WO1993003006A1

WO1993003006A1 - Amine oxide complexes

Info

Publication number: WO1993003006A1
Application number: PCT/US1992/005265
Authority: WO
Inventors: Kim Renae Smith; James Ellwood Borland; Joe Dean Sauer; Terry Crutcher
Original assignee: Ethyl Corporation
Priority date: 1991-07-26
Filing date: 1992-06-22
Publication date: 1993-02-18

Abstract

Novel perhydrates having utility as surfactants and bleaching agents are obtained by reacting an anhydrous amine oxide or an amine oxide monohydrate with hydrogen peroxide in such proportions as to provide a compound corresponding to the formula RR'R''NO.xH2O.yH2O2 in which R is a primary alkyl group containing 8-24 carbons; R' is methyl, ethyl, or 2-hydroxyethyl; R'' is independently selected from methyl, ehtyl, 2-hydroxyethyl, and primary alkyl groups containing 8-24 carbons; x is 0 or 1; y is 1 or 2; and x+y is «2. Cleaning compositions comprising the perhydrates form aqueous compositions in which the perhydrates may be employed alone or together with conventional cleaning and/or bleaching formulation ingredients.

Description

AMINE OXIDE COMPLEXES^'

Field of Invention

This invention relates to mixed amine oxide perhydrates, processes for preparing them, and their use as oxygen bleaches.

Background

It is known that many surfactants are useful in cleaning formulations, such as hard surface cleaners and solid or liquid laundry detergents. Among the surfactants which have been found to be particularly useful in these applications are mixed amine oxides, i.e., amine oxides in which the organic groups attached to the amino nitrogen include at least one long-chain group and at least one short- chain group.

The amine oxides employed in the cleaning compositions are most commonly dilute aqueous solutions, since they are ordinarily synthesized as such; but they are sometimes solids obtained by spray-drying, evaporating, or after-treating the dilute solutions.

As taught in U.S. Patent 5,075,501 (Borland et al.), solid amine oxides which have advantages over the dilute solutions and over the solids obtained by previously-known techniques can be produced by preparing the amine oxides completely or partially in dihydrate form and, if desired, then converting the product to an oxide containing a lesser amount of water, e.g., the monohydrate or anhydrous form.

The amine oxides and other surfactants employed in cleaning composi¬ tions are frequently employed in conjunction with bleaching agents, such as sodium percarbonate or perborate — materials which are not surface-active themselves. It would be advantageous to develop a material which could serve both as the surfactant and the bleaching agent in such compositions.

Oswald et al., Journal of the American Chemical Society, March 1963, pp. 651-657, teach that lower trialkylamine oxides can form unstable hydrogen peroxide adducts which are highly soluble in water and alcohol and only slightly soluble in ether, acetone, and benzene and some of which are crystallizable. Summary of Invention

The present invention resides in:

(1) novel amine oxide perhydrates corresponding to the formula:

in which R is a primary alkyl group containing 8-24 carbons; R' is methyl, ethyl, or 2-hydroxyethyl; R" is independently selected from methyl, ethyl, 2-hydroxyethyl, and primary alkyl groups containing 8-24 carbons; x is 0 or 1; y is 1 or 2; and x+y is <2, (2) processes for preparing the novel perhydrates by reacting an amine oxide or amine oxide monohydrate corresponding to the formula

with y molar proportion^) of hydrogen peroxide, (3) cleaning compositions comprising the novel perhydrates as surfactants and bleaching agents, and (4) processes for using those cleaning compositions.

Detailed Description

The amine oxides utilized in preparing the perhydrates of the invention may be any compounds corresponding to the formula RR'R"NO xH₂ in which R is a primary alkyl group containing 8-24 carbons; R' is methyl, ethyl, or 2-hydroxyethyl; R" is independently selected from methyl, ethyl, 2-hydroxyethyl, and primary alkyl groups containing 8-24 carbons; and x is 0 or 1. The primary alkyl groups in these compounds may be branched-chain groups; but the preferred compounds are those in which at least most of the primary alkyl groups have a straight chain.

Exemplary of these amine oxides are N-octyldimethylamine oxide, N,N-didecylmethylamine oxide, N-decyl-N-dodecylethylamine oxide, N-dodecyldi- memylamineoxide,N-tetradecyldimemylaι___n^ amine oxide, N-tetradecyl-N-emyl-2-hydroxyethylamine oxide, N,N-ditetradecyl-2- hydro_yethylamine oxide, N-hexadecyldimethylamine oxide, N-hexadecyldi-2- hydroxye ylamine oxide, N-octadecyldimemylamine oxide, N,N-dieicosylethylamine oxide, N-docosyl-N-2-hydroxyethylmethylamine oxide, N-tetracosyldimethylamine oxide, the corresponding monohydrates, and mixtures thereof. When the anhydrous amine oxide or amine oxide monohydrate to be reacted with the hydrogen peroxide is not commercially available, it may be obtained by conventional techniques, e.g., by oxidizing the appropriate tert-amine with hydrogen peroxide in dilute aqueous solution and then recovering an amine oxide in anhydrous or monohydrate form in any suitable manner, e.g., spray-drying or evaporation. However, the desired anhydrous or monohydrate compound can be produced more easily and economically by (1) preparing an a ine oxide in which at least some of the molecules are dihydrate molecules and (2) removing all or part of the water of hydration by any suitable means.

In one of the preferred methods of preparing an amine oxide for use in the present invention, (1) the appropriate tert-amine is reacted with concentrated hydrogen peroxide in the presence, during at least the later stages of the reaction, of an organic solvent in which both the amine and amine oxide are soluble at the reaction temperatures but in which the amine oxide is insoluble at a lower temperature, and (2) the water content of the product is adjusted, if necessary to achieve a water/amine oxide mol ratio no higher than about 2.1/1 before the amine oxide is recovered. In this reaction: (A) the aqueous hydrogen peroxide is employed in at least a stoichiometric amount, and its amount and concentration are preferably such as to make it unnecessary to adjust the water content of the product at the end of the reaction,

(B) the organic solvent is used in an amount sufficient to maintain a stirrable reaction mixture and is preferably ethyl acetate, although other substantially inert esters, hydrocarbons, halohydrocarbons, and highly polar aprotic solvents are also utilizable,

(C) the reaction is conducted by adding the aqueous hydrogen peroxide to the amine, preferably at a controlled rate and preferably in the presence of carbon dioxide and/or a chelating agent (such as diethylenetriamine- pentaacetic acid) to improve the reaction rate, at a temperature of 20-100 ^βC, preferably 25-80 ° C, and

(D) the reaction πrb-rture is cooled at the end of the reaction to precipitate the amine oxide. Another preferred amine oxide synthesis is similar to that described above except for utilizing a liquefied gas, preferably liquefied carbon dioxide, as the reaction medium instead of an organic solvent.

When an amine oxide product prepared by the above-described processes has a water/amine oxide mol ratio in the range of about 1.9-2.1/1 at the time that the amine oxide is recovered, the amine oxide is recovered as a dihydrate. When the water/amine oxide mol ratio is lower than about 1.9/1, the recovered amine oxide contains some dihydrate molecules as well as monohydrate and anhydrous molecules.

These dihydrate-containing products have too high a water content to be useful per se in the process of the present invention. However, having lower water contents than amine oxides prepared by conventional techniques, they are more easily and economically converted to monohydrate or anhydrous form. This conversion may be accomplished by any suitable technique, such as those mentioned above. However, it is generally preferred to remove the excess water by azeotropic distillation or by vacuum drying.

The amount of water to be removed from an amine oxide dihydrate- containing product to form a starting material suitable for use in the present invention depends on the particular perhydrate desired. If a perhydrate containing one complexed mol of water and one complexed mol of hydrogen peroxide per mol of amine oxide is desired, water is removed from the dihydrate only until the monohydrate is obtained. However, it is necessary to remove all of the water from the dihydrate (or from a monohydrate) so as to form an anhydrous material when the desired perhydrate is a product containing 1-2 complexed mols of hydrogen peroxide and no complexed water per mol of amine oxide.

In the synthesis of the perhydrates of the invention, the anhydrous amine oxide or amine oxide monohydrate is reacted with hydrogen peroxide in such proportions that the sum of the molar proportions of complexed water and hydrogen peroxide in the reaction mixture is not more than two molar proportions per molar proportion of the amine oxide. Thus, the amount of hydrogen peroxide employed may be as much as two mols per mol of amine oxide when the starting amine oxide is anhydrous but should not exceed one molar proportion when the starting amine oxide is a monohydrate. The use of a dihydrate or excess hydrogen peroxide in the reaction leads to gelation on crystallization.

As in the amine oxide dihydrate syntheses described above, the process of the invention is advantageously conducted in a solvent from which the product can be easily crystallized by simply lowering the temperature. It is thus preferred to conduct the reaction by (1) mixing the amine oxide starting material with the appropriate amount of a concentrated hydrogen peroxide, i.e., an aqueous hydrogen peroxide having a concentration of 50-80%, preferably 70%, by weight in such a solvent and (2) cooling the solution to crystallize the perhydrate thus formed. Exemplary of the solvents which may be used in the reaction are:

(1) saturated and unsaturated aliphatic, cycloaliphatic, and aromatic esters such as methyl formate, ethyl acetate, 1-butenyl formate, 2- isobutenyl propionate, cyclohexyl hexanoate, phenyl acetate, phenethyl propionate, ethyl 2-methyl benzoate, butyl 4-butoxybenzoate, ethylene glycol diacetate, glycerol monoleate, glycerol monostearate, glycerol distearate, glycerol tributyrate, and glucose dibutyrate,

(2) liquid aliphatic, cycloaliphatic, and aromatic hydrocar¬ bons such as hexane, isohexane, heptane, 2-ethylhexane, octane, isooctane, cyclohexane, cyclooctane, toluene, and mixtures thereof with up to about 10% (e.g., 2-10%) by weight of a polar co-solvent, such as isopropanol or other alcohol,

(3) aromatic halohydrocarbons such as chlorobenzene, dichlorobenzene, bromobenzene, chlorotoluene, and 2,4-dichlorotoluene, and

(4) highly polar aprotic solvents such as dimethylf ormamide, dimethylacetamide, diethylformamide, diethylacetamide, and mixtures thereof. Since alcohol and acetone are solvents in which the products of the invention are highly soluble and from which crystallization therefore would not be possible, they are not suitable for use in the process.

The preferred solvents for use in the reaction are the alkyl alkanolates, especially those in which the alkyl groups contain 1-5 carbons and the alkanoic moieties contain 2-5 carbons, e.g., the methyl, ethyl, propyl, isopropyl, butyl, sec- butyl, t-butyl, isobutyl, and amyl acetates, propionates, butyrates, and valerates. Ethyl acetate is particularly preferred.

The temperature at which the reaction is conducted may be any temperature at which the reaction will occur without decomposition of the product — usually a temperature in the range of 20-80 ° C. Since an elevated temperature is not required to achieve reaction, it is generally preferred to accomplish the reaction at room temperature.

When the reactants have been mixed at the desired reaction temperature, the desired perhydrate is formed, and the reaction mixture may then be immediately cooled to a temperature at which the product most easily crystallizes from the product solution or slurry, e.g., a temperature in the range of 0-15 "C. However, if desired, the product solution or slurry may be diluted with more of the same solvent used in the reaction and/or with a different solvent prior to crystallization. After the product has been crystallized, it may be recrystallized one or more times to increase its purity.

The crystallized product may be recovered by conventional means, e.g., filtration or centrifugation, and it is usually also desirable to dry it, e.g., by vacuum drying.

The products of the invention are perhydrates which, whether they have two hydrogen peroxide molecules, one hydrogen peroxide molecule, or one hydrogen peroxide molecule and one water molecule complexed with the amine oxide molecule, are surprisingly heat stable and thus capable of functioning both as bleaching agents and surfactants in applications such as laundry detergents, "color-safe" oxygen bleaches, and hard surface cleaners.

Aqueous compositions employed to clean and bleach soiled materials in the practice of the invention typically have an amine oxide content of 0.25-90% by weight and a peroxide content consistent with the nature of the particular perhydrate used in preparing them. They contain an amount of water which is both sufficient to dissolve the perhydrate and suitable for the type of washing to be accomplished, e.g., laundering of clothes, washing of dishes, cleaning of floors or walls, oven cleaning, or spot cleaning; and they may also contain additional ingredients, such as those conventionally employed in cleaning compositions, e.g., other surfactants, additional bleaching agents, bleach activators, pH modifiers, builders, perfumes, and processing aids.

The aqueous cleaning/bleaching compositions can be formed essentially just as they are about to be used, e.g., by (1) separately adding a small amount of the perhydrate, a normal amount of water, and any other materials desired to be utilized, such as a conventional solid or liquid laundry detergent and/or a conventional laundry bleach, to a laundry washing machine and forming a dilute aqueous composition in the washing machine itself or (2) combining a small amount of the perhydrate with any optional ingredients and the amount of water ordinarily used for dishwashing to form a somewhat more concentrated aqueous composition in a dishpan. Alternatively, the perhydrate may be premixed with one, some, or all of any other solid ingredients to be used and/or with at least some of the water to be employed so as to form an amine oxide-containing composition that can be packaged for later use.

It would be impractical, of course, to package an aqueous clean¬ ing/bleaching composition containing the total amount of water that would be utilized for normal dish- or laundry-washing. However, it could be desirable to prepare, package, and ship a concentrate containing a smaller amount of water, e.g., up to about 30% by weight of the composition, and (1) use such a concentrate in an application which would not require it to be diluted further, e.g., spot cleaning, or (2) dilute it to the desired concentration when it is to be used.

Whether it is preferable for the aqueous cleaning/bleaching composition to be formed solely from the amine oxide perhydrate and water or for it to contain additional ingredients depends mostly on the type of clean¬ ing/bleaching to be accomplished, although cost may also be a determining factor. In this connection, it should be noted that:

(1) As already indicated, the composition can accomplish both cleaning and bleaching without the aid of other ingredients. However, the performance of the composition can be improved by the inclusion of other materials. For example, it is very desirable to include one or more abrasives in a composition to be used for oven cleaning or the like, and the ability of the composition to clean and bleach laundry can be improved by the inclusion of sodium perborate.

(2) The inclusion of additional ingredients can sometimes decrease the total cost of the compositions, frequently without reducing their effectiveness, and at least occasionally with a beneficial impact on their effectiveness.

When it is desired to utilize ingredients in addition to the water and perhydrate in forming the aqueous compositions, comparable performance is achieved whether each of the ingredients is separately combined with the others at the same time or two or more of the ingredients are combined with one another before being mixed with the other ingredients. Thus, although it could be preferable from the aspect of convenience to use a packaged blend of all of the ingredients (except for any excessive amount of water), good results are also obtained, e.g., when the perhydrate, or a solution obtained by dissolving the perhydrate in water, is combined with the other ingredients during or just prior to the washing of the soiled materials to be cleaned and bleached.

The aqueous compositions of the invention and the solid compositions useful in preparing them, as already indicated, can contain any of the ingredients normally used in cleaning compositions (including the usual anionic, cationic, nonionic, and amphoteric surfactants) or bleaching compositions (including conventional bleaching agents and activators) as long as they also contain the essential perhydrate ingredient. Thus, when a solid composition suitable for packaging is to be prepared:

(1) it is frequently desirable to blend the perhydrate and any co- surfactant and/or co-bleaching agent with a pH modifier, such as sodium silicate; one or more processing aids, such as sodium sulfate or sodium carbonate; and optionally also a detergent builder, such as sodium tripolyphosphate, sodium mtrilo- triacetate, or a sodium aluminum silicate, as in the preparation of conventional hard surface cleaners, to form a solid composition comprising 1-20% by weight of surfactant, 1-20% by weight of bleaching agent, 1-20% by weight of pH modifier, 10-80% by weight of processing aid, and 0-50% by weight of builder,

(2) it can be desirable, as in the preparation of conventional laundry detergent powders, to blend the perhydrate with the aforementioned ingredients and with one or more anti-redeposition agents, such as sodium carboxymethyl- cellulose and sodium acrylates, to form a solid composition comprising 1-25% by weight of surfactant, 1-25% by weight of bleaching agent, 1-20% by weight of pH modifier, 10-80% by weight of processing aid, 0-50% by weight of builder, and 0.5- 5% by weight of anti-redeposition agent, and

(3) an improved oxygen bleach can be obtained by blending the perhydrate with sodium perborate and/or an activator, such as tetraacetylethylene- diamine, and optionally also with a builder and/or processing aid, such as those mentioned above, to form a solid composition containing 2-95% by weight of total bleaching agent, 5-80% by weight of processing aid, 0-50% by weight of builder, and 0-20% by weight of activator.

Particularly preferred embodiments of the invention include: (A) laundry detergent powders as described above in which the surfactant and bleaching agent are provided by a mixture of 25-75% by weight of the perhydrate and 75-25% by weight of sodium perborate,

(B) oxygen bleach powders as described above in which the bleaching agent makes up 5-95% of the total weight and is composed of a mixture of 25-75% by weight of the perhydrate and 75-25% by weight of sodium perborate,

(C) laundry detergent powders as described above containing 1-25% by weight of a mixture of 5-95% (preferably 25-75%) by weight of the perhydrate and 95-5% (preferably 75-25%) by weight of tetraacetylethylenediamine, and

(D) oxygen bleach powders as described above containing 5-95% by weight of a mixture of 5-95% (preferably 25-75%) by weight of the perhydrate and 95-5% (preferably 75-25%) by weight of tetraacetylethylenediamine.

In essence, the cleaning/bleaching compositions of the present invention may be regarded as conventional cleaning and/or bleaching compositions in which an amine oxide perhydrate has been used to replace all or part of the surfactant and/or all or part of the bleaching agent. They have the advantages of (1) utilizing a single material with both surfactant and bleaching properties, thus eliminating an actual need for two separate materials to accomplish those functions, (2) being able to effect cleaning and bleaching at temperatures of 40-50° C, thus making it unnecessary for abnormally high temperatures to be used, and (3) functioning well in the presence of the ingredients of conventional cleaning and/or bleaching compositions, thus permitting them to be used in conjunction with the known commercial compositions or components thereof.

The following examples are given to illustrate the invention and are not intended as a limitation thereof.

EXAMPLE I

Dissolve lOOg of N-tetradecyldimethylamine oxide monohydrate in 200 mL of ethyl acetate. Add 17.7g of 70% hydrogen peroxide and then cool the solution to 5 ° C to crystallize a product having the formula C₁₄H₂₉(CH₃)₂NO'H₂0'H₂0₂. Test the product for stability of the peroxide by heating it from 25 ° C to 200 ° C. Differential scanning calorimetry (DSC) shows no exotherm — evidence of the heat stability of the peroxide. EXAMPLE π

Repeat Example I except for replacing the N-tetradecyldimemylamine oxide monohydrate with an equimolar amount of anhydrous N-tetradecyldimethyl¬ amine oxide. Similar results are observed except that the product is a complex having the formula C₁₄H₂₉(CH₃)₂NO • H₂0₂.

EXAMPLE m Repeat Example II except for doubling the amount of hydrogen peroxide added. Similar results are observed except that the product is a complex having the formula C₁₄H₂₉(CH₃)₂NO-2H₂0₂.

COMPARATIVE EXAMPLE A

Repeat Example I except for adding 35g of the 70% hydrogen peroxide solution. Attempts to crystallize the product give gel rather than a solid product.

COMPARATIVE EXAMPLE B Repeat Example I except for replacing the monohydrate with N- tetradecyldimethylamine oxide dihydrate and adding 16.6g of 70% hydrogen peroxide. Attempts to crystallize the product give gel instead of a solid product.

EXAMPLE IV Part A Prepare two aqueous solutions of N-tetradecyldimethylamine oxide having an amine oxide content of 0.33% by weight by dissolving in water the appropriate amounts of N-tetradecyldimethylamine oxide monohydrate [i.e., C_L4H₂₉(CΗ₃)₂NO-H₂0] and N-tetradecyldimethylamine oxide monohydrate monoperhydrate [i.e., C₁₄H₂₉(CH₃)₂NO-H₂0-H₂0₂], respectively. Part B

Wash six swatches of red wine-stained cotton/polyester cloth at 38 ' C for 10 minutes in the solution formed from the monohydrate. Measure the reflectance of the washed swatches and compare it with the reflectance of the soiled swatches before washing. The change in reflectance is 9.9. Part C Repeat Part B except for using the solution formed from the monohy¬ drate/monoperhydrate. The change in reflectance is 12.1, showing that the use of the perhydrate in forming the solution provides a significantly cleaner cloth than the use of of an amine oxide having no perhydrate moiety.

EXAMPLE V

Repeat Example IV except for also including 0.4% by weight of tetraacetylethylenediamine (TAED) in each of the solutions. The changes in reflectance are 10.1 for the swatches washed in the solution formed from the monohydrate and 11.4 for the swatches washed in the solution formed from the monohydrate/monoperhydrate.

These results show that (1) the TAED conventionally used in some cleaning compositions to activate a sodium perborate-type bleaching agent may also be usefully employed in a hydrate- or perhydrate-derived amine oxide solution and (2) as in the absence of TAED, a cleaner cloth is provided by the perhydrate- derived solution. This ability of the perhydrate-derived amine oxide solution to be used in conjunction with TAED minimizes the modifications that would have to be made of commercial compositions to utilize the surfactant/bleaching agent of the invention.

EXAMPLE VI

Repeat Example IV except for employing blood-stained cot¬ ton/polyester as the soiled material and also including 0.4% by weight of sodium perborate in each of the solutions. The changes in reflectance are 27.5 for the swatches washed in the solution derived from the monohydrate and 34.8 for the swatches washed in the solution derived from the monohydrate/monoperhydrate. Thus, the sodium perborate most conventionally used as a bleaching agent in cleaning compositions can be used in the cleaning/bleaching compositions of the invention to enhance their performance and provide better cleaning than can be achieved when the perborate is used together with a solution derived from an amine oxide having no perhydrate moiety.

Claims

1. An amine oxide perhydrate corresponding to the formula:

wherein R is a primary alkyl group containing 8-24 carbons; R' is methyl, ethyl, or 2-hydroxyethyl; R" is independently selected from methyl, ethyl, 2-hydroxyethyl, and primary alkyl groups containing 8-24 carbons; x is 0 or 1; y is 1 or 2; and x+y is <2.

2. The perhydrate of claim 1 wherein both x and y are 1.

3. The perhydrate of claim 1 wherein x is 0 and y is 1.

4. The perhydrate of claim 1 wherein y is 2.

5. The perhydrate of any of the preceding claims wherein R' is methyl.

6. The perhydrate of claim 5 wherein R" is methyl and R is tetradecyl.

7. The perhydrate of claim 5 wherein R" is a primary alkyl group containing 8-24 carbons.

8. The perhydrate of claim 7 wherein R and R" are tetradecyl.

9. A process which comprises (1) reacting one molar proportion of an amine oxide corresponding to the formula RR'R'NO H₂0 with y molar proportions of an aqueous hydrogen peroxide having a concentration of 50-80% by weight in an organic solvent to form a solution of a perhydrate corresponding to the formula RR'R'NO -Λ:H₂0 JΗ₂0₂ and (2) cooling the solution to crystallize the perhydrate; R in the above formulas being a primary alkyl group containing 8-24 carbons; R' being methyl, ethyl, or 2-hydroxyethyl; R" being independently selected from methyl, ethyl, 2-hydroxyethyl, and primary alkyl groups containing 8-24 carbons; x being 0 or 1; y being 1 or 2; and the sum of x and y being <2.

10. A process which comprises washing a soiled material with an aqueous composition obtained by dissolving an amine oxide perhydrate of claim 1 in water to clean and bleach the soiled material.

11. The process of claim 10 wherein the aqueous composition contains at least one additional material selected from anionic, cationic, nonionic, and amphoteric co-surfactants, pH modifiers, processing aids, detergent builders, anti-redeposition agents, sodium perborate, and tetraacetylethylenediamine.

12. A cleaning formulation which is suitable for the production of an aqueous composition and which contains at least 1% by weight of an amine oxide perhydrate of claim 1 as a surfactant and bleaching agent.

13. The cleaning formulation of claim 12 which is a hard surface cleaning formulation having surfactant and bleaching agent contents of 1-20% by weight and also comprising 1-20% by weight of pH modifier, 10-80% by weight of processing aid, and 0-50% by weight of detergent builder.

14. The cleaning formulation of claim 12 which is a laundry detergent powder having surfactant and bleaching agent contents of 1-25% by weight and also comprising 1-20% by weight of pH modifier, 10-80% by weight of processing aid, 0-50% by weight of detergent builder, and 0.5-5% by weight of anti-redeposition agent.

15. The laundry detergent powder of claim 14 wherein the surfactant and bleaching agent are provided by a mixture of 25-75% by weight of the perhydrate and 75-25% by weight of sodium perborate.

16. A mixture of 25-75% by weight of an amine oxide perhydrate of claim 1 and 75-25% by weight of sodium perborate.

17. The laundry detergent powder of claim 14 containing 1-25% by weight of a mixture of 5-95% by weight of the perhydrate and 95-5% by weight of tetraacetylethylenediamine.

18. The laundry detergent powder of claim 17 wherein said mixture is composed of 25-75% by weight of the perhydrate and 75-25% by weight of tetraacetylethylenediamine.

19. A mixture of 5-95% by weight of an amine oxide perhydrate of claim 1 and 95-5% by weight of tetraacetylethylenediamine.

20. The mixture of claim 19 composed of 25-75% by weight of the perhydrate and 75-25% by weight of tetraacetylethylenediamine.

21. The cleaning formulation of claim 12 which is an oxygen bleach powder having a bleaching agent content of 2-95% by weight and also comprising 5-80% by weight of processing aid, 0-50% by weight of detergent builder, and 0-20% by weight of bleach activator.

22. The oxygen bleach powder of claim 21 containing 5-95% by weight of a bleaching agent which is a mixture of 25-75% by weight of the perhydrate and 75-25% by weight of sodium perborate.

23. The oxygen bleach powder of claim 21 containing 5-95% by weight of a mixture of 5-95% by weight of the perhydrate and 95-5% by weight of tetraacetylethylenediamine.

24. The oxygen bleach powder of claim 23 wherein said mixture is composed of 25-75% by weight of the perhydrate and 75-25% by weight of tetraacetylethylenediamine.