EP1104801A1 - Storage-stable bleach containing detergents - Google Patents

Abstract

Particulate detergent comprises surfactants and bleaching agents and is (partially) sprayed with a protective layer.

Description

The present invention relates to a particulate washing and cleaning agent, containing surfactants and bleaching agents and optionally other usual ingredients.

Detergents and cleaning agents have already been described many times in the literature, they usually contain surfactants, builders and often also bleaches and / or Enzymes. Bleaching agents and enzymes each have a targeted effect on so-called bleachable ones Soiling or on enzymatically removable soiling. Both the bleaches and enzymes lose a large part of them when stored Activity. Bleaching agents, which are usually peroxide-containing substances especially unstable to water, also air humidity, and decompose slowly into the corresponding oxides so that the bleaching activity is reduced.

For example, enzymes are sensitive to temperature and lose one when stored significant part of their enzyme activity when bleaching agents are present.

The development of new detergents and cleaning agents has been significant Efforts have been made to increase the washing activity of the agents. The increase The washing activity can usually only be carried out a short time after production watch, whereas after prolonged storage activity due to the above described interactions decrease significantly over time.

In the German patent application DE 196 51 446 for incorporation in Particulate detergent and cleaning agents described suitable enzyme granules Enzymes and inorganic and / or organic carrier material and a uniform have outer pigment-containing coating layer. The coating layer consists of a coating system which is 5% by weight to 70% by weight of finely divided water-insoluble Pigment, 45 wt% to 90 wt% water-soluble solid at room temperature organic matter with a melting point in the range from 40 ° C to 70 ° C and up to 20 Wt .-% free-flowing improver contains.

German patent application DE 196 44 244 describes a method for coating temperature-sensitive granules described in a fluidized bed apparatus, in which one uses a meltable coating material and that to a melting temperature molten coating material kept at a temperature exceeding 20 ° C. Spray air, which has at least the same temperature, via nozzles into one with sprayed granulate filled vortex chamber and the outer jacket on a Temperature of 20 to 50 ° C holds.

The present invention was based on the object of containing a storage-stable bleach To provide detergents and cleaning agents in solid form, which about is stable for a long period of time, which means that the activity of sensitive Substances hardly or not reduced at all over this period.

Surprisingly, it was found that when one washes in particulate and Detergents at least partially coat the particles with a protective coating provides the activity of the sensitive substances and thus the washing activity overall is preserved even over long storage periods.

The present invention accordingly relates to a particulate washing and Cleaning agents containing surfactants, bleaches and, if appropriate, other customary ones Ingredients, which is characterized in that the particles at least partially are provided with a protective layer.

The particulate detergents and cleaners according to the present invention can in the form of powders, granules, extrudates or moldings, in particular also in tablet form. The individual particulate components can have a uniform structure or a mixture of different be particulate components.

In the sense of the present invention means that the particles at least partially are provided with a protective layer that either all or only part of the total Particles present in the medium have such a protective layer, regardless of whether it is uniform particles (solids) or a mixture of different particles, which in their entirety the finished washing and Form detergent. A particularly good maintenance of washing activity is achieved when at least 65% of the particles present on average have a Protective layer are provided. The thickness of the protective layer is preferably 0.1 μm up to 100 µm.

Suitable coating agents for forming the protective layer according to the invention especially those substances and substance mixtures that solidify at room temperature are, in particular those which have a melting point in the range from 40 ° C. to 200 ° C. exhibit. Water-soluble organic substances with a Melting point in the range mentioned to 50 wt .-% to 100 wt .-% Protective layer used.

Among water-soluble substances as they are in the context of the present invention are used with particular preference, are understood to be those which occur in a Temperature of 30 ° C to at least 50 g / l, especially at least 80 g / l in water to solve. The protective layer can consist of up to 100% of these water-soluble substances consist.

The water-soluble substance which is solid at room temperature, preferably the The main component of the enveloping protective layer is formed in particular nonionic surfactants, such as alkoxylated alcohols, fatty acids, fatty acid amides and / or hydroxy fatty acid esters selected. It is preferably a Alcohol, especially a primary linear alcohol, with 16 to 22 carbon atoms, with an average of 45 to 120, especially 60 to 110 mole equivalents of alkylene oxide, in particular Ethylene oxide is etherified. The alcohols mentioned include in particular Stearyl alcohol, arachidyl alcohol, behenyl alcohol and mono- to tri-unsaturated Alcohols of corresponding chain length, it being essential that the above alkoxylated alcohol component with a melting point in the range from 40 ° C to 200 ° C, in particular from 50 ° C to 70 ° C, which is understood here as the temperature in which 100% of the substance is in liquid form when heated. Alternatively or in addition to the alcohol ethoxylates, ethoxylated fatty acids, ethoxylated fatty acid amides and / or ethoxylation products of hydroxy fatty acid esters with 1 to 6 carbon atoms in the alcohol part of the ester, for example ricinoleic acid glyceride, the degree of ethoxylation in each case preferably 45 to 120, in particular 60 to 110 is used. The fatty acid component of the substances mentioned has preferably 12 to 22, in particular 16 to 18 carbon atoms. To those in this Preferred alkoxylates include ethoxylation products So-called narrow homolog distribution (nre, "narrow range ethoxylates") as they according to the procedure of European patent EP 339 426 or international Patent application WO 90/13533 can be obtained. If desired, the ethoxy groups in the alkoxylation products mentioned at least partly by propoxy groups to be replaced. If mixtures of substances are used, it is also possible to use those which small proportions, usually below 15% by weight based on the mixture, at room temperature Liquid components included, as long as the entire mixture Room temperature appears solid and a solidification point in the range of 40 ° C to 200 ° C, in particular from 50 ° C to 70 ° C. The freezing point is the temperature at which when cooling to a temperature above the melting point Material solidification occurs. It can with the help of a rotating thermometer be determined according to the procedure of DIN ISO 2207. For the manufacturing process according to the invention substances which are mixed with the remaining components of the encapsulation system as homogeneous as possible Temperatures up to 120 ° C result in sprayable melt. As a guide, in This connection is used for liquids with viscosities up to about 500 mPas at the temperatures mentioned, as a rule without any problems, using devices provided for this purpose, as known for example from German patent application 196 44 244, can be sprayed and applied to enzyme granules.

The protective layer can contain water-insoluble inorganic Contain components, flow improvers and organic dyes.

If desired, in amounts of up to preferably 10% by weight in the protective layer usable water-insoluble inorganic components include z. B. inorganic Pigments, such as calcium carbonate, titanium dioxide, which in rutile or anatase crystal modification zinc oxide, zinc sulfide, lead white (basic lead carbonate), Barium sulfate, aluminum hydroxide, antimony oxide, lithopone (zinc sulfide barium sulfate), Kaolin, chalk, talc and / or mica. These are in such a finely divided form that they melt in the remaining components of the for the formation of the protective layer provided coating system can be dispersed. Usually that lies average particle size of such pigments in the range from 0.004 μm to 50 μm. Also the use of surface-modified pigments with dispersants is possible. Surface modification is preferably carried out with A1, Si, Zr or polyol compounds Titanium dioxide pigment, especially in rutile form, as it is for example under the Trade names Kronos® 2132 (Kronos-Titan) or Hombitan® R 522 (Sachtleben Chemie GmbH) is used. The Tiona® RLL, AG or can also be used VC types from Solvay as well as Bayertitan® RD, R-KB and AZ types from Bayer AG.

As a further component of that provided for the formation of the protective layer Coating system come pourability, if desired in quantities up preferably 10% by weight of the protective layer, in question. Among them are supposed to be active ingredients can be understood, the absence of which leads to a deterioration in the flowability of the coated granules. For example, aluminum silicates, zeolites, Sodium silicates or silicas, which are in finely divided form for application to the Enzmgranulate mixed homogeneously with the other components of the coating system be applied or separately after application of the remaining components can.

The protective layer can also contain organic dyes, with particular ones are suitable, the organic substances liquid in water or at room temperature are soluble or suspendable. For example, anionic colorants, e.g. anionic nitroso dyes. A possible colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which is a commercial product for example as Basacid® Green 970 (CAS No. 19381-50-1) from BASF, Ludwigshafen, is available, as well as mixtures of these with suitable blue dyes. Other colorants that can be used are Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (CI 45100), Basacid® Yellow 094 (CI 47005), Sicovit® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol® Blue GLW (CAS 12219-32-8, CI Acidblue 221)), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CI Acid Yellow 218) and / or Sandolan® Blue (CI Acid Blue 182, CAS 12219-26-0) for Come into play.

Other suitable colorants are Ponceau 4R (CAS No. 2611-82-7, CI 16255), Allura Red 40 (CAS No. 25956-17-6, CI 16035), aluminum red RLW (CI Mordant Red 83), Supranol® Red GW (CAS No. 61901-44-8), Basantol® Red 310 (CAS No. 61951-36-8), Supranol® Green 6 GW (anthraquinone dye preparation with Acid Green 81), Supranol® Green BW (anthraquinone dye preparation with Acid Green 84), Ultramarine Blue-6394 (CAS No. 57455-37-5, CI 77007), Acid Yellow 17 (CAS No. 6359-98-4, CI 18965) and Acid Yellow 23 (CAS No. 1934-21-0, CI 19140).

Also suitable are the substances known as optical brighteners, their use in Washing and cleaning agents are known from the prior art. This is what it is about are organic dyes that are part of the invisible UV radiation from sunlight convert into longer wave blue light. They essentially belong to five Structural groups, the stilbene, the diphenylstilbene, the coumarin, quinoline, the Diphenylpyrazoline group and the group of the combination of benzoxazole or Benzimidazole with conjugated systems. An overview of common brighteners is for example in G. Jakobi, A. Löhr "Detergents and Textile Washing", VCH-Verlag, Weinheim, 1987, pages 94 to 100. Suitable are e.g. Salts of 4,4'-bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] stilbene-2,2'-disulfonic acid or similar established compounds, which instead of the morpholino group Diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group wear. Brighteners of the type of substituted diphenylstyryl, e.g. the alkali salts of 4,4'-bis (2-sulfo-styryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl.

The dyes mentioned above can be used individually or as mixtures as one or multi-colored systems are used.

In a preferred embodiment of the present invention, the Protective layer made of a coating system, the 45 wt .-% to 100 wt .-% Room temperature solid water-soluble organic substance with a melting point in the Range from 40 ° C to 200 ° C, up to 10 wt .-%, preferably up to 5 wt .-% and in particular 0.5 wt .-% to 5 wt .-% finely divided inorganic water-insoluble Pigment, up to 20% by weight, preferably up to 10% by weight and in particular 1% by weight to 5% by weight flow improver and up to 1.5% by weight organic dye contains.

In a further embodiment, the coating system contains small amounts as an additional component, preferably 3% by weight to 10% by weight, in particular 4% by weight to 8% by weight, of a compound of the general formula I, R [O (C _n H _2n O) _m H] _x in which R is an organic radical having 3 to 12 carbon atoms, in particular 4 to 10 carbon atoms, n is 2 or 3, m is 1 to 15 and x is 2 or 3. Such components can be produced in a known manner by reacting alcohols R [OH] _x with ethylene oxide and / or propylene oxide and can be part of the above-mentioned portion which is liquid at room temperature. The preferred compounds according to general formula I include those which contain both ethoxy groups (n = 2) and 1,2-propoxy groups (n = 3), the average number of ethoxy groups per hydroxyl group of the alcohol R [OH] _x preferably up to 10 and the average number of propoxy groups per hydroxyl group of the alcohol R [OH] _{x is} preferably up to 5. Among these, those are preferably used in the production of which the alcohol mentioned has first been reacted with propylene oxide and then with ethylene oxide. Preferred alcohols R [OH] _x include 1,6-hexylene glycol, glycerin and trimethylolpropane.

In a preferred embodiment of the invention, the wrapping material system is concerned a mixture of 0.5 to 5 wt .-% water-insoluble inorganic Pigment, 10% by weight to 40% by weight, in particular 15% by weight to 30% by weight above-mentioned ethoxylated fatty acid, 15% by weight to 77% by weight, in particular 27% by weight up to 71% by weight of the above-mentioned ethoxylated fatty alcohol and 3% by weight to 10% by weight, in particular 4% by weight to 8% by weight of compound of the general formula I.

The agents coated according to the invention contain surfactants, e.g. B. nonionic, anionic and amphoteric surfactants - in addition to that which may be contained in the protective layer Surfactant content, and bleach, and possibly other usual ingredients.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferably used nonionic surfactants, which either as sole nonionic surfactant or in combination with other nonionic Surfactants used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 Carbon atoms in the alkyl chain, especially fatty acid methyl esters.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides. Alkypolyglycosides that can be used satisfy the general formula RO (G) _Z , in which R is a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (II),

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propxylierte Derivate dieses Restes. [Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielweise nach der Lehre der internationalen Patentanmeldung WO 95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. The group of polyhydroxy fatty acid amides also includes compounds of the formula (III)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this rest. [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerin with 1 up to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles Glycerin can be obtained. Preferred sulfonated fatty acid glycerol esters are Sulfation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, Stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Are suitable 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, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or Triethanolamine. The anionic surfactants are preferably in the form their sodium or potassium salts, especially in the form of the sodium salts.

Surfactants are in total in the cleaning or washing agents according to the invention an amount of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30 wt .-%, based on the finished agent, included.

The agents according to the invention contain bleaching agents as a further component. are Bleach and any existing bleach activator in the form of so-called Contain bleach and / or bleach activator compounds, so it has turned out to be special proved to be advantageous if they contain bleach or bleach activator Particles at least partially with the protective layer described above to be provided, wherein the particles are preferably coated to at least 65%. This ensures that the relatively reactive bleaching agents are not mixed with others optionally contained sensitive substances such as enzymes, in Come in contact and destroy the activity of these substances and at least one Losing parts of your own effectiveness.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further usable bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as persulfates or persulfuric acid. A combination of sodium percarbonate with sodium sesquicarbonate is preferred in particular when the agents according to the invention are used for textile washing. If the agents are used in particular for cleaning hard surfaces, for example in automatic dishwashing, they can, if desired, also contain bleaches from the group of organic bleaches. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxyidoperoxyacid, Carboxybenzamidoperoxy-caproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassyl acid, 1,4-doxydoxybutanoic acid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

To wash at temperatures of 60 ° C and below, and especially at the Pre-treatment of laundry to achieve an improved bleaching effect agents according to the invention contain bleach activators. Can be used as bleach activators Compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or result in optionally substituted perbenzoic acid can be used. Are suitable Substances containing O- and / or N-acyl groups of the number of carbon atoms mentioned and / or if appropriate carry substituted benzoyl groups. Multiple acylates are preferred Alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated Triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular 1,3,4,6-tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated Hydroxycarboxylic acids, such as triethyl-O-acetyl citrate (TEOC), carboxylic anhydrides, in particular phthalic anhydride, isatoic anhydride and / or succinic anhydride, Carboxamides, such as N-methyldiacetamide, glycolide, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, isopropenylacetate, 2,5-diacetoxy-2,5-dihydrofuran and from the German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol respectively those described in European patent application EP 0 525 239 Mixtures (SORMAN), acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine or gluconolactone, triazole or triazole derivatives and / or particulate caprolactams and / or caprolactam derivatives, preferably N-acylated Lactams, for example N-benzoylcaprolactam and N-acetylcaprolactam, which from international patent applications WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO-A-95/00626, WO-A-95/14759 and WO-A-95/17498 are known. From the German patent application DE-A-196 16 769 known hydrophilically substituted Acylacetale and those in the German patent application DE-A-196 16 770 and the international patent application WO-A-95/14075 described acyllactams also preferably used. Also from the German patent application DE-A-44 43 177 known combinations of conventional bleach activators can be used become. Nitrile derivatives such as cyanopyridines, nitrile quats and / or Cyanamide derivatives are used. Preferred bleach activators are sodium 4- (octanoyloxy) benzene sulfonate, Undecenoyloxybenzenesulfonate (UDOBS), sodium dodeconoyloxybenzenesulfonate (DOBS) and / or decanoyloxybenzoic acid (DOBA, OBC 10). Such bleach activators are, if desired, in the usual range of 0.01 to 20% by weight, preferably in amounts of 0.1 to 15% by weight, in particular 1 wt .-% to 10 wt .-%, based on the total composition.

In addition to the conventional bleach activators or in their place, too so-called bleach catalysts can be included. These substances are bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes are used as bleaching catalysts suitable.

The bleach content of the agents according to the invention is preferably 1 to 40 % By weight and in particular 10 to 20% by weight, with particular preference Perborate monohydrate and / or percarbonate is used.

The agents according to the invention generally contain one or more builders, especially zeolites, silicates, carbonates, organic cobuilders and - where none There are ecological prejudices against their use - including phosphates. The latter are in particular in detergents, such as detergent tablets, for mechanical use Dishwashers are preferred builders.

Suitable crystalline, layered sodium silicates have 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 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents 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.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example 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 in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Fine-crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na ₂ O (1-n) K ₂ O Al ₂ O ₃ (2 - 2.5) SiO ₂ (3.5 - 5.5) H ₂ O can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

The use of the generally known phosphates as builder substances is also possible, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry. Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance. Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, very easily soluble in water powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Madrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to the diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) a density of 2.536 gcm ^- 3. Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more easily soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry. Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) . Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4. Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of Sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of Potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of Sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

The organic cobuilders in particular can be used in the agents according to the invention Polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders and phosphonates are used become. These classes of substances are described below.

Usable organic builders are, for example, those in the form of their Polycarboxylic acids that can be used are sodium salts, with polycarboxylic acids being such Carboxylic acids are understood that carry more than one acid function. For example these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, Tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not for ecological reasons objectionable, and mixtures of these. Preferred salts are the salts of Polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. The acids have besides theirs Builder effect typically also the property of an acidifying component and thus also serve to set a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, To name glutaric acid, adipic acid, gluconic acid and any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight have from 2000 to 20,000 g / mol. Because of their superior solubility, can this group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As Copolymers of acrylic acid with maleic acid have proven particularly suitable Contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous one Solution are used. The content of the agents in (co) polymeric polycarboxylates is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

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

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or the as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.

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

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives.

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

Other 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 processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. 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 customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used. 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. An oxidized oligosaccharide is also suitable, although a product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable cobuilders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferred in the form of its sodium or magnesium salts used. Glycerol disuccinates are also preferred in this context and glycerol trisuccinates. Suitable amounts are in zeolite and / or formulations containing silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 carbon atoms and at least one Contain hydroxy group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder. It is preferably used as the sodium salt used, the disodium salt neutral and the tetrasodium salt alkaline (pH 9) responds. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reacting sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta-and Octa sodium salt of DTPMP, used. As a builder, the class becomes the Phosphonates preferably used HEDP. The aminoalkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, it can, in particular if the agents also contain bleach, aminoalkanephosphonates are preferred, use in particular DTPMP, or mixtures of the phosphonates mentioned use.

In addition, all compounds that are able to complex with To train alkaline earth ions are used as cobuilders.

The washing and cleaning agent according to the invention can be used as a further conventional one Ingredients especially enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as graying inhibitors, color transfer inhibitors, Foam regulators, additional bleach activators, colors and fragrances included.

Due to the protective layer applied according to the invention, enzymes and Bleach can be contained in the agent at the same time, without their activity also prolonged storage decreases significantly.

Enzymes that can be used in the agents come from the class of oxidases, Proteases, lipases, cutinases, amylases, pullulanases, cellulases, hemicellulases, Xylanases and peroxidases and mixtures thereof, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Alcalase®, Esperase® and / or Savinase®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, cellulases such as Celluzyme® and or Carezyme®. Are particularly suitable from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia enzymatic active substances obtained. Any used Enzymes can, as for example in the European patent EP 0 564 476 or described in international patent applications WO 94/23005, on carriers adsorbed and / or embedded in enveloping substances to protect them against premature Protect inactivation. They are preferred in the surfactant mixtures according to the invention in amounts up to 10% by weight, in particular from 0.2% by weight to 2% by weight, contain, particularly preferably enzymes stabilized against oxidative degradation be used.

In particular for use in machine washing or cleaning processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable 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-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes. The foam inhibitors, in particular silicone or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

The salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylene triamine pentamethylene phosphonate or ethylenediaminetetramethylenephosphonate in Amounts of 0.1 to 1.5 wt .-% used.

If the agent according to the invention is used as a so-called heavy-duty detergent, it contains preferably from 3 to 30% by weight of anionic surfactants, 2 to 20% by weight of nonionic Surfactants, 10 to 50% by weight of builder materials, 5 to 25% by weight of bleach, 1 to 10 % By weight bleach activators, 0.3 to 3% by weight enzymes, 0.3 to 8% by weight cobuilder and 0.1 to 6% by weight defoamer.

The washing and cleaning agents according to the invention are in the form of solid particles before, especially as powders, granules, extrudates or as moldings, so-called Tablets. The invention also includes those particles which are at least partially associated with a Protective layer are provided and in a further processing stage to granules, Extrudates or moldings are processed. The production of the individual forms can be carried out according to methods known from the prior art.

The protective layer can be applied, for example, in DE 196 44 244 described vortex apparatus. Aqueous solutions or Dispersions or melting of the coating substances on the to be coated sprayed particulate agent. In one possible embodiment, the Envelope substance in the form of its melt applied in a fluid bed apparatus. It is preferably sprayed to a melting temperature of at least 20 ° C. molten coating substance with spray air kept at a temperature exceeding has at least the same temperature, via nozzles in the to be coated Particle filled vortex chamber and holds the outer shell of the chamber on one Temperature of 20 to 50 ° C, preferably at most 40 ° C. The spray air can also serve to heat the feed channel for the melt.

Claims (15)

Particulate detergents and cleaning agents containing surfactants and Bleach and possibly other usual ingredients, thereby characterized in that the particles at least partially with a protective layer are provided. Agent according to claim 1, characterized in that at least 65% of the Particles are coated. Agent according to claim 1 or 2, characterized in that the protective layer Has thickness of 0.1 microns to 100 microns. Agent according to one of claims 1 to 3, characterized in that the Protective layer 50 wt .-% to 100 wt .-% water-soluble organic substances or Contains mixtures with a melting point in the range of 40 ° C to 200 ° C. Agent according to claim 4, characterized in that at room temperature solid water-soluble substance with an average of 45 to 120, in particular 60 to 110 molar equivalents of ethylene oxide etherified primary linear saturated or unsaturated Alcohol with 16 to 22 carbon atoms, an ethoxylated fatty acid ethoxylated fatty acid amide, an ethoxylation product of hydroxy fatty acid esters with 1 to 6 carbon atoms in the alcohol part of the ester, the degree of ethoxylation each is in particular 45 to 120, or is a mixture of these. Agent according to one of claims 1 to 5, characterized in that the Protective layer up to 10% by weight of water-insoluble inorganic components contains. Agent according to one of claims 1 to 6, characterized in that the Protective layer contains up to 10 wt .-% flow improver. Agent according to one of claims 1 to 6, characterized in that the Protective layer consists of a coating system that is 45% to 100% by weight water-soluble organic substance solid at room temperature with a Melting point in the range from 40 ° C to 200 ° C, up to 10 wt .-%, preferably up to 5% by weight and in particular 0.5% by weight to 5% by weight of finely divided inorganic water-insoluble pigment, up to 20% by weight, preferably up to 10% by weight and in particular 1% by weight to 5% by weight of pourability improver and up to 1.5 Contains wt .-% organic dye Agent according to claim 8, characterized in that the coating system small amounts of a compound according to general formula I, R [O (C _n H _2n O) _m H] _x in which R is an organic radical having 3 to 12 carbon atoms, in particular 4 to 10 carbon atoms, n is 2 or 3, m is 1 to 15 and x is 2 or 3. Agent according to claim 9, characterized in that the compounds according to formula I are prepared by reacting alcohols R [OH] _x with ethylene oxide and / or propylene oxide and in them both ethoxy groups (n = 2) and 1,2-propoxy groups (n = 3) are included, the average number of ethoxy groups per hydroxyl group of the alcohol R [OH] _x preferably being up to 10 and the average number of propoxy groups per hydroxyl group of the alcohol R [OH] _x preferably being up to 5. Agent according to one of claims 9 or 10, characterized in that the Compound according to general formula I in an amount of 4% by weight to 8% by weight are included. Agent according to one of claims 1 to 11, characterized in that it is builder, Enzymes, sequestering agents, electrolytes, pH regulators and others Auxiliaries, such as graying inhibitors, color transfer inhibitors, Contain foam regulators, bleach activators, colors and fragrances. Process for the production of detergents and cleaning agents containing surfactants and bleaches and, if appropriate, other customary ingredients, thereby characterized in that a protective layer is applied to the agents or parts thereof applies. A method according to claim 13, characterized in that one for the Protective layer used shell substance in the form of their melt in one Fluid bed apparatus applies. A method according to claim 14, characterized in that the die on a Melting temperature kept at a temperature exceeding at least 20 ° C melted shell substance with spray air, which is at least the same temperature has, via nozzles in the filled with the particles to be coated Swirl chamber sprayed and the outer jacket of the chamber to a temperature from 20 ° C to 50 ° C, preferably at most 40 ° C.