Liquid Washing or Cleaning Composition Comprising Particulate Peracid Bleach
Kind Code:

Aqueous, liquid compositions which comprise a surfactant, a bleaching agent and magnesium sulfate, wherein the bleaching agent comprises a particulate peroxocarboxylic acid which may optionally be coated, along with uses therefor are described.

Schmiedel, Peter (Dusseldorf, DE)
Bellomi, Luca (Dusseldorf, DE)
Von Rybinski, Wolfgang (Dusseldorf, DE)
Orlich, Bernhard (Dusseldorf, DE)
Jonke, Hermann (Dusseldorf, DE)
Application Number:
Publication Date:
Filing Date:
Henkel AG & Co. KGaA (Dusseldorf, DE)
Primary Class:
Other Classes:
257/E21.642, 257/E21.703, 257/E27.112, 257/E21.633
International Classes:
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Primary Examiner:
Attorney, Agent or Firm:
Henkel Corporation (Rocky Hill, CT, US)
1. 1-10. (canceled)

11. An aqueous, liquid composition comprising a surfactant, a bleaching agent and magnesium sulfate, wherein the bleaching agent comprises a particulate peroxocarboxylic acid.

12. The composition according to claim 11, wherein the particulate peroxocarboxylic acid is present in an amount of 1% to 25% by weight, based on the composition.

13. The composition according to claim 11, wherein the particulate peroxocarboxylic acid is present in an amount of 2% to 20% by weight, based on the composition.

14. The composition according to claim 11, wherein the particulate peroxocarboxylic acid is solid at room temperature.

15. The composition according to claim 11, wherein the particulate peroxocarboxylic acid is coated.

16. The composition according to claim 14, wherein the particulate peroxocarboxylic acid is coated.

17. The composition according to claim 12, wherein the particulate peroxocarboxylic acid is solid at room temperature.

18. The composition according to claim 12, wherein the particulate peroxocarboxylic acid is coated.

19. The composition according to claim 17, wherein the particulate peroxocarboxylic acid is coated.

20. The composition according to claim 11, wherein the particulate peroxocarboxylic acid comprises a phthalimidoperoxyalkanoic acid.

21. The composition according to claim 11, wherein the particulate peroxocarboxylic acid comprises 6-phthalimidoperoxyhexanoic acid.

22. The composition according to claim 12, wherein the particulate peroxocarboxylic acid comprises a phthalimidoperoxyalkanoic acid.

23. The composition according to claim 12, wherein the particulate peroxocarboxylic acid comprises 6-phthalimidoperoxyhexanoic acid.

24. The composition according to claim 11, wherein the magnesium sulfate is present in an amount of up to 30% by weight, based on the composition.

25. The composition according to claim 12, wherein the magnesium sulfate is present in an amount of up to 30% by weight, based on the composition.

26. The composition according to claim 11, wherein the magnesium sulfate is present in an amount of greater than 4% up to 20% by weight, based on the composition.

27. The composition according to claim 11, wherein the surfactant is present in an amount of 0.1% by weight to 50% by weight, based on the composition.

28. The composition according to claim 11, wherein the surfactant comprises a mixture of an anionic surfactant and a nonionic surfactant.

29. The composition according to claim 11, wherein the composition has a pH value of 2 to 6.

30. The composition according to claim 11, wherein the particulate peroxocarboxylic acid and a liquid phase of the composition have densities which differ from each other by no more than 10%.


The present invention concerns aqueous liquid washing or cleaning compositions comprising peroxocarboxylic acid particles.

Liquid washing or cleaning compositions are subject to negative interactions of their components that can result in reduction of their activity and thus to reduction of the washing ability of the composition because of chemical incompatibilities of the individual components, even on relatively brief storage, especially if they contain water, but even if they are free of water. This reduction in activity basically affects all the components of the washing composition that can carry out chemical reactions in the washing process to contribute to the result of the washing, especially bleaching agents and enzymes, although surfactant or sequestrant components responsible for dissolution processes or complexing steps, especially in the presence of those chemically reactive ingredients in liquid, especially aqueous, systems do not have unlimited storage stability.

The phthalimidoperoxoalkanoic acids, such as 6-phthalimidoperoxyhexanoic acid (PAP), are highly efficient bleaching agents, but they are particularly unstable in ordinary liquid washing composition formulations. They usually decompose completely within a few days. Even if potential reactants with the peroxocarboxylic acids, such as unsaturated compounds, aldehydes, amines, chloride, etc., are removed from these liquid compositions they nevertheless decompose in the presence of the surfactants, even if those are not oxidatively attacked. The reason for that may be that the phthalimidoperoxyalkanoic acids are stable only as substances with very low water solubility but dissolve in the presence of surfactants. In that form they are highly reactive and decompose in the solution not only through a bimolecular reaction with loss of singlet oxygen but also by hydrolysis to the phthalimidoalkanoic acid and H2O2. The latter, however, is practically inactive as a bleach, especially at low washing temperatures and in the concentrations that occur, so that, in sum, the bleaching action of the composition is lost on storage.

It has occasionally been suggested that the problem of inadequate stability of peroxocarboxylic acids in aqueous liquid washing compositions be solved by making up a high electrolyte concentration (for instance, up to 30% sodium sulfate in the liquid washing composition) to reduce the solubility of both the peroxocarboxylic acid and the surfactant as much as possible. That results in a system that is microscopically biphasic, with a typically liquid-crystalline surfactant-rich phase dispersed in a continuous aqueous phase that is almost free of surfactant. That measure can greatly reduce the dissolution of solid peroxocarboxylic acids, thus reducing the rate of decomposition.

However, such formulations with sodium sulfate, for example, have the problems of phase stability and storage stability, especially under varying climatic conditions. The solubility of sodium sulfate changes very greatly with climatic variation. That can result in precipitation and in the growth of sulfate crystals, some of them very large, in the liquid composition. Also, the flow behavior of these compositions is unsatisfactory and production is complicated in practice, because large crystals can form even during the production process due to formation of sodium sulfate hydrate, and they do not redissolve in the thickened formulation.

Another attempt to stabilize the bleaching agent consists of coating it. It is found, though, that just application of coating materials does not by any means always result in increasing the stability of PAP in particular. Coating often actually results in destabilization of the PAP, even with the materials such as paraffin that are chemically inert in the systems under consideration here. A coating that is intended to be soluble in use of the composition is generally a product that contains water and does not completely prevent diffusion of water. Thus such a coating may indeed suppress the dissolution of the PAP but not its hydrolysis to H2O2.

It has often also been suggested at times that the problem can be solved by not incorporating all the ingredients desirable for a good washing or cleaning result into the liquid medium at the same time. Instead, the user should be provided multiple components that are combined only just before or during the washing or cleaning process, and which contain only ingredients that are compatible with each other, which are used together only under the application conditions. But the user often considers the joint addition of multiple components too much trouble.

Thus there still remains the problem of preparing a storage-stable liquid composition that also contains all the components needed for good washing or cleaning, even if they are incompatible with each other.

The object of the present invention, that is intended to provide a contribution in this respect, is an aqueous liquid washing or cleaning composition containing surfactant and bleaching agent, comprising a particulate peroxocarboxylic acid, which is characterized in that it comprises magnesium sulfate.

The compositions according to the invention can contain magnesium sulfate in proportions of up to 30% by weight if desired. Proportions in the range from greater than 4% by weight to 20% by weight are preferred, and those in the range of 6% by weight to 10% by weight are particularly preferred. Magnesium sulfate can optionally also be used in mixtures with sodium sulfate and/or potassium sulfate.

The pH of compositions according to the invention is preferably between 2 and 6, especially between 3 and 5.5 and particularly preferably between 3.5 and 5. The composition according to the invention can contain water if desired in proportions up to 90% by weight, especially 20% by weight to 75% by weight. However, the proportion can be higher or lower than those ranges if desired.

The proportion of peroxocarboxylic acid in the compositions according to the invention is preferably 1% by weight to 25% by weight, especially 2% by weight to 20% by weight, and especially preferably 3% by weight to 15% by weight. If the peroxocarboxylic acid is not solid at room temperature, it can be formulated into particulate form using inert carrier materials in known ways. Preferably, though, a peroxocarboxylic acid that is solid at room temperature is used in an optionally coated form. The peroxocarboxylic acids, which can also be designated as organic peracids, can carry aliphatic and/or cyclic, including heterocyclic and/or aromatic groups. Those that can be considered include peroxoformic acid, peroxoacetic acid, peroxopropanoic acid, peroxohexanoic acid, peroxobenzoic acid and substituted derivatives of them such as m-chloro-peroxobenzoic acid, the mono- or di-peroxophthalic acids, 1,12-diperoxo-dodecanoic acid, nonylamidoperoxoadipic acid, 6-hydroxyperoxohexanoic acid, 4-phthalimidoperoxobutanoic acid, 5-phthalimidoperoxopentanoic acid, 6-phthalimidoperoxohexanoic acid, 7-phthalimidoperoxohexanoic acid, N,N′-terephthaloyl-di-6-aminoperoxohexanoic acid and mixtures of them. The preferred peracids include the phthalimidoperoxyalkanoic acids, especially 6-phthalimidoperoxyhexanoic acid (PAP).

The peroxocarboxylic acid particles in the composition according to the invention can if desired be coated. There it is important that the coating material have as little solubility as possible in the liquid composition surrounding the coated peroxocarboxylic acid particles, but that it release the coated peroxocarboxylic acid under the use conditions of the composition (high temperature, pH changes due to dilution with water, or the like). A preferred coating material is one comprising at least partially saturated fatty acids. Here the chain length of the fatty acid is preferably greater than C12. Stearic acid is particularly preferred. It was found that the stability of PAP in particular is very good, especially at low pH, so that a coating to stabilize PAP may be superfluous. It was found, though, that coating the peroxocarboxylic acid stabilizes the enzymes if they are included in a composition according to the invention. Thus a PAP coating is advantageous, especially in the presence of enzymes.

If a coating material is present, it is preferably applied to the particulate peroxocarboxylic acid in proportions such that the coated peroxocarboxylic acid particles comprise 5% by weight to 50% by weight coating material. The diameters of the coated peroxocarboxylic acid particles are preferably in the range of 100 μm to 1000 μm. Therefore one starts with appropriately finely divided peroxocarboxylic acid material and coats it with the coating material. It is preferable to proceed so that a fluidized bed of the peroxocarboxylic acid particles being coated is sprayed with a solution or suspension, preferably an aqueous solution, or with a melt of the coating material. Then the solvent or suspending agent, preferably water, if present, is removed by evaporation, or the melted coating material is solidified by cooling, and the coated peroxocarboxylic acid particles are removed from the fluidized bed in essentially the usual manner. For the coating with fatty acids as discussed, a melt coating is preferred.

Along with water, surfactant, magnesium sulfate and the optionally coated peroxocarboxylic acid particles, a liquid washing or cleaning composition according to the invention can contain all the ingredients usual in such compositions, such as, for example, solvents, builders, enzymes, and other additives such as soil repellants, thickeners, colorants and fragrances or the like.

A preferred embodiment contains nonionic surfactants and/or organic solvents as well as optionally anionic surfactants, cationic surfactants, and/or amphoteric surfactants.

Surfactants of the sulfonate type, alk(en)yl sulfates, alkoxylated alk(en)yl sulfates, ester sulfonates and/or soaps are preferred as anionic surfactants.

The surfactants of the sulfonate type that are considered preferable are C9-C13-alkylbenzenesulfonates, olefin sulfonates, i.e., mixtures of alkene and hydroxyalkane sulfonates, and disulfonates, such as are obtained, for instance, from C12-C18 monoolefins with terminal or internal double bonds, by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.

The preferred alk(en)yl sulfates are the alkali salts, preferably the sodium salts, of the sulfuric acid hemiesters of the C10-C18-fatty alcohols such as those of coco fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C8-C20-oxoalcohols and those hemiesters of secondary alcohols having that chain length. Also preferred are alk(en)yl sulfates of the specified chain length that contain a synthetic straight-chain alkyl group made on a petrochemical basis. The C12-C16-alkyl sulfates, C12-C15-alkyl sulfates, C14-C15-alkyl sulfates and C14-C16-alkyl sulfates are particularly preferred from the viewpoint of laundry technology. 2,3-alkyl sulfates, such as can be obtained as commercial products of the Shell Oil Company under the DAN® name, are also suitable anionic surfactants.

The sulfuric acid hemiesters of straight-chain or branched-chain C7-C21-alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl branched C9-C11-alcohols having an average of 3.5 moles of ethylene oxide (EO) or C12-C18-fatty alcohols having 1 to 4 EO are suitable. They are usually used only in relatively low proportions in laundry compositions because of their high foaming, for instance, in proportions of 0 to 5% by weight.

The esters of α-sulfofatty acids (ester sulfonates), such as the α-sulfonated methyl esters of hydrogenated coco, palm nut or tallow fatty acids are also suitable.

Soaps in particular can be considered as other anionic surfactants. Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and particularly those derived from natural fatty acids, such as coco, palm nut or tallow fatty acids. Particularly preferred soap mixtures are those made up of 50 to 100% by weight saturated C12-C24 fatty acids and 0 to 50% by weight of oleic acid soap.

A further class of anionic surfactants is the class of ether carboxylic acids accessible by reaction of fatty alcohol ethoxylates with sodium chloroacetate in the presence of basic catalysts. They have the general formula:


with R=C1-C18 and p=0.1 to 20. Ether carboxylic acids are not sensitive to water hardness and exhibit outstanding surfactant properties.

Cationic surfactants contain the high-molecular-weight hydrophobic group that causes the surface activity in the cation when they dissociate in aqueous solution. The major representatives of the cationic surfactants are the quaternary ammonium compounds having the general formula: (R1R2R3R4N+)X. Here R1 stands for C1-C8-alk(en)yl, R2 to R4, independently of each other, stand for CnH2n+1−p−x—(Y1(CO)R5)p—(Y2H)x, in which n stands for integers other than zero, and p and x stand for integers or zero. Y1 and Y2, independently of each other, stand for O, N or NH. R5 designates a C3-C23-alk(en)yl chain. X is a counterion, preferably selected from the group of alkyl sulfates and alkyl carbonates. Cationic surfactants in which the nitrogen group is substituted with two long acyl groups and two short alk(en)yl groups are especially preferred.

Amphoteric or ampholytic surfactants have multiple functional groups that can ionize in aqueous solution and, depending on the conditions of the medium, give the compounds anionic or cationic character. Near the isoelectric point the anionic surfactants form internal salts, so that they can be poorly soluble or insoluble in water. Amphoteric surfactants are subdivided into ampholytes and betaines, with the latter occurring as zwitterions in solution. Ampholytes are amphoteric electrolytes, i.e., compounds having both acidic and basic hydrophilic groups, which therefore act acidic or basic, depending on the conditions. Compounds having the atomic grouping R3N+—CH2—COO which exhibit the typical properties of zwitterions are called betaines.

The nonionic surfactants used preferably are alkoxylated and/or propoxylated, especially primary, alcohols having preferably 8 to 18 C atoms and an average of 1 to 12 moles of ethylene oxide (EO) and/or 1 to 10 moles of propylene oxide (PO) per mole of alcohol. C8-C16-alcohol alkoxylates are specially preferred, as are advantageously ethoxylated and/or propoxylated C10-C15-alcohol alkoxylates, especially C12-C14-alcohol alkoxylates having a degree of ethoxylation between 2 and 10, preferably between 3 and 8, and/or a degree of propoxylation between 1 and 6, preferably between 1.5 and 5. The stated degrees of ethoxylation and propoxylation are statistical averages, which can be integers or fractional numbers for a particular product. Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow range ethoxylates/propoxylates, NRE/NRP). In addition to those nonionic surfactants, it is also possible to use fatty alcohols with more than 12 EO. Examples of those are (tallow) fatty alcohols having 14 EO, 16 EO, 20 EO, 30 EO or 40 EO.

Alkyl glycosides having the general formula RO(G)x can also be used as other nonionic surfactants, e.g., as compounds, preferably with anionic surfactants, in which R indicates a primary straight-chain or methyl-branched aliphatic group, especially methyl-branched at the 2 position, having 8 to 22, preferably 12 to 18 C atoms, and G is the symbol for a glycose unit having 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization, x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10. Preferably, x is 1.1 to 1.4.

Another class of nonionic surfactants used preferably, either as the only nonionic surfactants or in combination with other nonionic surfactants, especially together with alkoxylated fatty alcohols and/or alkyl glycosides, is that of the alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters. The C12-C18-fatty acid methyl esters having an average of 3 to 15 EO, especially having an average of 5 to 12 EO, are particularly preferred.

Nonionic surfactants of the amine oxide type, such as N-cocoalkyl-N,N-dimethylamine oxide and N-tallow-alkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamides, can also be suitable. The proportion of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, particularly not more than half of that.

The so-called gemini surfactants can also be considered as surfactants. By this we mean generally those compounds that contain two hydrophilic groups and two hydrophobic groups per molecule. These groups are, as a rule, separated by a so-called “spacer”. This spacer is generally a carbon chain that should be long enough that the hydrophilic groups are separated sufficiently that they can act independently of each other. Such surfactants are generally distinguished by unusually low critical micelle concentrations and the ability to reduce greatly the surface tension of water. In special cases, though, the term ‘gemini surfactants’ is understood to mean not just dimeric but also trimeric surfactants.

Examples of suitable gemini surfactants include sulfated hydroxy-mixed ethers or dimer alcohol-bis and trimer alcohol-tris-sulfates and -ether sulfates. End-group capped dimeric and trimeric mixed ethers are particularly distinguished by their bifunctionality and multifunctionality. The end-group-capped surfactants have good wetting properties and are low-foaming, so that they are particularly suitable for use as machine washing or cleaning compositions.

Gemini-polyhydroxyfatty acid amides or poly-polyhydroxyfatty acid amides can also be used.

The proportion of surfactants in the compositions according to the invention is preferably 0.1% by weight to 50% by weight, especially 10% by weight to 40% by weight, and especially preferably 20% by weight to 70% by weight. It is preferable to use only mixtures of anionic and nonionic surfactants.

Polydiols, ethers, alcohols, ketones, amides and/or esters can be used preferably as organic solvents, in proportions of 0 to 90% by weight, preferably 0.1 to 70% by weight, particularly 0.1 to 60% by weight, based on the proportion of water present. Low-molecular-weight polar substances are preferred, such as methanol, ethanol, propylene carbonate, acetone, acetonylacetone, diacetone alcohol, ethyl acetate, 2-propanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, dipropylene glycol monomoethyl ether and dimethylformamide or mixtures of them.

Enzymes to be considered are in particular those of the class of hydrolases, such as the proteases, esterases, lipases or lipolytically acting enzymes, amylases, cellulases or other glycosylhydrolases, and mixture of the enzymes named. In the laundry, all these hydrolases contribute to removal of spots, such as spots containing protein, fat or starch, and graying. Cellulases and other glycosylhydrolases can contribute to color retention and to increasing the softness of the textile by removal of pilling and microfibrils. Oxidoreductases can also be used for bleaching or to limit color transfer.

Enzymatic agents obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly well suited. It is preferable to use proteases of the subtilisin type and especially proteases obtained from Bacillus lentus. Enzyme mixtures are of special interest, such as mixtures of protease and amylase, or protease and lipase or lipolytically acting enzymes, or protease and cellulase, or cellulase and lipase or lipolytically acting enzymes, or mixtures of protease, amylase and lipase or lipolytically acting enzymes, or protease, lipase or lipolytically acting enzymes and cellulase, but especially mixtures containing protease and/or lipase or mixtures with lipolytically acting enzymes. Examples of such lipolytically acting enzymes are the well-known cutinases. Peroxidases or oxidases have also proved suitable in some cases. The suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. The cellulases used preferably are cellobiohydrolases, endoglucanases and β-glucosidases, also called cellobiases, or mixtures of them. As the various cellulase types differ in their CMCase and Avicelase activities, the desired activities can be adjusted by deliberate mixtures of the cellulases.

The proportion of enzymes or enzyme mixtures can, for example, be about 0.1 to 5% by weight, preferably 0.1 to about 3% by weight. It is preferable to formulate them in particulate form in the compositions according to the invention.

Further components of laundry detergents can be builders, co-builders, soil repellants, alkaline salts, foam inhibitors, complexing agents, enzyme stabilizers, antiredeposition agents, optical brighteners and UV absorbers.

For example, finely crystalline synthetic zeolite containing bound water can be used as the builder, preferably Zeolite A and/or P. Zeolite MAP® (commercial product of Crosfield), for instance, is particularly preferred as Zeolite P. However, Zeolite X is also suitable, as are mixtures of A, X and/or P. A co-crystallized sodium potassium aluminum silicate of Zeolite A and Zeolite X, available as VEGOBOND AX® (commercial product of Condea) is also of special interest. The zeolite can preferably be used as the spray-dried powder. If the zeolite is used as the suspension, it can contain minor additions of nonionic surfactants as stabilizers, such as 1 to 3% by weight, based on the zeolite, of ethoxylated C12-C18 fatty alcohols having 2 to 5 ethylene oxide groups, C12—CO14 fatty alcohols having 4 to 5 ethylene oxide groups, or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measuring method: Coulter counter) and contain preferably 18 to 22% by weight, especially 20 to 22% by weight, bound water. Phosphates can also be used as builder substances.

Crystalline lamellar sodium silicates having the general formula NaMSixO2x+1.y H2O, in which M means sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, and preferred values for x are 2, 3 or 4, are suitable substitutes or partial substitutes for zeolites and phosphates. Preferred crystalline lamellar silicates having the formula stated are those in which M stands for sodium and x has the value of 2 or 3. In particular, both β- and δ-sodium disilicate, Na2Si2O5.y H2O.

The preferred builder substances also include amorphous sodium silicates with the Na2O:SiO2 ratio of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and particularly 1:2 to 1:2.6, with delayed dissolution and secondary washing properties. The delayed dissolution, in comparison with the ordinary commercial amorphous sodium silicates, can be produced in various ways, such as by surface treatment, compounding, compacting/compression or by overdrying. In the context of this invention the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates do not produce sharp X-ray reflections in X-ray diffraction experiments, such as are typical of crystalline substances, but always show one or more maxima of the scattered X-radiation with a width of several degrees of diffraction angle. However, there can be very good to particularly good builder properties if the silicate particles give diffuse or even sharp diffraction maxima in electron diffraction experiments. This can be interpreted that the products have microcrystalline regions of sizes of 10 to a few hundreds of nm, with values up to a maximum of 50 nm, and especially up to a maximum of 20 nm, preferred. Compressed/compacted amorphous silicates, compounded amorphous silicates, and overdried X-ray-amorphous silicates are particularly preferred.

It is obviously also possible to use the generally known phosphates as builder substances, as long as such use need not be avoided for ecological reasons. The sodium salts of the orthophosphates, the pyrophosphates, and particularly the tripolyphosphates are especially suitable. Their proportion is generally not greater than 25% by weight, preferably not greater than 20% by weight, based on the finished composition in each case. It has been found in some cases that tripolyphosphates in particular, even at low proportions up to a maximum of 10% by weight, based on the finished composition, combined with other builder substances, lead to a synergistic improvement of the secondary washing ability. Preferred proportions of phosphates are less than 10% by weight, especially 0% by weight.

Organic builders usable as co-builders are, for example, the polycarboxylic acids that are usable as their sodium salts. The term ‘polycarboxylic acids’ is understood to mean those carboxylic acids having more than one acid function. Examples of them are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their derivatives or mixtures of them. Preferred salts are the salts of the polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of those.

The acids themselves can also be used. Beside their builder action, the acids typically have the property of an acidification component, and so also serve to establish a lower and gentler pH for washing or cleaning compositions. Of those, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and arbitrary mixtures of them must be mentioned. Other usable acidification agents are the known pH regulators such as sodium bicarbonate and sodium bisulfate.

Polymeric polycarboxylates are also suitable as builders. Examples include the alkali metal salts of polyacrylic acid or polymethacrylic acids, such as those having a relative molecular weight of 500 to 70,000 g/mol.

In the sense of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molecular weights, Mw of the particular acid form, basically determined by gel permeation chromatography (GPC) using a UV detector. The measurement is made with respect to an external polyacrylic acid standard, which gives realistic molecular weight values because of its structural relation with the polymers being examined. These values differ clearly from the molecular weight figures found when polystyrene sulfonic acids are used as standards. The molecular weights measured versus polystyrene sulfonic acids are as a rule distinctly higher than the molecular weights stated in this document.

Suitable polymers are, in particular, polyacrylates, preferably having molecular weights of 2,000 to 20,000 g/mol. The short-chain polyacrylates having molecular weights of 2,000 to 10,000 g/mol, again, are preferred because of their superior solubility, with molecular weights of 3,000 to 5,000 g/mol particularly preferred.

Suitable polymers can also comprise substances consisting wholly or partially of units of vinyl alcohol or its derivatives.

Copolymeric polycarboxylates are also suitable, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid that contain 50 to 90% by weight acrylic acid and 50 to 10% by weight maleic acid have proved to be particularly suitable. Their relative molecular weights, based on the free acids, are generally 2,000 to 70,000 g/mol, preferably 20,000 to 50,000 g/mol, and particularly 30,000 to 40,000 g/mol. The (co)polymeric polycarboxylates can be used either as the aqueous solution or, preferably, as the powder.

The polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid as monomers to improve the water solubility.

Biodegradable polymers of more than two different monomer units are especially preferred, such as those containing as the monomers salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives, or containing as monomers salts of acrylic acid and of 2-alkylallylsulfonic acid and sugar derivatives.

Other preferred copolymers are those having as monomers preferably acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polycarboxylic acids having 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures of them, and from polyol carboxylic acids such as gluconic acid and/or glucoheptonic acid.

Other suitable organic builder substances are dextrins, such as oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be done by usual processes, such as acid-catalyzed or enzyme-catalyzed processes. They are preferably hydrolysis products with average molecular weights in the range of 400 to 500,000 g/mol, such as oligomers of polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be done by usual processes, such as acid-catalyzed or enzyme-catalyzed processes. They are preferably hydrolysis products with average molecular weights in the range of 400 to 500,000 g/mol. A polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, especially 3 to 30, is preferred, where DE is a useful measure of the reducing action of a polysaccharide in comparison with dextrose, which has a DE of 100. Maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 are usable, as are also the so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2,000 to 30,000 g/mol.

The oxidized derivatives of such dextrins are products of their reaction with oxidizing agents which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function. These are products oxidized at C6 and/or, in the case of ring opening of the saccharide ring at C2/C3. A product oxidized at C6 of the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable cobuilders. It is preferable to use ethylendiamine-N,N′-disuccinate (EDDS) in the form of its sodium or magnesium salt. Glycerol disuccinate and glycerol trisuccinate are also preferred in this connection. Suitable proportions are 3 to 15% by weight in formulations containing zeolite and/or silicate.

Other usable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which can optionally also be in the lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group, as well as no more than two acid groups.

The compositions can also contain components which positively influence the ability to wash oil and grease out of textiles. These are called soil repellants. This effect becomes particularly apparent if a textile previously washed several times with a laundry detergent according to the invention that contains these oil-dissolving and grease-dissolving components is made dirty. The preferred oil-dissolving and grease-dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose having 15 to 30% by weight methoxyl groups and 1 to 15% by weight hydroxypropyl groups, based in each case on the nonionic cellulose ether, as well as polymers of phthalic acid and/or terephthalic acid or their derivatives, known at the state of the art, especially polymers of ethylene terephthalates and/or or polyethylene glycol tetephthalates or anionically and/or nonionically modified derivatives of them. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

It can be advantageous to add the usual foam inhibitors to compositions for use in washing machines. Examples of suitable foam inhibitors are soaps of natural or synthetic origin having a high proportion of C18-C24 fatty acids. Suitable non-surfactant-like foam inhibitors include, for example, organopolysiloxanes and mixtures of them with microfine, optionally silanized silicic acid, as well as paraffins, waxes, microcrystalline waxes and mixtures of them with silanized silicic acid or bistearylethylenediamide. Mixtures of various foam inhibitors, such as mixtures of silicones, paraffins or waxes are also used to advantage.

The salts of polyphosphonic acids can be considered as complexing agents or as stabilizers, especially for enzymes that are sensitive to heavy metal ions. The sodium salts of, for example, 1-hydroxyethan-1,1-diphosphonate are used preferably, as well as those of diethylenetriaminepentamethylene phosphonate or ethylenediaminetetramethylene phosphonate, in proportions of 0.1% by weight to 5% by weight in the composition. Nitrogen-free complexing agents are preferred.

Antiredeposition agents have the function of keeping dirt removed from the fibers suspended in the liquor and thus preventing reattachment of the dirt. Colloids, mostly of organic nature, are suitable for this, such as the water-soluble salts of (co)polymeric carboxylic acids, glue, gelatins, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose, or salts of acidic sulfuric acid esters of cellulose or of starch. Polyamides containing water-soluble acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those named above can also be used, such as degraded starches, aldehyde starches, etc. Polyvinylpyrrolidone is also usable. However, it is preferable to use cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methyl hydroxyethylcellulose, methyl hydroxypropylcellulose, methyl carboxymethylcellulose, and mixtures of them, as well as polyvinylpyrrolidone at, for instance, proportions of 0.1 to 5% by weight, based on the composition.

The compositions can contain optical brighteners, such as derivatives of diaminostilbenesulfonic acid or their alkali metal salts. For example, salts of 4,4′-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2′-disulfonic acid or compounds of similar structure having in place of the morpholino group a diethanolamino group, a methylamino group, an anilino group, or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type can also be present, such as the alkali salts of 4,4′-bis(2-sulfostyryl)-diphenyl, 4,4′-bis(4-chloro-3-sulfostyryl)diphenyl, or 4-(4-chlorostyryl)-4′-(2-sulfostyryl)diphenyl). Mixtures of the brighteners named above can also be used.

UV absorbers can also be used. Those are compounds with marked ability to absorb ultraviolet radiation. They are light-protection agents (UV stabilizers) and contribute to improving the light resistance of dyes, pigments and textile fibers. They also protect the skin of the wearer of textile products from UV radiation penetrating through the textile. In general, these compounds that act by nonradiative deactivation are derivatives of benzophenone, with substituents such as hydroxy and/or alkoxy groups, mostly in the 2- and/or 4-positions. Substituted benzotriazoles are also suitable, as well as acrylates substituted with phenyl in the 3 position (cinnamic acid derivatives), optionally with cyano groups in the 2 position; salicylates; organic nickel complexes; and natural materials such as umbelliferone and the body's own urocanic acid. In a preferred embodiment, the UV absorbers absorb UV-A and UV-B radiation and optionally UV-C radiation, radiating back the wavelengths of blue light, so that they also have the effect of optical brighteners. Other preferred UV absorbers are triazine derivatives such as hydroxyaryl-1,3,5-triazines, sulfonated 1,3,5-triazine, o-hydroxyphenylbenzotriazole and 2-aryl-2H-benzotriazoles as well as bis(anilinotriazinylamino)stilbenedisulfonic acid and its derivatives. Pigments that absorb ultraviolet radiation, such as titanium dioxide, can also be used as UV absorbers.

The compositions can optionally also comprise other commonly used thickeners and antisettling agents as well as viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as quaternized and/or ethoxylated hexamethylenediamine and arbitrary mixtures of them. Preferred compositions have a viscosity between 100 and 100,000 mPa·s when measured with a Brookfield viscosimeter at a temperature of 20° C. and a shear rate of 20 min−1. The compositions can comprise other typical components of washing or cleaning compositions such as perfumes and/or colorants. The preferred colorants are those that have no, or negligible, staining action on the textiles being washed. Preferred proportions for the totality of colorants used are less than 1% by weight, and preferably less than 0.1% by weight, based on the composition. The composition can optionally comprise white pigments such as TiO2.

Preferred compositions have densities of 0.5 to 2 g/cm3, especially 0.7 to 1.5 g/cm3. The density difference between the peroxocarboxylic acid particles and the liquid phase of the composition is preferably not greater than 10% of the density of one of the two, and is particularly so low that the peroxocarboxylic acid particles and preferably other solid particles that may occur in the composition float in the liquid phase.


Example 1

Preparation of a Composition According to the Invention

A composition E1 with the following composition (in percent by weight) was prepared in a glass vessel with a propeller stirrer:

16.5% LAS (Maranil®, Cognis)

10% Dehydrol® LT 7 (Cognis)

1% Sequion® 10H 60 (Polygon Chemie)

0.3% Xanthan gum (Kelco)

8% Magnesium sulfate
3% Cinnamic acid
4% PAP Granulation (Eureco® W, Solvay), having a 20% by weight coating (based on the granulation) of stearic acid, made by melt-coating in a fluidized bed apparatus (Aeromatic)

3% Protease Granulation (Everlase®, Novozymes)

0.2% Silicone oil (Wacker Chemie)

1% Fragrance

NaOH to adjust the pH to 5.0
Water to make 100%.

Water was put into the stirred vessel and mixed with the xanthan gum. Then magnesium sulfate and citric acid were dissolved. Then the surfactant and phosphonate were added. After degassing, the solids, coated PAP and the enzyme granulation were added, and then the remaining components.

Example 2

Comparison Example 1

A composition V1 was made up as in Example 1, except that it contained no magnesium sulfate (replaced with water).

Example 3

Comparison Example 2

A composition V2 was made up as in Example 1, except that magnesium sulfate was replaced with the same amount of sodium sulfate.

Example 4


The compositions from Examples 1 to 3 were evaluated for phase stability and loss of the bleaching agent. The characterization was done after storage for 1 week under alternating climate conditions (temperature cycles between 25° C. and 40° C.) and a constant 35° C.

The following results were obtained:

Storage in alternating climate:
Crystal formation:E1: no; V1: no; V2: yes
Phase stability:E1: OK; V1: OK; V2: phase separation
Storage at 35° C.:
Crystal formation:E1: no; V1: no; V2: no
Phase stability:E1: OK; V1: OK; V2: OK
PAP loss:E1: 8%; V1: 25%; V2: not determined

V1 showed an unacceptable loss of bleaching agent. V2 showed crystal formation and phase instability under alternating climate conditions. The advantages of E1 are predominant.