US3402128A

US3402128A - Novel composition and method

Info

Publication number: US3402128A
Application number: US420180A
Authority: US
Inventors: Puchta Rolf; Fries Walter
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1964-01-04
Filing date: 1964-12-21
Publication date: 1968-09-17
Anticipated expiration: 1985-09-17
Also published as: BE657865A; GB1089998A; NL6414208A; FR1419437A; US3388069A; DE1271885B; CH467721A; DK120958B; DE1299092B; ES307775A1; GB1089997A

Description

3,402,128 NOVEL COMPOSITION AND METHOD (LIQUID CONCENTRATES CONTAINING ACTIVE OXYGEN AND HAVING SURFACE-ACTIVE PROPERTIES) Rolf Puchta, Hilden, Rhineland, and Walter Fries, Erkrath-Unterbach, Germany, assignors to Henkel & Cie, G.m.b.H., Dusseldorf, Germany, a corporation of Germany N Drawing. Filed Dec. 21, 1964, Ser. No. 420,180 Claims priority, applicatio; Germany, May 30, 1964,

,856 14 Claims. (Cl. 252-99) ABSTRACT OF THE DISCLOSURE Liquid storage-stable, active-oxygen containing concentrates are disclosed which are composed of water, hydrogen peroxide (free or bound) and a surface active aminoxide of the formula:

R4 R|X(R20)n-R3N O R wherein R is alkyl having 6 to 20 carbon atoms, X is oxygen, sulfur, selenium or telurium, R is ethylene, propylene or oxypropylene, n is a whole number from 0 to 18, R is alkyl or alkylol, each having up to 4 carbon atoms and R and R are each alkyl or alkylol each having up to 5 carbon atoms, as stabilizer for the hydrogen peroxide.

The aminoxide is present in the amounts of from 2 to 40% by weight of the total composition and with reference to the hydrogen peroxide (concentrate contains hydrogen peroxide in an amount of from 3 to 90 wt.-percent) in an amount of from to 200% by weight.

This invention relates to liquid concentrates containing active oxygen and having surface-active properties. More specifically, this invention relates to aqueous concentrates of per-oxygen compounds, such as hydrogen peroxide and the like, and a surface-active aminoxide stabilizer.

It is difiicult to stablize active oxygen compounds contained in a liquid, such as aqueous concentrates of percompounds, specifically hydrogen peroxide and the like in aqueous media in the presence of tensides, so that the concentrates will have adequate storage life when stocked for either industrial or domestic use, such as industrial laundries, hairdressers shops and domestic cleaning agents. This is due to the fact that most of the known tensides induce the premature splitting of active oxygen from percompounds. Findings to the contrary are infrequent, as discussed in German Auslegeschrift 1,121,594.

Stabilizing agents comprising non-tenside compounds are Well known and include inorganic and organic acids, such as orthoor polyphosphoric acids, tannic acids, citric acid, barbituric acid, ascorbic acids, and the like, in addition to acid salts, such as acid sodium pyrophosphate, and many other organic compounds, such as acetophenetidin, acetanilide or 8-oxyquinoline, to name only a few. Other compounds are disclosed in Das Wasserstoifperoxyd und die Perverbindungen, W. Machu, 2nd edition, Vienna, 1951, pp. 195 to 208.

Many of the stabilizers are known and described in the prior art, such as magnesium salts, and especially magnesium silicates, in addition to alkali-pyrophosphates or alkali polyphosphates, alkali stannates, alkali silicates, and others are used for regulating the degree to which oxygen is liberated in diluted and ready-touse washing and States Patent bleaching fluids containing per-oxygen compounds. These stabilizers are also used accordingly the concentrate has a pH of from 1 to 10 and preferably has a pH within the range of from 3 to 9 to prevent fiber damage in washing and bleaching processes. 0n the other hand, most of the known stabilizing agents, with the exception of the abovenamed acids, acid salts, and a small number of organic compounds, are not suitable for manufacturing liquid concentrates containing oxygen, which are capable of long storage life.

It has been relatively diflicult to stabilize percompounds utilizing the compositions and methods of the prior art, and especially concentrates with peroxide contents of at least 3 weight percent hydrogen peroxide and even substantially higher active-oxygen contents, so that they may be stored in commerce, trade and industry for a number of days or even weeks, in ready-to-use form, but without danger of decomposition.

It is therefore an object of this invention to provide a method for stabilizing per-compounds, specifically peroxygen compounds, and the like, for long periods of time without decomposition. Another object of this invention is to provide a liquid concentrate containing active oxygen and having surface-active properties, whereby the surfaceactive agent (tenside) will not induce premature splitting of the active oxygen in the per-compound. It is another object of this invention to provide a novel and useful surface-active compound. It is another object of this invention to provide a novel stabilizing compound that, additionally, has surface-active properties and will act as a per-compound stabilizer.

These and other objects have been achieved by the discovery that surface-active aminoxides are especially well suited for the stabilization of active oxygen contained in liquids, especially aqueous concentrates of per-compounds, such as hydrogen peroxides or its adducts.

The surface-active aminoxides of this invention are valuable tensides which have detergent or wetting properties which vary according to the nature and structure of the alkyl side-chains attached to the amine compound. These properties of high-molecular-weight aminoxide now make it possible to manufacture a combined detergentbleaching concentrate, in which the bleaching compound comprises active-oxygen-containing materials, such as compounds of hydrogen peroxide or adducts of hydrogen peroxide to urea, melamine, alkali borates, alkali ortho-phosphates, alkali polyphosphates, or the like. The compositions of this invention are in marked contrast to prior art compositions which employ stabilizing agents that lack surface-active properties. The surface-active properties of prior art compositions are obtained by the addition of tensides to the oxygen compound, which, as a rule, nullify or counteract the stabilizing agents and promote relatively rapid loss of active oxygen from the composition.

It has now been found that aminoxides having a nitrogen On an aliphatic radical linked in the manner of an ether to the remaining part of the molecule (=aminoxide radical), so that the aminoxide nitrogen and ether oxygen are separated from one another by at least 3 carbon atoms and can be used as surface-active aminoxides having stabilizing properties. Glycol or polyglycol ether groups may be located between the hydrophobic part of the molecule and the aminoxide radical.

The aminoxides of this invention comprise compounds of the general formula /R4 R1X(R --0)nR N 0 where R signifies a saturated higher alkyl radical with 6 to 20 carbon atoms, X a chalcogen such as oxygen, sulfur, selenium and telurium, oxygen or sulfur atom being preferred, R an ethylene, propylene or oxypropylene radical, n a whole number from to 18, perferably from 0 to 10, R a radical with at least 3 or 4 carbon atoms and containing, if desired, free hydroxy groups, and R and R signify lower saturated alkyl or alkylol radicals with at most 5, preferably with at most 3, carbon atoms. The manufacture of these aminoxides is described in German Auslegeschrift 1,163,850.

The ether oxygen atom or thioether sulfur atom present in the surface-active aminoxides to be used according to the invention improves the solubility of the products, which is still further improved by any glycolether or polyglycolether radicals that may be present. For this reason, substantially more than 24 carbon atoms may be present in the aminoxides to be used according to this invention; the maximum of 24 carbon atoms mentioned refers to the hydrophobic part of the molecule which, in the aboverepresented formula, refers to the radical R The advantages of these aminoxides are not limited merely to the better solubility of the compounds, but are also to be seen in a better stabilizing effect. If the active oxygen is present as hydrogen peroxide, the upper limit of the hydrogen peroxide content of the concentrates lies preferably at 60 weight percent H 0 The surface-active aminoxides of this invention have especially pronounced stabilizing effects in an acid-toneutral milieu, i.e., at a pH from 1 to 7. For example, the aminoxide may be used in a strongly acid (pH of 2 to 4), or weakly acid (from 4 to 68) environment. Stabilization, however, may also be achieved from several days to several weeks in a weakly alkaline milieu, i.e., at a pH from 7.2 to 8.

If the shelf life requirements are less stringent, as, for example, in the laundry industry, the pH of the environment may be made more strongly alkaline. For example, a pH up to about is suitable for this purpose. The shelf life of the concentrates, however, decreases as the alkalinity increases, so that pH values over 10.5 do not give optimum results with respect to stability, however, concentrates having higher pH values may also be used.

The compositions of this invention may be stored as concentrates in a weakly acid, or neutral, or weakly alkaline mixture, which are adjusted to the desired higher pH values by the addition of alkaline or acidic compounds upon being used. Conventional alkaline reagents may be used for increasing the pH of the milieu. Alkaline salts are especially useful, such as those commonly used as additives in bleaching and washing, for example, the alkaline or alkali carbonates, bicarbonates, ortho-phosphates, pyro-phosphates, and polyphosphates such as tripolyphosphates, borates, silicates, and the like, and various mixtures thereof. If the composition supplying the active oxygen comprises the perhydrates of the above-mentioned inorganic salts, the alkaline materials will generally be present in sufiicient quantities, so that addition of other alkaline compounds will not generally be necessary.

Acidic substances may also be added to the compositions of this invention in order to lower the pH value to 9 or less. If condensed phosphates are to be used, the weakly acid glassy phosphates of the Graham salt type have proven to be particularly well suited for this purpose.

Non-reducing inorganic or organic acids or acid salts are used for adjusting the pH values in the acid range, if necessary. Phosphoric acid as well as the polyphosphoric acids, as mentioned above, are suitable in addition to sulfuric acid, citric acid, malonic acid, tartaric acid, ascorbic acid, and the like, or various mixtures thereof. Some of these acids are already well known in the prior art as oxygen stabilizers and, in some cases, permit a reduction of the amount of aminoxides present in the composition of this invention, or their replacement by other tensides.

The expression tenside shall be construed in the spec- 1' ification and claims of this application to mean any organic surface-active compound or the like, or surfactant, as known and used in the prior art.

The amount of aminoxides serving as stabilizers in accord with this invention can vary within Wide limits. These compounds may be present in quantities amounting to 2 to 40 percent by weight, and preferably 5 to 25 percent by weight of the total composition. With reference to the hydrogen peroxide present in the free or bound state, the aminoxides are present in quantities of at least 10 percent by weight, however, may be used in amounts of up to 200 percent by weight, and preferably in amounts from 30 to 100 percent by weight.

The aminoxides of this invention may be used in combination with other substances in the preparation of compositions containing active oxygen. These substances generally comprise tensides of the carboxylate, sulfate and sulfonate type having saturated molecular hydrophobic radicals attached thereto. Non-ionogenic tensides are particularly suitable, especially those comprising the addition of ethylene oxide to either fatty acids or fatty alcohols in addition to the ethylene oxide addition products of saturated alkyl phenols, such as the nonyl phenols. The

mixed ethylene'oxide-propylene oxide products of the pluronic or tetronic types are also suitable. Pluronic compounds are generally high-molecular-weight polypropylene glycol ethers, which are rendered water-soluble by the addition of ethylene oxide to the molecular chain, whereas the tetronic types generally comprise addition products of propylene oxide and diamines such as ethylene diamine. Other compounds suitable in this respect comprise alkali metal pyrophosphates or polyphosphates. These compounds may be used in the form of their acid salts or as acidified preparations. Additionally, hydrotropic substances may also be used in the compositions of this invention. Examples of suitable hydrotropic compounds comprise the alkali metal salts of toluenesulfonic acid or xylenesulfonic acid. Dirt holders, such as carboxymethylcelluloses or oxidation-resistant optical brighteners, can also be present.

The term liquid concentrates containing active oxygen shall be understood hereby to mean aqueous solutions with a content of at least 3 to weight percent, and pref: erably 10 to 70 weight percent and most preferably 10 to 40 weight percent, of H 0 The H 0 may also be preent, wholly or partially, in the form of addition products which it forms with urea, melamine, alkali borates, alkali ortho-phosphates or polyphosphates, or the like, which have been dissolved or suspended in water. The concentration of any undissolved hydrogen peroxide compounds that may be present in the liquid concentrates containing active oxygen ranges from 3 to 40 weight percent, and preferably from 10 to 25 weight percent.

The following non-limiting examples are given as certain preferred embodiments of the invention and are not to be construed as narrowing the novel and inventive method and composition of the applicants. In all of the examples below standard commercial hydrogen peroxide of technical quality was used.

EXAMPLES I-IV Using an aminoxide of the formula (:11, C12iaalkyl- O C sHc.-N O

CH; where alkyl is derived from coconut fatty acid, per concentrates of different compositions are prepared. These concentrates and concentrates composed in like manner but free of aminoxides (designated by A and B) are stored for 6 weeks in colorless polyethylene flasks at room temperature, so that they are exposed to daylight, but not to direct sunlight. The active-oxygen contents were measured at various intervals 'by titration with potassium permanganate. The compositions of the concentrates studied and the measured losses of active oxygen are given in Table I below:

TABLE I Active oxygen concentrate according to Example Component or the concentrate:

Wt. percent H202 3 3 3 5 5 5 Wt. percent aminoxide" 0 5 10 Wt. percent K4P207 20 20 20 20 20 20 Wt. percent toluenesulionate 8 8 8 8 8 8 pH value of concentrate 9.0 9. 0 8. 9 8.8 8. 8 8.6 Active oxygen loss in percent of initial value=100, attorays 11.0 2.7 6.0 0.6 6.0 2.8 1 week 16.5 6.0 7.5 15.0 8.0 5.5 2weoks .266 12.5 13.1 21.2 13.9 9.0 4weeks 39.0 18.0 18.5 34.5 21.5 17.5 6weeks 46.0 24.5 24.0 42.0 26.5 23.0

Thus, there has been described a very effective method and composition for stabilization of liquid concentrates containing active oxygen by means of aminoxides in a strongly or weakly acid, neutral or weakly alkaline medium, and as such signifies a considerable advance in the art. The compositions of this invention are useful in such applications as cleaning and bleaching of textiles, the bleaching of human hair, the fixing of hairdos and other cosmetic treatments, and can be performed directly with such concentrates without requiring neutralization.

The C -alkyl group being present in the aminoxide as used in the Examples I-IV was derived from coconut fatty acids.

For the purpose of the invention there are preferably to be used the aminoxides as described in German Auslegeschrift 1,163,850. When using these aminoxides instead of the aminoxide of the Examples I-IV, similar results are obtained.

Although the invention has been described with reference to certain preferred embodiments, it is not the invention of the applicants to be limited thereby, and certain obvious modifications of the novel composition of matter and method are intended to be included within the broad scope of the invention, as embodied in the following claims.

What is claimed is:

1. A liquid storage-stable active-oxygen containing detergent bleaching concentrate consisting essentially of water, hydrogen peroxide in an amount of from 3 to 90 wt.-percent and a surface active aminoxide of the formula:

wherein R is saturated alkyl having 6 to 20 carbon atoms, X is oxygen, R is a member selected from the group consisting of ethylene, propylene and oxypropylene, n is 1, R is a member selected from the group consisting of saturated alkyl and alkylol each having at least 3 carbon atoms and R and R are each selected from the group consisting of saturated alkyl and alkylol having at the most 5 carbon atoms, in an amount of from 2 to 40 wt.- percent, the quantity of aminoxide amounting to 10 to 200 wt.-percent referred to the hydrogen peroxide present.

2. A liquid storage-stable active-oxygen containing detergent-bleaching concentrate according to claim 1 wherein R contains from 3 to 4 carbon atoms.

3. A liquid storage-stable active-oxygen containing detergent-bleaching concentrate according to claim 1 wherein R and R each have at the most 3 carbon atoms.

4. A liquid storage-stable active-oxygen containing detergent-bleaching concentrate according to claim 1 wherein said concentrate has a pH of from 1 to 10.

5. A liquid storage-stable active-oxygen containing detergent-bleaching concentrate according to claim 1 wherein said concentrate has a pH of from 3 to 9.

6. A liquid storage-stable active-oxygen containing detergent-bleaching concentrate according to claim 1 wherein said hydrogen peroxide is present in an amount of from 10 to wt-percent.

7. A liquid storage-stable active-oxygen containing detergent-bleaching concentrate according to claim 1 wherein said hydrogen peroxide is present in an amount of from 10 to 40 Wt.-percent.

8. A liquid storage-stable, active-oxygen containing dctergent-bleaching concentrate according to claim 1 wherein said aminoxide is present in an amount of from 5 to 25 wt.-percent.

9. A liquid storage-stable, active-oxygen containing detergent-bleaching concentrate according to claim 1 wherein the quantity of aminoxide referred to the hydrogen peroxide amounts to from 30 to wt.-percent.

10. A liquid storage-stable, active-oxygen containing dctergent-bleaching concentrate according to claim 1 wherein said aminoxide has the formula:

tergent-bleaching concentrate according to claim 10 consisting essentially of- Wt.-percent H202 3 Aminoxide 5 K P O 20 Toluene sulfonate 8 12. A liquid storage-stable, active-oxygen containing de- 0 tergent-bleaching concentrate according to claim 10 consisting essentially of- Wt.-percent H 0 3 Aminoxide l0 K P O 20 Toluene sulfonate 8 13. A liquid storage-stable, active-oxygen containing detergent-bleaching concentrate according to claim 10 consisting essentially of- Wt.-percent H 0 5 Aminoxide 5 K P O 20 Toluene sulfonate 8 14. A liquid storage-stable, active-oxygen containing detergent-bleaching concentrate according to claim 10 consisting essentially of Wt.-percent H 0 5 Aminoxide 10 K P O 20 Toluene sulfonate 8 References Cited UNITED STATES PATENTS 3,194,768 7/1965 Lindner et al 252186 X 3,202,714 8/1965 Zimmerer et al. 252117 X 3,206,512 9/1965 Koebner et al. 252152 3,252,979 5/1965 Oswald et al. 260-584 FOREIGN PATENTS 626,979 6/ 1963 Belgium.

LEON D. ROSDOL, Primary Examiner.

MAYER WEINBLATT, Assistant Examiner.

U.S. DEPARTMENT OF COMMERCE PATENT OFFICE Washington, D .C. 20231 UNITED STATES PATENT OFFICE CERTIFICATE CORRECTION v Patent No. 3,402,128 September 17, 1968 Rolf Puchta et a1.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 4, line 23, beginning withFThemixed" cancel all to and including "generally comprise" in line: 29, same column 4, and insert Mixed ethylene oxide-propylene oxide products are also suitable and include high-molecular-weight.polypropylene glycol ethers, which are rendered water-soluble by the addition of ethylene oxide to the molecular chain and Column 6, line 69, "626,979" should read 626 ,505

Signed and sealed this 24th day of February 1970.

(SEAL) Attest:

Edward M. Fletcher, Jr. WILLIAM E. SCHUYLER,

Attesting Officer Commissioner of Patents