# Patent

## Title
Coated sodium percarbonate particles

## Abstract

Sodium percarbonate particles with a coating layer which comprises from 70 to 99.8% by weight of anhydrous sodium sulfate and from 0.2 to 20% by weight of a sodium borate, and whose proportion by weight is from 1 to 10% based on the mass of the sodium percarbonate particle, exhibit a high storage stability in detergent and cleaning composition formulations through a synergistic effect of sodium sulfate and sodium borate on the storage stability, and at the same time only have a small content of boron.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
The present application is US national stage of international application PCT/EP2007/056404, which had an international filing date of Jun. 27, 2007, and which was published in German under PCT Article 21(2) on Jan. 31, 2008. The international application claims priority to European application EP 06117988.3, filed on Jul. 27, 2006. These prior applications are hereby incorporated by reference in their entirety.
The invention provides coated sodium percarbonate particles with high storage stability in detergents and cleaning compositions.
Sodium percarbonate is increasingly being used as a bleaching constituent in detergents and cleaning compositions. For this application, sodium percarbonate must have sufficient storage stability in detergent and cleaning composition formulations, since there is otherwise undesired loss of active oxygen and hence of bleaching action in the course of storage of the detergents and cleaning compositions. Sodium percarbonate is moisture-sensitive and decomposes in detergent and cleaning composition formulations under the action of moisture with loss of active oxygen. To produce detergents or cleaning compositions, sodium percarbonate is therefore typically used in coated form, the coating layers preventing the action of moisture on the coated sodium percarbonate particles. Suitable coating layer of inorganic hydrate-forming salts, for example sodium carbonate, sodium sulfate or magnesium sulfate and mixtures of such salts, are known, for example, from DE 24 17 572, EP-A 0 863 842 and U.S. Pat. No. 4,325,933.
U.S. Pat. No. 4,526,698 discloses sodium percarbonate particles which are coated with a borate-containing coating layer. The coating layer may, as well as the borate, comprise further organic or inorganic compounds. Examples of inorganic compounds mentioned are sodium carbonate, Glauber's salt and magnesium sulfate. It is evident from the working examples that, for the combination of sodium borate with polyethylene glycol, organic complexing agents, sodium silicates or magnesium compounds, a synergistic effect occurs in the stabilization, while no synergy was observed with sodium carbonate.
WO 95/15292 discloses a process for producing alkali metal percarbonate particles with a boric acid-containing coating layer by spraying on an aqueous solution which, in addition to boric acid, also comprises a neutral alkali metal or ammonium salt which increases the solubility of boric acid. Preferred salts mentioned include sodium chloride, potassium chloride, sodium sulfate and potassium sulfate. It is also mentioned that, in addition to boric acid or instead of boric acid, it is also possible to use alkali metal borates. The combination of a neutral alkali metal salt with a borate is intended to bring about reduced agglomeration of the alkali metal percarbonate particles. WO 98/15292 does not contain any disclosure as to the stability of alkali metal percarbonate particles with a borate-containing coating layer.
EP 567 140 discloses a process for producing coated sodium percarbonate particles by applying a first coating component selected from boric acids, borates and alkali metal silicates, and a second coating component selected from carbonates, hydrogencarbonates and sulfates, in which at least one of the coating components is applied in the form of an aqueous suspension. Working examples 2, 4 and 5 disclose sodium percarbonate particles with coating layers composed of 5.5% by weight of sodium metaborate tetrahydrate in combination with 5% by weight of soda, sodium hydrogencarbonate or sodium sulfate. It is evident from working examples 30 to 32 that the sodium percarbonate particles coated with a combination of borate and sodium sulfate exhibited a lower storage stability in a detergent than the sodium percarbonate particles coated with a combination of borate and soda, or borate and sodium hydrogencarbonate.
DE 27 12 139 discloses sodium percarbonate particles with a coating composed of dewatered sodium perborate and a sodium silicate which additionally comprises water-binding inert substances. Suitable water-binding inert substances mentioned are sodium tripolyphosphate, calcined soda, sodium sulfate and sodium percarbonate. The sodium percarbonate particles described contain sodium perborate monohydrate in amounts of 5% by weight and more and accordingly have high contents of boron.
The sodium percarbonate particles which have a borate-containing coating layer and are known from the prior art have the disadvantage that the coating layer contains a relatively large amount of boron and, as a result, in the case of use of the sodium percarbonate particles detergents or cleaning compositions, an undesirably high amount of borate gets into the wastewater obtained in the course of use.
It has now been found that, surprisingly, in the case of sodium percarbonate particles comprising from 1 to 10% by weight of a coating layer which comprises 70% by weight or more of sodium sulfate and up to 20% by weight of a sodium borate, a synergistic effect of sodium sulfate and sodium borate on the stabilization of the sodium percarbonate particles in detergent and cleaning composition formulations occurs, i.e. such a coating layer brings about better stabilization than is achieved with a coating layer composed of sodium sulfate or sodium borate alone.
The invention therefore provides sodium percarbonate particles with a coating layer which comprises 70 to 99.8% by weight of anhydrous sodium sulfate and from 0.2 to 20% by weight of a sodium borate, and the proportion by weight of the coating layer is from 1 to 10% based on the mass of the sodium percarbonate particle.
The inventive sodium percarbonate particles comprise a core which consists essentially of sodium carbonate perhydrate of composition 2 Na2CO3.3H2O2. They may additionally also comprise small amounts of known stabilizers for peroxygen compounds, for example magnesium salts, silicates, phosphates and/or chelate complexing agents. The proportion of sodium percarbonate in the core of the inventive sodium percarbonate particles is preferably more than 80% by weight and more preferably more than 95% by weight. The proportion of organic carbon compounds in the core is preferably less than 1% by weight, more preferably less than 0.1% by weight.
In a preferred embodiment, the core comprises small amounts of additives which have a stabilizing effect on the active oxygen content, in which case the proportion of stabilizing additives in the core is preferably less than 2% by weight. The stability-increasing additives used are preferably magnesium salts, waterglass, stannates, pyrophosphates, polyphosphates, and chelate complexing agents from the group of the hydroxycarboxylic acids, aminocarboxylic acids, aminophosphonic acids, phosphonocarboxylic and hydroxyphosphonic acids, and the alkali metal, ammonium or magnesium salts thereof. In a particularly preferred embodiment, the core comprises, as a stabilizing additive, an alkali metal silicate, preferably waterglass with an SiO2/Na2O modulus in the range from 1 to 3, in an amount of from 0.1 to 1% by weight. In the most preferred embodiment, the core, in addition to this amount of alkali metal silicate, also comprises a magnesium compound in an amount of from 50 to 2000 ppm of Mg2+.
The core of the inventive sodium percarbonate particles can be obtained by one of the known preparation processes for sodium percarbonate. A suitable preparation process for sodium percarbonate is the crystallization of sodium percarbonate from aqueous solutions of hydrogen peroxide and sodium carbonate, the crystallization being performable either in the presence or in the absence of a salt precipitant, for which reference is made by way of example to EP-A 0 703 190 and DE 2 744 574. Sodium percarbonate particles prepared by the crystallization process in the presence of a salt precipitant may still comprise small amounts of the salt precipitant used, for example sodium chloride. Likewise suitable is fluidized bed buildup granulation by spraying of aqueous hydrogen peroxide solution and aqueous soda solution onto sodium percarbonate seeds in a fluidized bed with simultaneous evaporation of water; reference is made by way of example to WO 95/06615. In addition, the reaction of solid sodium carbonate with an aqueous hydrogen peroxide solution and subsequent drying is another suitable preparation process.
In a preferred embodiment, the inventive sodium percarbonate particles have a core of sodium percarbonate which is obtainable by fluidized bed granulation from aqueous solutions of hydrogen peroxide and sodium carbonate. Such a fluidized bed granulation affords a core material which differs from the core materials obtained by other preparation processes by a particularly dense, shell-like structure and a smoother surface. Inventive coated sodium percarbonate particles whose core has been produced by fluidized bed buildup granulation exhibit an improved storage stability in detergent and cleaning composition formulations compared to particles whose core has been produced by another process.
The inventive coated sodium percarbonate particles comprise, in addition to the core composed of sodium percarbonate, also a coating layer which comprises 70 to 99.8% by weight of anhydrous sodium sulfate and from 0.2 to 20% by weight of a sodium borate, and the proportion by weight of the coating layer is from 1 to 10% based on the mass of the sodium percarbonate particle. The coating layer preferably comprises at least 80% by weight, more preferably at least 90% by weight, of sodium sulfate. The proportion of sodium borate in the coating layer is preferably 0.2 to less than 10% by weight, more preferably 0.5 to 5% by weight. The amounts stated for sodium borate are based on a calculation as anhydrous sodium metaborate NaBO2. The sodium borate may, however, also be present in the coating layer in other compositions, for example in the form of sodium tetraborate Na2B4O7, sodium octaborate Na2B8O13 or sodium pentaborate Na2B10O16.
The proportion by weight of the coating layer based on the mass of the sodium percarbonate particle is preferably from 2 to 8%, more preferably from 2 to 6%. In a particularly preferred embodiment, the proportion of sodium borate in the coating layer and the amount of the coating layer are selected such that the content of boron in the inventive coated sodium percarbonate particles is in the range from 20 to 700 ppm of boron, especially from 50 to 350 ppm of boron.
The inventive coated sodium percarbonate particles may additionally comprise up to 25% by weight of sodium carbonate, sodium hydrogencarbonate or mixtures thereof in the coating layer which comprises sodium sulfate and a sodium borate. Sodium carbonate and sodium hydrogencarbonate may also be present in the form of mixed salts with sodium sulfate, and sodium carbonate preferably in the form of a mixed salt of the composition 2 Na2SO4.Na2CO3. The coating layer which comprises sodium sulfate and a sodium borate preferably comprises, in addition to sodium sulfate, sodium borate, sodium carbonate, sodium hydrogencarbonate and mixed salts thereof, not more than 5% by weight of further compounds.
In addition to the inventive coating layer which comprises sodium sulfate and a sodium borate, the inventive sodium percarbonate particles may also comprise one or more further coating layers, which may be disposed either between the core and the inventive coating layer or outside the inventive coating layer. The inventive coating layer is preferably present immediately on the core material of sodium percarbonate.
Between the coating layers and between the innermost coating layer and the core, there may exist a sharp boundary at which the composition changes abruptly. In general, however, there will be a transition zone in each case between the individual coating layers and between the innermost coating layer and the core, said transition zone comprising the components of both adjacent layers. Such transition zones form, for example, as a result of the application of a coating layer in the form of an aqueous solution, a portion of the layer below being partly dissolved at the start of the layer buildup, so as to form a transition zone which comprises the constituents of both layers. In the preferred embodiment, in which the inventive coating layer is present immediately on the core material of sodium percarbonate, a transition layer which comprises sodium sulfate, sodium borate, sodium carbonate, sodium hydrogencarbonate, and also mixed salts of these components, may thus form between the core and the inventive coating layer.
The inventive coating layer which comprises sodium sulfate and a sodium borate is preferably configured such that it covers the material below it to an extent of more than 95%, preferably to an extent of more than 98% and especially completely.
In a preferred embodiment, the inventive sodium percarbonate particles have a coating layer which is produced by spraying an aqueous solution which comprises sodium sulfate and a sodium borate in dissolved form, and evaporating water in a fluidized bed. The coated sodium percarbonate particles thus obtainable differ from sodium percarbonate particles in which one of the components of the coating layer is applied in solid form by a homogeneous distribution of sodium sulfate and sodium borate in the coating layer and have a better storage stability in detergent and cleaning composition formulations compared with sodium percarbonate particles with inhomogeneous distribution of sodium sulfate and sodium borate in the coating layer.
In a particularly preferred embodiment, the inventive sodium percarbonate particles have a coating layer which is obtained by spray application of an aqueous solution which comprises dissolved sodium sulfate and a sodium borate and comprises a total of not more than 25% by weight of dissolved salts. While the prior art teaches use of highly concentrated solutions of the coating components to apply a coating layer, in order to minimize the amount of water to be evaporated, it has now been found that, surprisingly, sodium percarbonate particles with an inventive coating layer which comprises sodium sulfate and a sodium borate and which is obtainable by spray application of an aqueous solution comprising not more than 25% by weight of dissolved salts have a better storage stability in detergent and cleaning composition formulations than sodium percarbonate particles which are obtainable by spray application of an aqueous solution with a higher content of dissolved salts.
Solutions which are obtained by dissolving sodium sulfate and an alkali metal borate in water can be used to apply the inventive coating layer which comprises sodium sulfate and a sodium borate. If the alkali metal borate contains a different alkali metal than sodium, the sodium borate of the coating layer forms in the course of spraying of the solution with sodium ions which originate from the sodium sulfate.
During the spray application of the aqueous solution which comprises dissolved sodium sulfate and a sodium borate, the majority of the water present therein, especially more than 90% of the water present in the aqueous solution, is preferably already evaporated as a result of supply of heat, such that only a small portion of the material below it is partly dissolved again during the spray application of the coating layer and a solid coating layer forms already during the spray application. The inventive coating layer is applied preferably by spraying an aqueous solution comprising sodium sulfate and a sodium borate in a fluidized bed and more preferably by the process described in EP-A 0 970 917, with which it is possible to achieve a dense coating layer even with small amounts of coating layer material. The coating layer is applied in a fluidized bed preferably with supply of a drying gas to the fluidized bed, such that a temperature in the range from 30 to 90° C., preferably from 50 to 70° C., is established in the fluidized bed.
The inventive coated sodium percarbonate particles having a coating layer which comprises sodium sulfate and a sodium borate surprisingly exhibit a better storage stability in detergent and cleaning composition formulations than uncoated sodium percarbonate particles which have only one of the two components in the coating layer. Their storage stability is also improved over sodium percarbonate particles which, instead of sodium sulfate, comprise in the coating layer another water-binding salt, for example sodium carbonate or sodium hydrogencarbonate, in the same amount in combination with a sodium borate. The improved storage stability in detergent and cleaning composition formulations leads to lower losses of active oxygen content during the storage of the detergent and cleaning composition formulations in a moist environment.
The sodium percarbonate particles coated in accordance with the invention also exhibit no caking under the action of pressure and only a small release of heat in substance and can therefore be stored safely in a silo, without there being any caking in the silo or any self-heating of the silo contents.
Furthermore, detergent and cleaning composition formulations which comprise sodium percarbonate particles coated in accordance with the invention have improved safety when being stored in silo vessels, since they exhibit only slight self-heating, if any, in the case of adiabatic warm storage.
In a further embodiment of the invention, the coated sodium percarbonate particles may have an additional coating layer which, as the main constituent, comprises an alkali metal silicate having an SiO2 to alkali metal oxide modulus of more than 2.5. The additional coating layer is preferably present on top of the inventive coating layer. The additional coating layer comprises an alkali metal silicate as the main constituent when it does not comprise any further component in a proportion by weight greater than the proportion of alkali metal silicate. The modulus of the alkali metal silicate is preferably in the range from 3 to 5 and more preferably in the range from 3.2 to 4.2. The proportion of the additional coating layer in the inventive coated sodium percarbonate particles is preferably in the range from 0.2 to 3% by weight. The proportion of alkali metal silicate in the material of the additional coating layer is preferably more than 50% by weight and more preferably more than 80% by weight. The alkali metal silicate used in the additional coating layer is preferably sodium silicate and more preferably sodium waterglass.
Sodium percarbonate particles which have been coated in accordance with the invention and have an additional coating layer which comprises, as the main constituent, an alkali metal silicate having an SiO2 to alkali metal oxide modulus of more than 2.5 additionally exhibit a retarded dissolution time in water and an improved storage stability in aqueous liquid or gel-form media at water contents of up to 15% by weight. They can therefore be used advantageously to produce liquid or gel-form detergent or cleaning composition formulations.
In a further embodiment of the invention, the coated sodium percarbonate particles may additionally have, on their surface, from 0.01 to 1% by weight, preferably from 0.1 to 0.5% by weight, of a fine oxide of the elements Si, Al or Ti, or of a mixed oxide of these elements. Suitable fine oxides are, for example, pyrogenic oxides which are obtained by flame hydrolysis of volatile compounds of the elements silicon, aluminum or titanium, or of mixtures of these compounds. The pyrogenic oxides or mixed oxides obtainable by this route preferably have a mean primary particle size of less than 50 nm and may be aggregated to larger particles whose mean particle size is preferably less than 20 μm. Likewise suitable are precipitated oxides which have been precipitated from aqueous solutions of compounds of the elements silicon, aluminum or titanium, or mixtures of these compounds. The precipitated oxides or mixed oxides may, as well as silicon, aluminum and/or titanium, also comprise small amounts of alkali metal or alkaline earth metal ions. The mean particle size of the precipitated oxides is preferably less than 50 μm and more preferably less than 20 μm. The specific BET surface area of the fine oxides is preferably in the range from 100 to 300 m2/g.
The coated sodium percarbonate particles preferably have, on their surface, a hydrophobized fine oxide and more preferably a hydrophobized fumed or precipitated silica. Hydrophobized oxides in the context of the invention are oxides which have, on their surface, organic radicals bonded via chemical bonds and are not wetted by water. Hydrophobized oxides can be prepared, for example, by reacting pyrogenic or precipitated oxides with organosilanes, silazanes or polysiloxanes. Suitable silicon compounds for preparing hydrophobized oxides are known from EP-A 0 722 992, page 3 line 9 to page 6 line 6. Particular preference is given to hydrophobized oxides which have been prepared by reacting a fine oxide with a silicon compound of compound classes (a) to (e) and (k) to (m) listed in EP-A 0 722 992. The hydrophobized fine oxides preferably have a methanol wettability of at least 40.
Sodium percarbonate particles which have been coated in accordance with the invention and additionally have, on their surface, a fine oxide exhibit an even lower tendency to cake in the course of storage, in particular in the course of storage under pressure stress, and therefore have even better silo storability. Furthermore, such particles in detergent and cleaning composition formulations have a further increased storage stability.
The inventive sodium percarbonate particles preferably have a mean particle size in the range from 0.2 to 5 mm and more preferably in the range from 0.5 to 2 mm. Preference is given to sodium percarbonate particles having a low fines fraction, preferably having a fraction of less than 10% by weight of particles smaller than 0.2 mm and more preferably less than 10% by weight of particles having a particle size of less than 0.3 mm.
The inventive sodium percarbonate particles preferably have an essentially spherical shape with a smooth surface. Particles with a smooth surface have a surface roughness of less than 10% of the particle diameter and preferably of less than 5% of the particle diameter.
An appropriate selection of the particle size and particle form allows the storage stability of the inventive sodium percarbonate particles in detergent and cleaning composition formulations to be improved further.
The inventive coated sodium percarbonate particles can advantageously be used as a bleaching constituent in detergents and cleaning compositions. Detergents in the context of the invention are all formulations which are suitable for cleaning textiles in an aqueous wash liquor. Cleaning compositions in the context of the invention are all formulations which, in interaction with water, are suitable for cleaning surfaces which absorb only a small amount of water, if any. A form of cleaning compositions preferred in the context of the invention is that of machine dishwasher detergents which are suitable for machine cleaning of dishware and cutlery.
The invention further provides detergents and cleaning compositions which comprise sodium percarbonate particles coated in accordance with the invention. The inventive detergents and cleaning compositions comprise the inventive coated sodium percarbonate particles preferably in an amount of from 1 to 40% by weight based on the total amount of detergent or cleaning composition.
The inventive detergents and cleaning compositions may be in solid form and may then also comprise further components in the form of powder or in the form of granules beside the inventive coated sodium percarbonate particles. Furthermore, they may also comprise press-shaped bodies, in which case the inventive coated sodium percarbonate particles may be part of the press-shaped bodies. Such press-shaped bodies in the form of extrudates, pellets, briquettes or tablets can be produced by processes for pressing agglomeration, especially by extrusion, strand pressing, perforation pressing, roller compaction or tableting. For the performance of the pressing agglomeration, the inventive detergents or cleaning compositions may additionally comprise a binder which imparts a higher strength to the shaped bodies in the course of pressing agglomeration. However, for inventive detergents and cleaning compositions comprising press-shaped bodies preference is given to not using any additional binder and one of the wash-active constituents, for example a nonionic surfactant, fulfills the function of the binder.
The inventive detergents and cleaning compositions may additionally also be in liquid form or gel form and comprise the inventive coated sodium percarbonate particles dispersed in a liquid phase, or a gel phase. In addition to the inventive coated sodium percarbonate particles, further particles may be dispersed in the liquid phase, or the gel phase. The Theological properties of the liquid phase, or of the gel phase are preferably adjusted such that the particles dispersed therein remain suspended and do not settle during storage. The composition of a liquid phase is preferably selected in such a way that it has thixotropic or pseudoplastic flow properties. To establish such flow properties, suspension auxiliaries, such as swelling clays, especially montmorillonites, precipitated and fumed silicas, vegetable gums, especially xanthans, and polymeric gelling agents, such as vinyl polymers containing carboxyl groups, may be added.
Inventive detergents and cleaning compositions in liquid form or gel form preferably comprise inventive coated sodium percarbonate particles with an additional coating layer which, as the main constituent, comprises an alkali metal silicate having an SiO2 to alkali metal oxide modulus of more than 2.5 In this embodiment, the detergents and cleaning compositions may comprise up to 15% by weight of water without there being any partial dissolution of the coated sodium percarbonate particles and a resulting release of hydrogen peroxide into the liquid phase or gel phase during storage.
The inventive detergents and cleaning compositions may, as well as the inventive coated sodium percarbonate particles, comprise, as further components, for example, also surfactants, builders, alkaline components, bleach activators, enzymes, chelating complexing agents, graying inhibitors, foam inhibitors, optical brighteners, fragrances and dyes.
Suitable surfactants for the inventive detergents and cleaning compositions are in particular anionic, nonionic and cationic surfactants.
Suitable anionic surfactants are, for example, surfactants with sulfonate groups, preferably alkylbenzenesulfonates, alkanesulfonates, alpha-olefinsulfonates, alpha-sulfo fatty acid esters or sulfosuccinates. In the case of alkylbenzenesulfonates, preference is given to those having a straight-chain or branched alkyl group having from 8 to 20 carbon atoms, especially having from 10 to 16 carbon atoms. Preferred alkanesulfonates are those with straight alkyl chains having from 12 to 18 carbon atoms. In the case of alpha-olefinsulfonates, preference is given to the reaction products of the sulfonation of alpha-olefins having from 12 to 18 carbon atoms. In the case of the alpha-sulfo fatty acid esters, preference is given to sulfonation products of fatty acid esters formed from fatty acids having from 12 to 18 carbon atoms and short-chain alcohols having from 1 to 3 carbon atoms. Suitable anionic surfactants also include surfactants having a sulfate group in the molecule, preferably alkyl sulfates and ether sulfates. Preferred alkyl sulfates are those with straight-chain alkyl radicals having from 12 to 18 carbon atoms. Also suitable are beta-branched alkyl sulfates and alkyl sulfates mono- or poly-alkyl-substituted in the middle of the longest alkyl chain. Preferred ether sulfates are the alkyl ether sulfates which are obtained by ethoxylating linear alcohols having from 12 to 18 carbon atoms with from 2 to 6 ethylene oxide units and then sulfating. The anionic surfactants used may finally also be soaps, for example alkali metal salts of lauric acid, myristic acid, palmitic acid, stearic acid and/or natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids.
Suitable nonionic surfactants are, for example, alkoxylated compounds, especially ethoxylated and propoxylated compounds. Particularly suitable nonionic surfactants are condensation products of alkylphenols or fatty alcohols with from 1 to 50 mol, preferably from 1 to 10 mol, of ethylene oxide and/or propylene oxide. Likewise suitable are polyhydroxy fatty acid amides in which an organic radical having one or more hydroxyl groups which may also be alkoxylated is bonded to the amide nitrogen. Likewise suitable as nonionic surfactants are alkylglycosides with a straight-chain or branched alkyl group having from 8 to 22 carbon atoms, especially having from 12 to 18 carbon atoms, and a mono- or diglycoside radical, which is preferably derived from glucose.
Suitable cationic surfactants are, for example, mono- and dialkoxylated quaternary amines having a C6- to C18-alkyl radical bonded to the nitrogen and one or two hydroxyalkyl groups.
The inventive detergents and cleaning compositions further comprise builders which are capable of binding calcium and magnesium ions dissolved in water in the course of use. Suitable builders are alkali metal phosphates and alkali metal polyphosphates, especially pentasodium triphosphate; water-soluble and water-insoluble sodium silicates, especially sheet silicates of the formula Na5Si2O5; zeolites of the A, X and/or P structures; and trisodium citrate. In addition to the builders, it is also possible to use organic cobuilders, for example polyacrylic acid, polyaspartic acid and/or acrylic acid copolymers with methacrylic acid, acrolein or vinyl monomers containing sulfonic acid, and the alkali metal salts thereof.
The inventive detergents and cleaning compositions generally also comprise alkaline components which upon the intended use bring about a pH in the range from 8 to 12 in the wash liquor, or the aqueous cleaning composition solution. Suitable alkaline components are in particular sodium carbonate, sodium sesquicarbonate, sodium metasilicate and other soluble alkali metal silicates.
Suitable bleach activators for the inventive detergents and cleaning compositions are in particular compounds having one or more perhydrolyzable acyl groups bonded to nitrogen or to oxygen, which react with the hydrogen peroxide released from the sodium percarbonate particles in the wash liquor, or the aqueous cleaning composition solution, to give peroxycarboxylic acids. Examples of such compounds are polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED); acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT); acylated glycolurils, especially tetraacetylglycoluril (TAGU); N-acylimides, especially N-nonanoylsuccinimide (NOSI); acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS); carboxylic anhydrides such as phthalic anhydride; acylated polyhydric alcohols such as ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, acetylated sorbitol and mannitol, and acylated sugars such as pentaacetylglucose; enol esters; and N-acylated lactams, especially N-acylcaprolactams and N-acylvalerolactams. Likewise suitable as bleach activators are amino-functionalized nitrites and salts thereof (nitrile quats), which are known, for example, from the journal Tenside Surf. Det. 1997, 34(6), pages 404-409. The bleach activators used may also be transition metal complexes which can activate hydrogen peroxide for bleaching stain removal. Suitable transition metal complexes are, for example, known from EP-A 0 544 490 page 2 line 4 to page 3 line 57; WO 00/52124 page 5 line 9 to page 8 line 7 and page 8 line 19 to page 11, line 14; WO 04/039932 page 2 line 25 to page 10 line 21; WO 00/12808 page 6 line 29 to page 33 line 29; WO 00/60043 page 6 line 9 to page 17 line 22; WO 00/27975 page 2 lines 1 to 18 and page 3 line 7 to page 4 line 6; WO 01/05925 page 1 line 28 to page 3 line 14; WO 99/64156 page 2 line 25 to page 9 line 18; and GB-A 2 309 976 page 3 line 1 to page 8 line 32.
The inventive detergents and cleaning compositions may further comprise enzymes which enhance the cleaning action, especially lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and/or peroxidases. The enzymes may be adsorbed on carrier substances or be embedded into coating substances in order to protect them from decomposition.
The inventive detergents and cleaning compositions may also comprise chelating complexing agents for transition metals, with which a catalytic decomposition of active oxygen compounds in the wash liquor, or the aqueous cleaning composition solution, can be prevented. Suitable examples are phosphonates, such as hydroxyethane-1,1-disphosphonate, nitrilotrimethylenephosphonate, diethylenetriaminepenta-(methylenephosphonate), ethylenediaminetetra(methylenephosphonate), hexamethylenediaminetetra(methylenephosphonate) and the alkali metal salts thereof. Likewise suitable are nitrilotriacetic acid and polyaminocarboxylic acids, especially ethylenediaminetetraacetic acid, diethylenetriaminopentaacetic acid, ethylenediamine-N,N′-disuccinic acid, methylglycinediacetic acid and polyaspartates, and the alkali metal and ammonium salts thereof. Finally, polybasic carboxylic acids and especially hydroxycarboxylic acids, especially tartaric acid and citric acid, are also suitable as chelating complexing agents.
The inventive detergents may additionally comprise graying inhibitors which keep soil detached from the fiber suspended and prevent reattachment of the soil to the fiber. Suitable graying inhibitors are, for example, cellulose ethers such as carboxymethylcellulose and the alkali metal salts thereof, methylcellulose, hydroxyethylcellulose and hydroxypropylcellulose. Polyvinylpyrrolidone is likewise suitable.
The inventive detergents and cleaning compositions may further also comprise foam inhibitors which reduce foam formation in the wash liquor. Suitable foam inhibitors are, for example, organopolysiloxanes such as polydimethylsiloxane, paraffins and/or waxes, and mixtures thereof with fine silicas.
The inventive detergents may optionally comprise optical brighteners which attach to the fiber, absorb light in the UV range and fluoresce in a blue color in order to compensate for yellowing of the fiber. Suitable optical brighteners are, for example, derivatives of diaminostilbenedisulfonic acid, such as alkali metal salts of 4,4′-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2′-disulfonic acid, or substituted diphenylstyryls, such as alkali metal salts of 4,4′-bis(2-sulfostyryl)diphenyl.
The inventive detergents and cleaning compositions may finally also comprise fragrances and dyes.
Inventive detergents and cleaning compositions in liquid form or gel form may additionally also comprise up to 30% by weight of organic solvent, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, glycerol, diethylene glycol, ethylene glycol methyl ether, ethanolamine, diethanolamine and/or triethanolamine.
As compared with detergents and cleaning compositions which do not comprise sodium percarbonate particles coated in accordance with the invention, the inventive detergents and cleaning compositions exhibit a better storage stability with lower losses of active oxygen content in the course of storage under moist conditions.
One embodiment of the inventive cleaning compositions is that of machine dishwasher detergents, preferably in the form of tablets, in which case the dishwasher detergents may also comprise a silver anticorrosive beside the inventive coated sodium percarbonate particles. Silver anticorrosives are agents which reduce or prevent the tarnishing of nonferrous metals, especially of silver, during machine cleaning with the machine dishwasher detergent. Suitable silver anticorrosives are compounds from the group of the triazoles, benzotriazoles, bisbenzotriazoles, aminotriazole and alkylaminotriazoles. The compounds of the substance classes mentioned may also have substituents, for example linear or branched alkyl groups having from 1 to 20 carbon atoms, as well as vinyl, hydroxyl, thiol or halogen radicals. In the case of bisbenzotriazoles, preference is given to compounds in which the two benzotriazole groups are each bonded in the 6 position via an X group, where X may be a bond, a straight-chain alkylene group which is optionally substituted by one or more C1- to C4-alkyl groups and has preferably from 1 to 6 carbon atoms, a cycloalkyl radical having at least 5 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. A particularly preferred silver anticorrosive is tolyltriazole.


EXAMPLES
Preparation of Coated Sodium Percarbonate Particles
To produce the coated sodium percarbonate particles, sodium percarbonate particles were used which had been prepared by the process described in EP-B 0 716 640 by fluidized bed buildup granulation from aqueous hydrogen peroxide solution and aqueous sodium carbonate solution and had a mean particle diameter x50 of 0.78 mm and a fines fraction of smaller than 0.2 mm of less than 2% by weight. The coating layer was applied to these particles by the process described in EP-B 0 863 842 in paragraph [0021] by spraying on a 20% by weight aqueous solution of the coating substances in a fluidized bed at a fluidized bed temperature of from 55 to 60° C. and simultaneously evaporating water and subsequently drying at a temperature of not more than 90° C. for 30 min. The amounts of coating substance reported in percent by weight in table 1 are based on the total amount of coating substances sprayed on, calculated without water of crystallization, relative to the total amount of sodium percarbonate particles and coating substances used.
Storage Stability in Washing Powder
To determine the storage stability in washing powder, 405 g of zeolite-containing heavy-duty powder detergent IEC-A* BASE (wfk-Testgewebe GmbH, Krefeld) were mixed with 15 g of TAED and 80 g of sodium percarbonate in a tumbling mixer for at least 10 min. The mixture was filled into an E2 detergent package (dimensions 19×14×4.5 cm) having a water-repellent impregnation, which was sealed with hotmelt adhesive. The detergent package was then stored in a climate-controlled cabinet at 35° C. and 80% relative air humidity. After the detergent package had been cooled to room temperature outside the climate-controlled cabinet, the contents of the detergent package were divided by means of a sample divider into samples of 12 g each. The active oxygen content before and after storage was determined by permanganometry in a customary manner. The active oxygen content before the storage and the active oxygen content after 8 weeks of storage were used to determine the retention of the active oxygen content (Oa retention) in percent as a measure of the storage stability in washing powder.







TABLE 1







Storage stability of coated sodium percarbonate


particles in washing powder









Storage stability as a



function of the amount of



coating substance [Oa


Composition of
retention in percent]










the coating layer
4% by weight
3% by weight
2% by weight


in parts by
of coating
of coating
of coating


weight
substances
substances
substances





Na2SO4 100*
51
48
43


Na2SO4/NaBO2
59
54
37


99.5:0.5


Na2SO4/NaBO2 99:1
62
51
45


Na2SO4/NaBO2
71
59
46


97.5:2.5


Na2SO4/NaBO2 95:5
81
59
53


Na2SO4/NaBO2 90:10
79


Na2SO4/NaBO2 80:20
76


Na2SO4/NaBO2
71


50:50*





*noninventive






The tests were repeated for a coating substance composition of 95 parts by weight of sodium sulfate and 5 parts by weight of sodium metaborate or pure sodium sulfate, by spraying on 4% by weight of coating substances at a constant spray rate of 11 g/min and varying the concentration of the coating substances in the solution sprayed from 15 to 30% by weight.







TABLE 2







Storage stability of coated sodium percarbonate


particles in washing powder








Composition
Storage stability as


of the
a function of the


coating
concentration of the


layer in
solution sprayed on


parts by
[Oa retention in percent]











weight
15% by wt.
20% by wt.
25% by wt.
30% by wt.





Na2SO4 100*
45
53
43
44


Na2SO4/
83
79
74
63


NaBO2 95:5





*noninventive

## Claims

1. Sodium percarbonate particles comprising a coating layer, wherein said coating layer comprises 80 to 95% by weight of anhydrous sodium sulphate and 5 to 20% by weight of a sodium borate, and the weight proportion of the coating layer based on the mass of the sodium percarbonate particle is from 3 to 4% and wherein the distribution of the anhydrous sodium sulphate and the sodium borate in the coating layer is homogeneous.

2. The sodium percarbonate particles of claim 1, wherein the coating layer comprises less than 10% by weight of a sodium borate.

3. The sodium percarbonate particles of claim 1, having a content of boron in the range of 20 to 700 ppm based on the mass of the sodium percarbonate particles.

4. The sodium percarbonate particles of claim 1, wherein the coating layer further comprises up to 25% by weight of sodium carbonate, sodium hydrogencarbonate or mixtures thereof.

5. The sodium percarbonate particles of claim 1, wherein said coating layer is obtained by spraying an aqueous solution of sodium sulphate and sodium borate in dissolved form and evaporating water in a fluidized bed, and wherein said aqueous solution contains not more than 25% by weight of dissolved salts.

6. The sodium percarbonate particles of claim 5, wherein said aqueous solution is sprayed onto a sodium percarbonate particle which is obtained from aqueous solutions of hydrogen peroxide and sodium carbonate by fluidized bed granulation.

7. Detergent, comprising sodium percarbonate particles according to claim 1.

8. The detergent of claim 7, wherein the coating layer of said sodium percarbonate particles comprises less than 10% by weight of a sodium borate.

9. The detergent of claim 7, wherein said sodium percarbonate particles comprise boron in the range of 20 to 700 ppm based on the mass of the sodium percarbonate particles.

10. The detergent of claim 7, wherein the coating layer of said sodium percarbonate particles further comprises up to 25% by weight of sodium carbonate, sodium hydrogencarbonate or mixtures thereof.

11. The detergent of claim 7, wherein the coating layer of said sodium percarbonate particles is obtained by spraying an aqueous solution of sodium sulphate and sodium borate in dissolved form and evaporating water in a fluidized bed, and wherein said aqueous solution contains not more than 25% by weight of dissolved salts.

12. The detergent of claim 7, wherein said aqueous solution is sprayed onto a sodium percarbonate particle which is obtained from aqueous solutions of hydrogen peroxide and sodium carbonate by fluidized bed granulation.

13. Cleaning composition, comprising sodium percarbonate particles according to claim 1.

14. The cleaning composition of claim 13, wherein the coating layer of said sodium percarbonate particles comprises less than 10% by weight of a sodium borate.

15. The cleaning composition of claim 13, wherein said sodium percarbonate particles comprise boron in the range of 20 to 700 ppm based on the mass of the sodium percarbonate particles.

16. The cleaning composition of claim 13, wherein the coating layer of said sodium percarbonate particles further comprises up to 25% by weight of sodium carbonate, sodium hydrogencarbonate or mixtures thereof.

17. The cleaning composition of claim 13, wherein the coating layer on said sodium percarbonate particles is obtained by spraying an aqueous solution of sodium sulphate and sodium borate in dissolved form and evaporating water in a fluidized bed, and wherein said aqueous solution contains not more than 25% by weight of dissolved salts.

18. The sodium percarbonate particles of claim 1, wherein the particles comprise a core consisting of essentially of sodium carbonate perhydrate of composition 2Na2CO3.3H2O2 and less than 2% of stabilizers for peroxygen compounds selected from the group consisting of: magnesium salts, silicates, phosphates and chelate complexing agents.

19. The sodium percarbonate particles of claim 1, wherein the particles have a mean particle size in the range from 0.5 to 2 mm.