EP1979453B1 - Liquid washing or cleaning composition comprising particulate peracid bleach - Google Patents

Abstract

Aqueous surfactant- and bleaching agent containing liquid washing or cleaning agent, comprises particulate peroxycarboxylic acid and magnesium sulfate.

Description

The present patent application relates to hydrous liquid detergents or cleaners which contain peroxycarboxylic acid particles.

In detergents and cleaners in liquid form, especially if they contain water but also if they are anhydrous, it may due to chemical incompatibility of the individual ingredients to negative interactions of these ingredients with each other and to decrease their activity and thus decrease the washing performance of the agent as a whole come, even if it is stored relatively short. This decrease in activity relates in principle to all detergent ingredients which carry out chemical reactions in the washing process in order to contribute to the washing result, in particular bleaches and enzymes, although surfactant or sequestering ingredients which are responsible for solution processes or complexing steps, in particular in the presence of said chemically reactive ingredients in liquid, especially aqueous systems are not unlimited shelf life.

The phthalimidoperoxoalkanoic acids, such as 6-phthalimidoperoxohexanoic acid (PAP) are highly efficient bleaches, but are chemically very unstable in conventional liquid detergent formulations. In most cases, they completely decompose in a few days. Even if these liquid agents are freed from possible reactants of the peroxycarboxylic acid, such as unsaturated compounds, aldehydes, amines, chloride, etc., they still decompose in the presence of the surfactants, even if they are not oxidatively attacked. The reason for this may be that although the phthalimidoperoxoalkanoic acids are stable as only slightly water-soluble solids, they dissolve in the presence of surfactants, are highly reactive in this form, and are soluble in solution both via a bimolecular reaction with elimination of singlet oxygen and through hydrolysis the Phthalimidoalkansäure and H ₂ O ₂ decompose. However, the latter is practically not at low washing temperatures and in the concentrations occurring bleach active, so that in total the bleaching action of the agent is lost during storage.

Out EP 0 890 635 A2 Surfactant-containing liquid compositions are known which contain unimpregnated phthalimidoperoxohexanoic acid umd a maximum of 4 wt .-% magnesium sulfate. GB 2 281 744 A describes acidic liquid bleaches containing surfactants, uncovered amido-peracid, xanthan gum and a pH-jump system, and optionally magnesium sulfate. In EP 0 504 952 A1 The opinion is expressed that magnesium sulfate increases the water solubility of amido peracids by Mg salt formation. US 5,073,285 proposes to increase the stability of bleach particles in liquid detergents by lowering the pH and additionally adding stability-increasing polymers EP 0 240 481 A1 For example, liquid bleaches containing alkanediperoxyacids, linear alkylbenzenesulfonate and magnesium sulfate are known. EP 0 435 379 A1 describes imidoperoxycarboxylic acids which are coated with water-impermeable materials and which can be used in liquid agents, wherein they are stabilized in them by alkali alkylbenzenesulfonates.

It has been proposed on several occasions to solve the problem of the lack of stability of peroxycarboxylic acids in aqueous surfactant-containing liquid detergents by adjusting the solubility of both the peroxycarboxylic acid and the surfactant by setting a high electrolyte concentration (for example up to 30% Na sulfate in the liquid detergent) minimizes as much as possible. The systems thereby become microscopically biphasic, with a typically liquid-crystalline surfactant-rich phase being dispersed in a nearly surfactant-free continuous aqueous phase. By this measure, the dissolution of solid peroxycarboxylic acids can be greatly slowed down, whereby the decomposition rate decreases.

A problem with such formulations with, for example, sodium sulfate, however, is the phase stability and the storage stability, especially under climatic changing conditions. Under alternating climate, the solubility of the sodium sulfate changes very strongly, which can lead to precipitation and the growth of partially very large sulfate crystals in the liquid agents. In addition, the flow behavior of these agents is satisfactory and the production is complicated in practice, since also during the Manufacturing process due to the hydrate formation of sodium sulfate can first form large crystals that do not dissolve again in the thickened recipe.

Another approach to stabilize the bleaching agent is to coat it. It has been found, however, that the mere application of coating materials by no means always leads to an increase in the stability of the PAP. Coating, even with chemically inert materials such as paraffin in the systems under consideration, often even destabilizes the PAP. A coating that should be soluble in the application of the agent, usually in a water-containing product not completely diffusion-tight against water. Thus, although such a coating may possibly suppress the dissolution of the PAP, it does not suppress its hydrolysis to H ₂ O _2.

To solve the problem, it has also been proposed on various occasions not to incorporate all ingredients desirable for a good wash or remnant result into a liquid agent at the same time, but to provide the user of the composition with several components which he or she only shortly before or during the wash - Or cleaning process together and contain the only mutually compatible ingredients, which come together under the conditions of use used. The common dosing of several components is compared to dosing only a single liquid agent, however, often perceived by the user to be too expensive.

There is therefore still the problem of providing a storage-stable liquid agent, which also contains as many as possible, even incompatible with each other, necessary for a good washing or cleaning result ingredients.

The present invention, which aims to contribute to this, is an aqueous surfactant and bleach-containing liquid washing or cleaning agent having a particulate peroxycarboxylic acid and characterized in that it is the peroxycarboxylic acid which is solid at room temperature and which is a phthalimidoperoxoalkanoic acid Form and from over 4 wt .-% to 30 wt .-% magnesium sulfate.

Magnesium sulfate may be present in compositions of the invention in amounts up to 30% by weight. Preferably, amounts in the range of about 4 wt .-% to 20 wt.%, In particular in the range of 6 wt .-% to 10 wt.%. Magnesium sulfate may optionally also be used in mixtures with sodium and / or potassium sulfate.

The pH of compositions according to the invention is preferably between 2 and 6, in particular between 3 and 5.5 and more preferably between 3.5 and 5. If desired, water in inventive compositions can be added in amounts of up to 90% by weight, in particular 20% by weight. % to 75 wt .-%, be included; if necessary, however, these areas can also be exceeded or fallen short of.

The content of peroxycarboxylic acid in the compositions according to the invention is preferably 1% by weight to 25% by weight, in particular 2% by weight to 20% by weight and especially preferably 3% to 15% by weight. For example, 4-phthalimidoperoxobutanoic acid, 5-phthalimidoperoxopentanoic acid, 6-phthalimidoperoxohexanoic acid, 7-phthalimidoperoxoheptanoic acid and mixtures of these come into consideration. Preferred peracids include 6-phthalimidoperoxohexanoic acid (PAP).

The Peroxocarbonsäureteilchen contained in the agent according to the invention are coated. It is important that the coating material dissolves as little as possible in the liquid surrounding the coated Peroxocarbonsäureteilchen, but under the conditions of use of the agent (at higher temperature, by dilution with water changing pH, or the like) releases the coated peroxycarboxylic acid. A preferred coating material is one which consists, at least in part, of saturated fatty acid. The chain length of the fatty acid is preferably greater than C ₁₂ , particularly preferred is stearic acid. It has been found that, especially at low pH, the stability of PAP is very good, so that a coating for stabilizing the PAP may be unnecessary. However, it has been found that a coating of the peroxycarboxylic acid stabilizes enzymes when they are contained in an agent according to the invention. In particular, in the presence of enzymes, therefore, a PAP coating is advantageous.

A wrapping material is preferably applied to the particulate peroxycarboxylic acid in amounts such that the coated peroxycarboxylic acid particles consist of from 5% to 50% by weight of the wrapping material. The diameters of the coated Peroxocarbonsäureteilchen are preferably in Range from 100 μm to 1000 μm; Therefore, it starts from correspondingly finely divided Peroxocarbonsäurematerial and covers it with the wrapping material. Preferably, the procedure is to spray a fluidized bed of the peroxycarboxylic acid particles to be coated with a solution or slurry, preferably an aqueous solution, or a melt of the coating material, if present, removing the solvent or slurry, preferably water, by evaporation or solidified melted wrapping material by cooling and discharges the coated Peroxocarbonsäureteilchen in a conventional manner from the fluidized bed. In the case of the mentioned coating with fatty acids, preference is given to melt-coating.

In addition to water, surfactant, magnesium sulfate and the coated Peroxocarbonsäureteilchen a liquid detergent or cleaning agent according to the invention may contain all conventional ingredients in such agents, such as solvents, builders, enzymes and other auxiliaries such as soil repellants, thickeners, dyes and perfumes or the like.

In a preferred embodiment, it contains nonionic surfactants and / or organic solvents and optionally anionic surfactants, cationic surfactants and / or amphoteric surfactants.

Surfactants of the sulfonate type, alk (en) ylsulfates, alkoxylated alk (en) ylsulfates, ester sulfonates and / or soaps are preferably used as anionic surfactants.

As surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and Hydroxyalkansulfonaten and disulfonates, such as those from C ₁₂ -C ₁₈ monoolefins having terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₀ -C ₁₈ fatty alcohols, for example of coconut fatty alcohol, Tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₈ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis. Of washing-technical interest, C ₁₂ -C ₁₆ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates and C ₁₄ -C ₁₅ -alkyl sulfates and C ₁₄ -C ₁₆ -alkyl sulfates are particularly preferred. 2,3-alkyl sulfates, which may for example be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Also, the sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ -alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ -alcohols having on average 3.5 mol of ethylene oxide (EO) or C ₁₂ -C ₁₈ Fatty alcohols containing 1 to 4 EO are suitable. Due to their high foaming behavior, they are usually used in detergents only in relatively small amounts, for example in amounts of from 0 to 5% by weight.

Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), e.g. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

As further anionic surfactants are particularly soaps into consideration. Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, for. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. In particular, those soap mixtures are preferred which are composed of 50 to 100 wt .-% of saturated C ₁₂ -C ₁₄ fatty acid soaps and 0 to 50 wt .-% of oleic acid soap.

Another class of anionic surfactants is the class of ether carboxylic acids obtainable by the reaction of fatty alcohol ethoxylates with sodium chloroacetate in the presence of basic catalysts. They have the general formula: RO- (CH ₂ -CH ₂ -O) _p -CH ₂ -COOH with R = C ₁ -C ₁₈ and p = 0.1 to 20. Ethercarboxylic acids are water hardness insensitive and have excellent surfactant properties. Cationic surfactants contain the surface activity of the high molecular weight hydrophobic residue upon dissociation in aqueous solution in the cation. The most important representatives of the cationic surfactants are the quaternary ammonium compounds of the general formula: (R ¹ R ² R ³ R ⁴ N ⁺ ) X ^- . Where R _{1 is} C ₁ -C ₈ -alk (en) yl, R ² to R ⁴ are each independently C _n H _{2n + 1-px} - (Y ¹ (CO) R ⁵ ) _p - (Y ² H) _x , where n stands for integers without 0 and p and x stand for integers or 0. Y ¹ and Y ² are each independently O, N or NH. R ⁵ denotes a C ₃ -C ₂₃ -alk (en) yl chain. X is a counterion, which is preferably selected from the group of alkyl sulfates and alkyl carbonates. Particularly preferred are cationic surfactants in which the nitrogen group is substituted by two long acyl and two short alk (en) yl radicals.

Amphoteric or ampholytic surfactants have a plurality of functional groups which can ionize in aqueous solution and thereby - depending on the conditions of the medium - give the compounds anionic or cationic character. Near the isoelectric point, the amphoteric surfactants form internal salts, rendering them difficult or insoluble in water. Amphoteric surfactants are subdivided into ampholytes and betaines, the latter being present in solution as zwitterions. Ampholytes are amphoteric electrolytes, ie, compounds that have both acidic and basic hydrophilic groups and thus behave acidic or basic depending on the condition. Betaines are compounds with the atomic group R ₃ N ⁺ -CH ₂ -COO ^- which show typical properties of zwitterions.

The nonionic surfactants used are preferably alkoxylated and / or propoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and on average 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per mole of alcohol. Particular preference is given to C ₈ -C ₁₆ -alcohol alkoxylates, advantageously ethoxylated and / or propoxylated C ₁₀ -C ₁₅ -alcohol alkoxylates, in particular C ₁₂ -C ₁₄ -alcohol alkoxylates, having a degree of ethoxylation of 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 represent statistical averages, which may be an integer or a fractional number for a particular product. Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow range ethoxylates / propoxylates, NRE / NRP). additionally Fatty alcohols with more than 12 EO can also be used for these nonionic surfactants. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x , z. B. as compounds, especially with anionic surfactants, are used, in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol that represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.1 to 1.4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester. Particularly preferred are C ₁₂ -C ₁₈ fatty acid methyl esters having an average of 3 to 15 EO, in particular having an average of 5 to 12 EO.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is usually a carbon chain which should be long enough for the hydrophilic groups to have a carbon chain have enough distance to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.

Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.

However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides.

The amount of surfactants present in the agents according to the invention is preferably 0.1% by weight to 50% by weight, in particular 10% by weight to 40% by weight, and particularly preferably 20% by weight to 70% by weight. -%. Preferably, only mixtures of anionic and nonionic surfactants are used.

Polydiols, ethers, alcohols, ketones, amides and / or esters, in amounts of from 0 to 90% by weight, preferably 0.1 to 70% by weight, in particular 0.1 to 60% by weight, may preferably be used as organic solvents. %, in each case based on the amount of water available. Preference is given to low molecular weight polar substances, such as, for example, methanol, ethanol, propylene carbonate, acetone, acetonylacetone, diacetone alcohol, ethyl acetate, 2-propanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, dipropylene glycol monomethyl ether and dimethylformamide or mixtures thereof.

Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these Hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains, and graying. Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.

Particularly suitable are enzymatic agents obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities.

The proportion of enzymes or enzyme mixtures may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 3 wt .-%. They are preferably used in preparations according to the invention in particulate form.

Further detergent ingredients may be builders, cobuilders, soil repellents, alkaline salts and foam inhibitors, complexing agents, enzyme stabilizers, grayness inhibitors, optical brighteners and UV absorbers.

As a builder, for example, fine crystalline, synthetic and bound water-containing zeolite can be used, preferably zeolite A and / or P. As zeolite P zeolite MAP ^® (commercial product from Crosfield) is particularly preferred. Also suitable however are zeolite X and mixtures of A, X and / or P. Of particular interest is a co-crystallized sodium / potassium aluminum silicate of zeolite A and zeolite X, which as VEGOBOND AX ^® (a product of Condea) commercially available is. The zeolite may preferably be used as a spray-dried powder. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ 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 preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. In addition, phosphates can also be used as builders.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _2x-1 .yH ₂ O, where M is 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. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

The preferred builder substances also include amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delay-delayed and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" also "X-ray amorphous" understood. This means that in X-ray diffraction experiments, the silicates do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Especially preferred are densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates. Their content is generally not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished agent. In some cases it has been shown that in particular tripolyphosphates, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing power. Preferred amounts of phosphates are below 10 wt .-%, especially at 0 wt .-%.

Suitable organic builder substances which are useful as co-builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, 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 and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder effect, the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here. Further useable acidulants are known pH regulators, such as sodium bicarbonate and sodium hydrogen sulfate.

Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, may again be preferred from this group.

Suitable polymers may also include substances consisting partly or wholly of units of vinyl alcohol or its derivatives.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. When Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven particularly suitable. Their relative molecular weight, based on free acids, is generally from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol. The (co) polymeric polycarboxylates can be used either as an aqueous solution or, preferably, as a powder.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

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

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500 000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose which has a DE of 100. Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also yellow dextrins and white dextrins with relatively high molecular weights in the range from 2 000 to 30 000 g / mol are useful.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. These are products oxidized at C ₆ and / or with ring opening at C ₂ / C _{3 of} the saccharide ring. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

In addition, the compositions may also contain components which positively influence the oil and Fettauswaschbarkeit from textiles, so-called soil repellents. This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component. The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, and known from the prior art polymers phthalic acid and / or terephthalic acid or their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

When used in automatic washing processes, it may be advantageous to add conventional foam inhibitors to the compositions. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicones, paraffins or waxes.

As complexing agents or as stabilizers in particular for enzymes that are sensitive to heavy metal ions, the salts of polyphosphonic come into consideration. Here, the sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, but also diethylene triamine penta methylene phosphonate or ethylenediamine tetramethylene phosphonate are preferably used in amounts of from 0.1% to 5% by weight of the composition. Preference is given to nitrogen-free complexing agents.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of (co) polymeric carboxylic acids, glue, gelatin, salts of ethercarboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, for. Degraded starch, aldehyde levels, etc. Also, polyvinylpyrrolidone is useful. However, preference is given to cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, Hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and polyvinylpyrrolidone, for example, in amounts of 0.1 to 5 wt.%, Based on the means used.

The funds can optical brighteners such. B. derivatives of Diaminostilbendisulfonsäure or their alkali metal salts. Suitable z. B. 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, instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g. 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). Mixtures of the aforementioned brightener can be used.

In addition, UV absorbers can also be used. These are compounds with pronounced ultraviolet radiation absorptivity which contribute to improving the light fastness of dyes and pigments as well as textile fibers as light stabilizers (UV stabilizers) and also protect the wearer's skin from textile exposure to UV radiation. In general, the compounds which are active by radiationless deactivation are derivatives of benzophenone whose substituents, such as hydroxyl and / or alkoxy groups, are usually in the 2- and / or 4-position. Furthermore, substituted benzotriazoles are also suitable, furthermore in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic nickel complexes and natural products 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 and radiate back with wavelengths of blue light, so that they additionally have the effect of an optical brightener. Preferred UV absorbers are also triazine derivatives, eg. B. hydroxyaryl-1,3,5-triazine, sulfonated 1,3,5-triazine, o-hydroxyphenylbenzotriazole and 2-aryl-2H-benzotriazole and bis (anilinotriazinylamino) stilbene disulfonic acid and derivatives thereof. When UV absorbers can also be used to absorb ultraviolet radiation pigments such as titanium dioxide.

If desired, the compositions may contain further conventional thickeners and anti-settling agents and also viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as quaternized and / or ethoxylated hexamethylenediamines and any desired mixtures thereof. Preferred agents have a viscosity between 100 and 10,000 mPa.s when measured with a Brookfield viscometer at a temperature of 20 ° C and a shear rate of 20 min ^-1 . The compositions may contain other typical detergent and cleaner components such as perfumes and / or dyes, preference being given to those dyes which have no or negligible coloring action on the textiles to be washed. Preferred quantitative ranges of the totality of the dyes used are less than 1% by weight, preferably less than 0.1% by weight, based on the agent. The agents may optionally also white pigments such. B. TiO ₂ included.

Preferred agents have densities of 0.5 to 2.0 g / cm ³ , in particular 0.7 to 1.5 g / cm ³ , on. The density difference between the Peroxocarbonsäureteilchen and the liquid phase of the composition is preferably not more than 10% of the density of the two and is particularly so low that the Peroxocarbonsäureteilchen and preferably also optionally other suspended in the funds solid particles float in the liquid phase.

Examples Example 1: Preparation of an agent according to the invention

• 16,5% LAS (Maranil®, Cognis)
• 10 % Dehydol® LT 7 (Cognis)
• 1 % Sequion® 10 H 60 (Polygon Chemie)
• 0,3% Xanthan-Gum (Kelco)
• 8% Magnesiumsulfat
• 3% Zitronensäure
• 4% PAP-Granulat (Eureco® W, Solvay), versehen mit einem 20-gewichtsprozentigen Coating aus Stearinsäure (bezogen auf das Granulat), das durch Schmelzcoating in einer Wirbelschichtanlage (Aeromatic) hergestellt wurde.
• 3% Proteasegranulat (Everlase®, Novozymes)
• 0,2% Siliconöl (Wacker Chemie)
• 1 % Duftstoff
• NaOH zur Einstellung des pH-Wertes auf 5,0
• Wasser auf 100%

In a glass vessel with a propeller stirrer, an agent E1 according to the invention with the following composition (percentages by weight) was prepared:

• 16.5% LAS (Maranil®, Cognis)
• 10% Dehydol® LT 7 (Cognis)
• 1% Sequion® 10 H 60 (polygon chemistry)
• 0.3% xanthan gum (kelco)
• 8% magnesium sulfate
• 3% citric acid
• 4% PAP granules (Eureco® W, Solvay), provided with a 20% by weight coating of stearic acid (relative to the granules), which was produced by melt-coating in a fluidized bed system (Aeromatic).
• 3% protease granules (Everlase®, Novozymes)
• 0.2% silicone oil (Wacker Chemie)
• 1% perfume
• NaOH to adjust the pH to 5.0
• Water to 100%

Water was placed in the mixing vessel and mixed with the xanthan gum. Thereafter, magnesium sulfate and citric acid were dissolved therein. Thereafter, the surfactants and the phosphonate were added. After degassing, the solids were coated with PAP and enzyme granules and then the remaining ingredients added.

Example 2: Comparative Example 1

An agent V1 was otherwise prepared as in Example 1, but containing no magnesium sulfate (replaced by water).

Example 3: Comparative Example 2

An agent V2 was otherwise prepared as in Example 1, but magnesium sulfate was replaced with the same amount of sodium sulfate.

Example 4: Characterization

The agents of Examples 1 to 3 were evaluated for phase stability and bleach loss. The characterization was carried out after a storage period of 1 week under changing climatic conditions (temperature cycles between 25 ° C and 40 ° C) and constant 35 ° C.

The following results were obtained:

• Kristallbildung: E1: nein; V1: nein; V2: ja
• Phasenstabilität: E1: o.k.; V1: o.k. V2: Phasentrennung

• 35°C-Lagerung:

• Kristallbildung: E1: nein; V1: nein; V2: nein
• Phasenstabilität: E1: o.k.; V1: o.k. V2: o.k.
• PAP-Verlust: E1 : 8%; V1: 25%; V2: nicht bestimmt

Storage in alternating climate:

• Crystal formation: E1: no; V1: no; V2: yes
• Phase stability: E1: ok; V1: ok V2: phase separation

• 35 ° C storage:

• 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 unacceptable bleach loss. V2 showed crystal formation and phase instability under alternating climate storage conditions. The benefits of E1 outweigh.

Claims (9)

1. An aqueous surfactant- and bleach-containing liquid washing or cleaning agent, which comprises a particulate peroxocarboxylic acid, characterized in that it contains the peroxocarboxylic acid, solid at room temperature, which is a phthalimidoperoxoalkanoic acid, in coated form and from more than 4% by weight to 30% by weight of magnesium sulfate.
2. The agent according to claim 1, characterized in that it contains 1% by weight to 25% by weight, in particular 2% by weight to 20% by weight of peroxocarboxylic acid.
3. The agent according to claim 1 or 2, characterized in that the peroxocarboxylic acid is 6-phthalimidoperoxohexanoic acid (PAP).
4. The agent according to one of claims 1 to 3, characterized in that it contains up to 20% by weight of magnesium sulfate.
5. The agent according to one of claims 1 to 4, characterized in that it contains from 6% by weight to 10% by weight of magnesium sulfate.
6. The agent according to one of claims 1 to 5, characterized in that it contains 0.1% by weight to 50% by weight, in particular from 10% by weight to 40% by weight of surfactant.
7. The agent according to one of claims 1 to 6, characterized in that it contains a mixture of anionic and non-ionic surfactants.
8. The agent according to one of claims 1 to 7, characterized in that it has a pH value in the range from 2 to 6, in particular between 3 and 5.5.
9. The agent according to one of claims 1 to 8, characterized in that it the densities of the optionally coated peroxocarboxylic acid particles and the liquid phase of the agent do not deviate from each other by more than 10%.