EP1735423B1 - Liquid washing or cleaning agent having a bleaching agent that is enveloped with a water-soluble material - Google Patents

Abstract

An anhydrous liquid washing or cleaning agent, which contains a bleaching agent and a particulate peroxycarboxylic acid that is enveloped with a water-soluble material.

Description

The present patent application relates to anhydrous liquid detergents or cleaners containing water-soluble coated Peroxocarbonsäureteilchen.

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, especially in the presence of said chemically reactive ingredients in liquid, especially aqueous systems are not unlimited shelf life.

The WO-A-98/00515 discloses anhydrous liquid cleaners containing bleach and coated bleach activator.

In order to solve this problem, it has been proposed on various occasions not to incorporate all ingredients desirable for a good washing or cleaning result into a liquid agent at the same time, but to provide the user of the composition with several components that he or she only shortly before or during washing. or should combine cleaning process and containing only compatible with each 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 consequently the problem of providing a storage-stable liquid agent which contains as many as possible, even incompatible, necessary for a good washing or cleaning result ingredients.

The present invention, which seeks to remedy this, is an anhydrous bleach-containing liquid detergent or cleaning agent, which is characterized in that it contains a particulate peroxocarboxylic acid, which is coated with a water-soluble material.

By anhydrous is meant an agent which contains not more than 10% by weight, in particular not more than 5% by weight, of water. The term "water-soluble" should be understood to mean that the so-called material dissolves without residue to at least 3 g / l, in particular at least 6 g / l in water of pH 7 at room temperature. Preferably, a water-soluble material at the concentration, which results from the amount of the coated with him particle in the final washing or cleaning agent in the usual washing or cleaning conditions, residue-free soluble.

The content of peroxycarboxylic acid which results from the amounts of peroxycarboxylic acid particles coated is preferably from 1% by weight to 25% by weight, in particular from 2% by weight to 20% by weight and particularly preferably 3, in the compositions according to the invention % to 15% by weight. If the peroxycarboxylic acid is not in solid form at room temperature, it may have been formulated in a known manner prior to wrapping with the water-soluble material using inert carrier materials in particulate form; However, a peroxycarboxylic acid which is solid at room temperature is preferably used in encased form. The peroxycarboxylic acid, which may also be referred to as organic peracid, may carry aliphatic and / or cyclic, including heterocyclic and / or aromatic, radicals. There are, for example, peroxoic acid, peroxoacetic acid, peroxopropionic acid, peroxohexanoic acid, peroxobenzoic acid and their substituted derivatives such as m-chloroperoxobenzoic acid, mono- or di-peroxophthalic acids, 1,12-diperoxododecanedioic acid, nonylamidoperoxoadipic acid, 6-hydroxyperoxohexanoic acid, 4-phthalimidoperoxobutanoic acid, 5-phthalimidoperoxopentanoic acid, 6 Phthalimidoperoxohexanoic acid, 7-phthalimidoperoxoheptanoic acid, N, N'-terephthaloyl-di-6-aminoperoxohexanoic acid, and mixtures of these. Preferred peracids include 6-phthalimidoperoxohexanoic acid.

Coating materials for the peroxycarboxylic acids must have said water solubility and be capable of being applied to the peroxycarboxylic acid as a melt or as a solution in water or in another vaporizable solvent, in devices commonly used for coating particles, for example granulators or fluid bed equipment can.

As wrapping material, for example, below-mentioned nonionic surfactants and / or organic polymers are suitable. Polymeric polycarboxylates, in particular polymerization products of acrylic acid, methacrylic acid or maleic acid or copolymers of at least two of these, are suitable, which can also be used in completely or at least partially neutralized form, in particular in the form of the alkali metal salts. Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. Alternatively or in addition to polymeric polycarboxylate, it is also possible to use phosphonic acids or optionally functionally modified phosphonic acids, for example hydroxy- or aminoalkanephosphonic acids, and / or their alkali metal salts. Examples of phosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or the dialkali salt or the tetraalkali salt of this acid, ethylenediamine tetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and their higher homologs. In the said alkali metal salts and also in all other parts of the present text, sodium is the respectively preferred alkali metal.

Also with the aid of ether bonds anionic or nonionic modified celluloses, especially alkali carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose or methylhydroxypropyl cellulose, alone or in mixtures with one another, or corresponding starch derivatives can be used as a wrapping material.

Also useful as the wrapping material are polyvinyl alcohols. These are not accessible by direct polymerization, since the necessary basic monomer vinyl alcohol does not exist. Polyvinyl alcohols are therefore polymer-analogous reactions by hydrolysis, but technically especially by alkali-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol) in solution produced. Commercially available polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range of about 500-2500 (corresponding to molar masses of about 20000-100000 g / mol) have different degrees of hydrolysis of 98-99 wt .-% or 87-89 mole%. So they are partially hydrolyzed polyvinyl acetates with a residual content of acetyl groups of about 1-2 wt .-% and 11-13 mol%. The polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity. Conversion temperatures of the polyvinyl alcohols are dependent on the acetyl group content, the distribution of the acetyl groups along the chain and the tacticity of the polymers. Fully saponified polyvinyl alcohols have a glass transition temperature of 85 ° and a melting point of 228 °. The corresponding values for partially hydrolyzed (87-89%) products are considerably lower at approx. 58 ° and 186 °, respectively. Polyvinyl alcohols, which normally have a density of about 1.2-1.3 g / cm ³ , are soluble in water and a few highly polar organic solvents such as formamide, dimethylformamide, and dimethylsulfoxide, of (chlorinated) hydrocarbons, esters, depending on the degree of hydrolysis. Fats and oils are not attacked. Polyvinyl alcohols are classified as toxicologically harmless and are at least partially biodegradable. Preferably, polyvinyl alcohols are used which have a saponification number in the range from 20 to 350, in particular in the range from 100 to 300 and particularly preferably from 150 to 250. The degree of polymerization is preferably in the range from 100 to 3000, in particular from 150 to 2000 and particularly preferably from 250 to 500.

In a preferred embodiment of the invention, the wrapping material is selected from polyvinyl alcohols, alkyl cellulose ethers, hydroxyalkyl cellulose ethers, alkyl hydroxyalkyl cellulose ethers, and mixtures thereof.

The 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 the range of 100 microns to 1000 microns; Therefore, it starts from correspondingly finely divided Peroxocarbonsäurematerial and covers it with the wrapping material. Preferably, this is done by spraying a fluidized bed of the peroxycarboxylic acid particles to be coated with a solution or slurry, preferably an aqueous solution, of the coating material, thereby removing by evaporation the solvent or slurry, preferably water, and discharging the coated peroxycarboxylic acid particles from the fluidized bed in a manner which is in principle conventional.

In addition to the coated Peroxocarbonsäureteilchen an inventive anhydrous liquid detergent or cleaning agent may contain all conventional ingredients in such agents, such as surfactants, 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. It is further preferred that the solvents or solvent mixtures used in the liquid phase of the agent are surfactants or at least contain a proportion which corresponds in particular to 10% by weight to 99% by weight of the total solvent to 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, 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 prefers. 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. Also 2,3-alkyl sulfates, which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 are manufactured and can 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 ₂₄ 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.

Production and application are for example in Soaps, oils, fats, waxes 101, 37 (1975 ); 115, 235 (1989 ) and Surfactants Deterg. 25, 308 (1988 ).

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 formyl: (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 halides, 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 - depending on the conditions of the medium - give the compounds anionic or cationic character (see DIN 53900, July 1972). Near the isoelectric point (around pH 4), the amphoteric surfactants form internal salts, making 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 degrees of ethoxylation and propoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow range ethoxylates / propoxylates, NRE / NRP). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. 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, in particular fatty acid methyl ester, as described for example in the Japanese patent application JP-A-58/217 598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods. 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, in particular 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 that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them 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 according to the German patent application DE-A-43 21 022 or dimer alcohol bis- and trimeralcohol tris-sulfates and ether sulfates according to the international patent application WO-A-96/23768 , End-capped dimeric and trimeric mixed ethers according to the German patent application DE-A-195 13 391 They are characterized 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, as described in international patent applications WO 95/19953 . WO 95/19954 and WO95-A- / 19955 to be discribed.

The amount of surfactants contained in the agents according to the invention is preferably from 0.1% by weight to 90% by weight, in particular from 10% by weight to 80% by weight, and particularly preferably from 20% by weight to 70% by weight. -%.

Such surfactants can account for the total liquid content of the composition of the invention, but also entirely or at least proportionally by other organic Solvents that are preferably water-miscible, replaced or supplemented. In this latter case, solid representatives of the surfactants mentioned can also be used at room temperature in amounts such that a liquid agent still results.

As organic solvents here are preferably polydiols, ethers, alcohols, ketones, amides and / or esters, in amounts of 0 to 90 wt .-%, preferably 0.1 to 70 wt .-%, in particular 0.1 to 60 wt. -% used. 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 of 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. These are 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 .-%.

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 sub-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. Such crystalline layered silicates are described, for example, in the European patent application EP-A-0 164 514 described. 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, wherein β-sodium disilicate can be obtained, for example, by the process described in International Patent Application WO-A-91/08171 is described.

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" is also understood to mean "X-ray amorphous". 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. Such so-called X-ray-amorphous silicates, which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in the German patent application DE-A-44 00 024 described. 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 respective acidic telephones, 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. 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 to be 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 allylsulfonic acids, such as in the EP-B-0 727 448 Allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example, those according to the DE-A-43 00 772 as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to the DE-C-42 21 381 as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymers are those described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particularly preferred are polyaspartic acids or their salts and derivatives, of which in the German patent application DE-A-195 40 086 is disclosed that they also have a bleach-stabilizing effect in addition to Cobuilder properties.

Further suitable builder substances are polyacetals which are obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as in the European patent application EP-A-0 280 223 described, can be obtained. 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 from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrups having a DE of between 20 and 37, and so-called yellow dextrins and white dextrins having higher molecular weights in the range of 2,000 to 30,000 g / mol. A preferred dextrin is in the British patent application 94 19 091 described.

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. Such oxidized dextrins and methods of their preparation are, for example, from the European patent applications EP-A-0 232 202 . EP-A-0 427 349 . EP-A-0 472 042 and EP-A-0 542 496 as well as the international patent applications WO-A-92/18542 . WO-A-93/08251 . WO-A-93/16110 . WO 94/28030 . WO-A-95/07303 . WO 95/12619 and WO 95/20608 known. Also suitable is an oxidized oligosaccharide according to the German patent application DE-A-196 00 018 , 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), the synthesis of which, for example, in US 3,158,615 is described, preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat US 4,524,009 . US 4,639,325 in the European patent application EP-A-0 15 0 930 and Japanese Patent Application JP-A-93 / 339,896 to be discribed. 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. Such co-builders are described, for example, in the international patent application WO 95/20029 described.

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 polymers of phthalic acid and / or terephthalic acid or derivatives thereof known from the prior art, 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.

Other suitable ingredients of the compositions are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof; In particular, alkali metal carbonate and amorphous alkali metal silicate, especially sodium silicate with a molar ratio of Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.

Preferred agents include alkaline salts, builder and / or co-builders, preferably sodium carbonate, zeolite, crystalline layered sodium silicates and / or trisodium citrate, in amounts of from 0.5 to 70% by weight, preferably 0.5 to 50% by weight. , in particular 0.5 to 30 wt .-% anhydrous substance.

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. With advantages are also mixtures used from various foam inhibitors, for example those of silicones, paraffins or waxes. The foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamides are preferred.

Suitable complexing agents or stabilizers, in particular for per compounds and enzymes which are sensitive to heavy metal ions, are the salts of polyphosphonic acids. Here, the sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriamine penta-methylenephosphonate or ethylenediamine tetramethylenephosphonate in amounts of from 0.1 to 5% by weight are preferably used.

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 from 0.1 to 5% by weight, based on the compositions, 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 those in the European patent applications EP-A-0 374 751 . EP-A-0 659 877 . EP-A-0 682 145 . EP-A-0 728 749 and EP-A-0 825 188 disclosed UV absorbers such as 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. As UV absorbers, it is also possible to use pigments which absorb ultraviolet radiation, such as titanium dioxide.

The compositions may contain other conventional thickeners and anti-settling agents and 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 mixtures thereof. Preferred agents exhibit measurements with a Brookfield viscometer at a temperature of 20 ° C and a shear rate of 50 min ^-1, a viscosity below 10 000 mPa · s.

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 can 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 difference in density between the coated 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 coated Peroxocarbonsäureteilchen and preferably also optionally other particles contained in the solid particles float in the liquid phase, which optionally can be facilitated by the use of a thickening agent mentioned above.

Claims (10)

1. Water-free bleach-containing liquid washing or cleaning composition, characterized in that it comprises a particulate peroxocarboxylic acid enveloped with a water-soluble material.
2. Composition according to Claim 1, characterized in that the enveloped peroxocarboxylic acid particles consist of the enveloping material to an extent of 5% by weight to 50% by weight.
3. Composition according to Claim 1 or 2, characterized in that the diameters of the enveloped peroxocarboxylic acid particles are in the range of 100 µm to 1000 µm.
4. Composition according to any one of Claims 1 to 3, characterized in that the peroxocarboxylic acid is 6-phthalimidoperoxohexanoic acid.
5. Composition according to one of Claims 1 to 4, characterized in that the enveloping material is an organic polymer.
6. Composition according to Claim 5, characterized in that the enveloping material is selected from polyvinyl alcohols, alkyl cellulose ethers, hydroxyalkyl cellulose ethers, alkyl hydroxyalkyl cellulose ethers and mixtures thereof.
7. Composition according to any one of Claims 1 to 6, characterized in that it contains 1% by weight to 25% by weight, especially 2% by weight to 20% by weight, of peroxocarboxylic acid.
8. Composition according to any one of Claims 1 to 7, characterized in that the solvent or solvent mixtures used in the liquid phase of the composition are surfactants, or contain at least a proportion of surfactants which corresponds especially to 10% by weight to 99% by weight of the overall solvent.
9. Composition according to any one of Claims 1 to 8, characterized in that it has a density in the range from 0.5 to 2.0 g/cm³, especially 0.7 to 1.5 g/cm³.
10. Composition according to any one of Claims 1 to 9, characterized in that the densities of the enveloped peroxocarboxylic acid particles and of the liquid phase of the composition differ from one another by no more than 10%.