic bases, as well as alkaline reacting salts. Thus, for example, amines or alkylolamines and even alkali salts of weak organic acids, such as for example alkali acetates may be used for this purpose.

Besides the components already mentioned, the acid and/or alkaline concentrates may be separately charged with various other conventional ingredients useful in washing procedures. Among these are the inorganic wash active agents, sequestration agents, solvents, thickening agents, disinfecting agents, compounds having dirtcarrying effect, fiber and/ or skin protecting agents, oxygen stabilizers, foam-stabilizers, foam-breaking agents, corrosion protection agents, dye stuffs, optical brighteners, perfumes, etc. These materials may be used individually or in admixture with one another in the particular concentrate for convenient addition, together therewith, to the wash water for the clothing to be treated.

As to the additives to the acid component concentrate, only those additives are used together, of course, which do not impair the stability of the compounds containing the active oxygen, and which, in addition, possess the necessary stability to acid. This is true with respect to some sequestration agents, disinfecting agents, oxygen stabilizers, corrosion protecting agents, dye stuffs and optical brighteners. In this connection, polyphosphates may suitably be used as sequestration agents, formaldehyde, formic acid, lactic acid, and the like may be used as acid stable bactericidal additions, and water soluble magnesium salts, proteins as well as their decomposition products, condensation products of albumin hydrolysates with higher molecular sulfonic acids, fatty acid methyltaurines, sulfonation products of imidazoles, polyvinyl alcohol, polyvinyl pyrrolidone, etc. may be used as oxygen stabilizers. Moreover, specific corrosion protection agents, such as chromic acid, chromates, and bichromates, may also be employed in the acid concentrate.

With respect to the additives to the alkaline component concentrate, these include in particular alkali carbonates, alkali silicates, as wash active materials, sequestration agents of the type represented by the alkali salts of ethyl ene diamine tetraacetic acid or nitrile-triacetic acid, thickening agents of the type represented by polyacrylates, disinfecting agents of the phenolic type, dirt-carrying agents, such as alkali salts of carboxymethylcellulose, foam stabilizers, such as fatty acid ethanolamides, oxygen stabilizers, suchas magnesium silicates, and certain dye stuffs, brighteners, and particularly perfume compositions. Moreover, solvents, such as hydrocarbons, chlorinated hydrocarbons, alcohols, and the like, may also be used, the same frequently even contributing to the liquefying and clarifying disposition of the alkaline concentrate.

In any case, care must be taken that the additives do not detrimentally influence the stability and homogeneity of the particular aqueous concentrate. Such concentrate should possess the character of true or colloidal solutions or at least of stable suspensions.

The following examples are set forth for the purpose of illustrating the composition of the acid and alkaline concentrates and to indicate in greater detail the scope of the present invention. It will be understood that the examples are not to be considered as limiting the invention thereto.

Example I centrate formed in this manner possesses a pH value of 3.5. This concentrate may be filled into polyethylene flasks and, contained in this manner, will retain for months practically all of its active oxygen content.

Example 2 In a similar manner. to that described with respect to the procedure of Example 1, 5 parts by weight of an ethoxylated coconut oil alcohol (having ethoxyl groups), 0.3 part by weight of potassium toluene sulfonate, 11 parts by weight of K P 0 -3.5H O and 21.3 parts by weight of hydrogen peroxide (30% concentration) are dissolved in 60 parts by weight of distilled water. The adjustment of the pH value to 3.2 is carried out by acidifying the reaction mixture with pyrophosphoric acid. The acidification may also be carried out using sulfuric acid. In either case, the acid concentrate obtained is stable in plastic flasks for weeks without any significant or noteworthy loss of oxygen. The same is true where the acid concentrate is contained within bags or packets of polyethylene sealed from the atmosphere.

Example 3 6 quently, 17 parts by weight of a technical alkyl-sulfonic acid albumin condensate containing 38% active substance and 30 parts by weight of hydrogen peroxide (30% concentration) arestirred in. The pH value of the acid concentrate formed amounts to 3.45. This product in the same way is stable even after extended periods of storing.

Example 4 An alkaline concentrate is produced by admixing 50 parts by weight of distilled water with 15 parts by weight of a coconut oil acid (cocinic acid)-albumin condensate (Na-salt; 36%), 10 parts by weight of a fatty acid methyltauride (Na-salt; 64%), 2 parts by weight of potassium toluene sulfonate, 25 parts by weight of tetra-potassium pyrophosphate and 5 parts by weight of sodium meta-silicate-9 hydrate. Thereafter, 4 parts by weight of caustic potash are dissolved into the completely homogeneous weakly opalescent solution. 4

Example 5 An alkaline component concentrate is prepared by dissolving into 50 parts by weight of distilled water, 15 parts by weight of a technical mixture of the potassium salts of an albumin condemate and of an alkylbenzene eulfonate (35% active substances), 10 parts by weight of a fatty acid methy-l-tauride (Na-salt; 64%), 2 parts by weight of potasium toluene sulfonate, 0.9 part by weight of the tetrasodium salt of ethylene diamine tetraacetic acid and 25 parts by weight of tetrapotassium pyrophosphate. .A homogeneous opalescent solution is thereby formed. This solution is standardized with 3 parts by weight of caustic potash to obtain the required alkalinity.

Example 6 An alkaline component concentrate is prepared by dissolving into 56 parts by weight of distilled water, 5 parts by weight of a high molecular alkylsulfonate (Na-salt; 10 parts by weight of a fatty acid isethionate (Nasalt; 60%), 2 parts by weight of potassium toluene sulfonate, 0.9 part by weight of the tetrasod'ium salt of ethylene diamine tetraacetic acid and 18 parts by weight of tetrapotassium pyrophosphate. The resulting homogeneous opalescent solution is adjusted to the desired alkalinity with 4 parts by weight of solid caustic potash.

Example 7 Into 50 parts by weight of distilled water are dissolved for the production of an alkaline component concentrate, 12.5 parts by weight of a tri ethanol amine salt of a dodecyl-benzene sulfonic acid (40%), 6 parts by weight of a coconut oil alcohol-3-ethylene oxide-sulfate (Na-salt; 35%), 10 parts by weight of oleic potash soap (46% fatty acid), 3.4 parts by weight of the tetrasodium salt of ethylene diamine tetraacet-ic acid, 1.8 parts by weight of potassium toluene sulfonate, and 5 parts by weight of solid caustic potash. Thereafter 8 parts by weight of methylcyclohexanol are stirred into the resulting solution.

By dissolving the alkaline concentrates prepared in accordance with Examples 4-7, or produced in like manner, together with the acid concentrates prepared in accordance with the procedure of Examples 1-3, or produced in like manner, in water, using equal quantities of each concentrate, i.e. one alkaline concentrate with one acid concentrate, suitable washing solutions of alkaline reaction are obtained. Such solutions possess a pH value which is situated between 8.8 and 9.5, the pH value depending upon the particular alkaline concentrate used with the particular acid concentrate as well as the amounts of ingnedients in each, as the artisan will appreciate. Since it is often inadvisable to expose the material to be washed, such as laundry clothing, or the vessels containing the same, to acid treatment, as a rule the alkaline concentrate is first dissolved into the washing solution, i.e. water, and thereafter the acid concentrate is added. In acid stable clothing or other laundry material to be washed, such as for example woolen articles, it is also possible to 7 invert the order of audition and first add the acid concentrate and thereafter the sdkaline concentrate to the laundry in water.

Moreover, a simultaneous dissolution of the concentrates is frequently permissible. Besides this, the concentrates may be admixed with one another before they are introduced into the wash water for dissolving therein. 'lherefore, it is basically posible either to add first the alkaline and acid concentrates to water in order to form a wash water and thereafter introduce the laundry or clothing to be washed into this wash water, or to first prepare the laundry or clothing to be washed in water and thereafter introduce the acid and alkaline concentrates therein, either together or in any desired ordinal sequence depending upon the stability of the clothing or laundry to the particular concentrates.

While commercial or industrial consumers, such as commercial self-service laundries, may store the concentrates in accordance with the invention in large amounts, such that measured amounts may be taken for a particular load of laundry, it is preferred in the case of household laundry work to provide the concentrates in separate individual packages or containers in a convenient dosage for use with a typical load of wash. This may be carried out by providing the packages or containers in the form of flasks, bags, packets, or the like or in any other suitable form permitting a simple manipulation for adding the desired concentrates to the wash water. Such containers may be made from glass, plastics, paper or cardboard which has been rendered impermeable to liquids, metal, and the like. The individual packages or containers may be connected with one another, such as in the case of packets of plastic tubular material seam-welded at either end, double flasks, double bags, etc. having a common intermediate wall and the like. The provision for the concentrates in the individual packages or containers is effected such that in each instance the acid and/or alkaline liquid concentrate is contained in a balanced quantity with respect to the other concentrate for carrying out the washing prcces.

In accordance with the foregoing, it will be appreciated that a suitable washing process may be carried out in a household drum type washing machine. Thus, for example, where kilograms of dry wash (clothing) is placed in a household drum washing machine, 200 grams each of the concentrates according to Example 1 (acid concentrateyand Example 4 (alkaline concentrate) may be Each of these concentrates is supplied in a polyethylene p cket or bagmade in the form of a double packing;-ee'am-welded a1ong grieumningeagesfxaer the washing machine has been loaded with the washing material (laundry) and the required quantity of water added, the packet containing the alkaline liquid concentrate is emptied into the drum, whereupon after a few revolutions of the drum, the acid liquid concentrate is emptied from the other packet into the washing liquid. As aforesaid, other equally effective procedures for washing with the concentrates in accordance with the invention may be employed with the same favorable results, -i.e. pre-measured quantities, easy dissolution into the washing liquid, saving in time, etc.

Nevertheless, by means of suitable dosage devices, the quantities of the concentrates in accordance with the invention may be introduced into the washing machine. In the case of household washing of laundry using a wash tub, a similar manner of operation is concerned, wherein it is quite suitable, particularly where strongly soiled laundry is involved, to prepare at first the wash water in admixture with the alkaline concentrate, then to introduce the laundry, and only after a sufficient period of pre-treatment of the laundry in the cold or moderately heated alkaline wash solution to add the acid concentrate. It will be noted that care should be taken to thoroughly work the clothing and agitate the liquid to assure a thorough mixing of the concentrates for achieving the desired pH value of the washing liquor. The foregoing procedure 8 may also be used in automatic washing machines, such that the washing process is divided into a preliminary washing treatment in which the clothing is agitated wth the alkaline concentrate in the wash water, for example, and thereafter the main washing process which is carried out when the acid concentrate has been added.

Naturally, according to the type of washing material or laundry to be treated, the pH value of the final washing liquid may be adjusted by changing the amount of or potential pH value of the acid adjusted and/or alkaliadjusted agents in the two concentrates. While for most hot-water washing processes, particularly for white, coarse, and also colored wash of cellulose or cotton textiles, final pH values between 8.5 and 10.5 have provided to be particularly suitable, it has been found that for favorable washing of woolen articles, textiles, or knitted goods, composed of chemical fibers (synthetics), silk or rayons, as well as finely colored articles, it is preferred to employ the milder conditions of lower washing temperatures and weaker alkaline adjustments of the overall washing liquid. In such cases, pH values between 7.5 and 8.5, for example, are employed and such pH values are achieved by predetermining the acid and alkali dosages of the two concentrates respectively.

What is claimed is:

1. Process for washing and bleaching articles in a washing medium which comprises applying to the article to be treated liquid water-containing concentrates in the form of (a) an acid component concentrate having an acid stabilized active oxygen-containing compound and an acid-stable organic washing agent in aqueous acid medium, said acid-stable organic washing agent being selected from the group consisting of an alkylene oxide adduct of an organic compound having a saturated alkyl group containing an active hydrogen atom, condensation products of high-molecular alkyl sulfonic acid with albumin hydrolysates, condensation products of high-molecular alkaryl sulfonic acids with albumin hydrolysates, acidstable high-molecular aliphatic sulfonic acids, and acidstable high-molecular aliphatic-aromatic sulfonic acids, an (b) an alkaline component concentrate having an alkaline-stable organic washing agent and an alkaline reacting compound in aqueous alkaline medium; said alkaline-stable organic washing agent being selected from the group consisting of an alkylene oxide adduct of an organic compound having an alkyl group containing an active hydrogen atom, fatty acids, acylated hydroxy-alkanesulfonates, acylated amino-alkane-sulfonates, soluble alkyl sulfates, alkyl-ether-sulfates, fatty acid-alkylol-amidesulfates, alkylbenzene-sulfonates, soaps, salts of nitrogenbascs, and mixtures thereof, the amount of alkaline reacting compound being adjusted to render the overall washing medium formed of sufficient pH for effecting the washing and bleaching treatment.

2. Process according to claim 1, wherein the acid-stable organic washing agent is selected from the group consisting of non-ionic and anionic washing agents.

3. Process according to claim 1, wherein the alkalinestable organic washing agent is selected from the group consisting of non-ionic and anionic washing agents.

4. Process according to claim 1, wherein the acid component concentrate is an acid stabilized aqueous peroxide solution containing an alkylene oxide adduct of a member selected from the group consisting of fatty alcohols, fatty acids, fatty amines, fatty acid amides, fatty acid alkylol-amides, mercaptans, alkyl phenols and alkylnapththols.

5. Process according to claim 4, wherein said adduct is an ethylene oxide adduct of a higher molecular weight saturated fatty alcohol having from 5 to 16 ethoxyl groups in the molecule.

6. Process according to claim 4, wherein said adduct is an ethylene oxide adduct of a higher molecular weight saturated alkyl-phenol having from 5 to 16 ethoxy groups in the molecule.

11. Process according to claim 1 wherein said adduct is an ethylene oxide adduct of a fatty alcohol.

12. Process according to claim 1, wherein said adduct is an ethylene oxide adduct of an alkylphenol.

13. Process according to claim 1, wherein the alkaline component concentrate additionally contains a solution promoter selected from the group consisting of lowmolecular alkyl-aromatic sulfonic acids and alkali salts thereof.

14. Process according to claim 1, wherein the alkaline component concentrate alkaline reacting compound is an alkali.

15. Process according to claim 14, wherein said alkali is selected from the group consisting of caustic alkali, alkali carbonate, alkali-orthophosphates, alkali metal-silicates, alkaline reacting organic nitrogen bases, and alkali salts of weak organic acids.

16. Process according to claim 1, wherein the overall washing medium formed additionally contains at least one of the following: inorganic washing agent, sequestration agent, solvent, thickening agent, disinfecting agent, dirtcarrying-efiect-compounds, fiber-protecting agent, skinprotecting agent, oxygen stabilizer, foam-stabilizer, foambreaking agent, corrosion protection agent, dyestufi, optical brightener and perfume.

17. Process according to claim 1, wherein the alkaline component liquid water-containing concentrate is added to the washing medium for the article to be treated prior to the adding of the acid component liquid water'containing concentrate.

18. Process according to claim 1, wherein the alkaline component liquid water-containing concentrate is applied to the article to be treated in the washing medium therefor, and after a pre-washing treatment, the acid component liquid water-containing concentrate is added and the washing treatment is completed.

19. In washing, the step which comprises applying to an article to be washed and bleached in a washing medium liquid water-containing concentrates in the form of (a) an acid component concentrate having an acid stabilized active oxygencontaining compound and an acidstable organic washing agent in aqueous acid medium, said acid-stable organic washing agent being selected from the group consisting of an alkylene oxide adduct of an organic compound having a saturated alkyl group containing an active hydrogen atom, condensation products of high-molecular alkyl sulfonic acid with albumin hydrolysates, condensation products of high-molecular alkaryl sulfonic acids with albumin hydrolysates, acid-stable highmolecular aliphatic sulfonic acids, and acid-stable highmoiecular aliphatic-aromatic sulfonic acids, and (b) an alkaline component concentrate having an alkaline-stable organic washing agent and an alkaline reacting compound in aqueous alkaline medium, said alkaline-stable organic washing agent being selected from the group consisting of an alkylene oxide adduct of an organic compound having an alkyl group containing an active hydrogen atom, fatty acids, acylated hydroxy-alkane-sulfonates, acylated amino-alkane-sulfonates, soluble alkyl sulfates, alkylether-sulfates, fatty acid-alkylol-amide-sulfates, alkylbenzene-sulfonates, soaps, salts, of nitrogen-bases, and mixtures thereof, the amount of alkaline reacting compound being adjusted to render the overall washing medium formed of suflicient pH for effecting the washing and bleaching treatment.

References Cited in the file of this patent UNITED STATES PATENTS 2,730,428 Lindner Ian. 10, 1956 2,920,045 Hearn et a1 Jan. 5, 1960 2,947,702 Coskie Aug. 2, 1960 3,003,910 Dithmar Oct. 10, 1961 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,131,991 May 5, 1964 Kurt Lindner et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 64, for "dye stuff-" read dye stuffs column 5, line 33, for "concentrate" read concentrates column 8, line 41, for "an", first occurrence, read and line 43, for "medium" read medium, column 9, lines 27 and 28, for "metal-silicates" read meta-silicates Signed and sealed this 15th day of September 1964.

: (SEAL) I Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents UNITED-STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 131 ,991 May 5, 1964 Kurt Lindner et a1,

It is hereby certified. that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected" below;

Column 2, line 64, for "dye stuff-" read dye stuffs, column 5, line 33, for "concentrate read concentrates column 8, line 41, for "an", first occurrence, read and line 43, for "medium; read medium, column 9, lines 27 and 28, for "metal-silicates" read meta-silicates Signed and sealed this 15th day of September 1964,.

(SEAL) Attest:

I ERNEST W. SW I'DER EDWARD J. BRENNER- Attesting'Officer" Commissioner of Patents-

Claims (1)

19. IN WASHING, THE STEP WHICH COMPRISES APPLYING TO AN ARTICLE TO BE WASHED AND BLEACHED IN A WASHING MEDIUM LIQUID WATER-CONTAINING CONCENTRATES IN THE FORM OF (A) AN ACID COMPONENT CONCENTRATE HAVING AN ACID STABILIZED ACTIVE OXYGEN-CONTAINING COMPOUND AND AN ACIDSTABLE ORGANIC WASHING AGENT IN AQUEOUS ACID MEDIUM, SAID ACID-STABLE ORGANIC WASHING AGENT BEING SELECTED FROM THE GROUP CONSISTING OF AN ALKYLENE OXIDE ADDUCT OF AN ORGANIC COMPOUND HAVING A SATURATED ALKYL GROUP CONTAINING AN ACTIVE HYDROGEN ATOM, CONDENSATION PRODUCTS OF HIGH-MOLECULAR ALKYL SULFONIC ACID WITH ALBUMIN HYDROLYSATES, CONDENSATION PRODUCTS OF HIGH-MOLECULAR ALKARYL SULFONIC ACIDS WITH ALBUMIN HYDROLYSATES, ACID-STABLE HIGHMOLECULAR ALIPHATIC SULFONIC ACIDS, ANDACID-STABLE HIGHMOLECULAR ALIPHATIC-AROMATIC SULFONIC ACIDS, AND (B) AN ALKALINE COMPONENT CONCENTRATE HAVING AN ALKALINE-STABLE ORGANIC WASHING AGENT AND AN ALKALINE REACTING COMPOUND IN AQUEOUS ALKALINE MEDIUM, SAID ALKALINE-STABLE ORGANIC WASHING AGENT BEING SELECTED FROM THE GROUP CONSISTING OF AN ALKYLENE OXIDE ADDUCT OF AN ORGANIC COMPOUND HAVING AN ALKYL GROUP CONTAINING AN ACTIVE HYDROGEN ATOM, FATTY ACIDS, ACYLATED HYDROXY-ALKANE-SULFONATES, ACYLATED AMINO-ALKANE-SULFONATES, SOLUBLE ALKYL SULFATES, ALKYLETHER-SULFATES, FATTY ACID-ALKYLOL-AMIDE-SULFATES, ALKYLBENZENE-SULFONATES, SOAPS, SALTS, OF NITROGEN-BASES, AND MIXTURES THEREOF, THE AMOUNT OF ALKALINE REACTING COMPOUND BEING ADJUSTED TO RENDER THE OVERALL WASHING MEDIUM FORMED OF SUFFICIENT PH FOR EFFECTING THE WASHING AND BLEACHING TREATMENT.