EP1824783A1 - Corps moules comprimes contenant des particules de percarbonate de sodium enrobees - Google Patents

Corps moules comprimes contenant des particules de percarbonate de sodium enrobees

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Publication number
EP1824783A1
EP1824783A1 EP05810720A EP05810720A EP1824783A1 EP 1824783 A1 EP1824783 A1 EP 1824783A1 EP 05810720 A EP05810720 A EP 05810720A EP 05810720 A EP05810720 A EP 05810720A EP 1824783 A1 EP1824783 A1 EP 1824783A1
Authority
EP
European Patent Office
Prior art keywords
sodium percarbonate
alkali metal
percarbonate particles
shell layer
metal silicate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05810720A
Other languages
German (de)
English (en)
Inventor
Harald Jakob
Klaus Zimmermann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Publication of EP1824783A1 publication Critical patent/EP1824783A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/055—Peroxyhydrates; Peroxyacids or salts thereof
    • C01B15/10—Peroxyhydrates; Peroxyacids or salts thereof containing carbon
    • C01B15/106—Stabilisation of the solid compounds, subsequent to the preparation or to the crystallisation, by additives or by coating
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the invention is directed to pressed molded articles which contain coated sodium percarbonate particles and which have improved storage stability with a low loss of active oxygen content.
  • Sodium percarbonate is increasingly used as a bleaching active ingredient in detergents and cleaners.
  • sodium percarbonate must have adequate storage stability in detergent and cleaner preparations, since otherwise undesirable losses of active oxygen and thus bleaching effect occur during storage of the detergents and cleaners.
  • Sodium percarbonate is sensitive to moisture and decomposes in detergent and cleaner formulations upon exposure to moisture with loss of active oxygen. For this reason, sodium percarbonate is usually used in coated form for the production of detergents or cleaners, the coating layer preventing the action of moisture on the coated sodium percarbonate.
  • Suitable shell layers of inorganic hydrate-forming salts such as, 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 US Pat. No. 4,325,933.
  • Detergents and cleaning agents are increasingly marketed in the form of compressed molded articles which have advantages for the user, such as a Clean handling without dusting or spilling a powder and a lower tendency to form caking in the dispenser of a washing machine.
  • Such compressed molded articles also have advantages in the metering of detergents and cleaning agents when shaped articles in the form of tablets or blocks are used in a size which contain the amount of detergent or cleaning agent required for a washing cycle in a washing machine or dishwasher.
  • EP-A 0 634 478, EP-A 0 672 749 and EP-A 0 690 122 disclose machine dishwashing detergents containing an oxygen-releasing bleaching agent.
  • Preferred bleaching agents are sodium perborate and sodium percarbonate called.
  • Sodium percarbonate is preferably used in coated form, with a mixed salt of an alkali metal sulfate and an alkali metal carbonate being mentioned as the preferred coating material.
  • Sodium silicate with a SiO 2 : Na 2 O ratio of 1.6 to 3.4 is also mentioned as a suitable shell material.
  • the documents also reveal that the machine dishwashing detergents can be formulated in the form of powders, granules, pastes, liquids, gels or tablets. The documents, however, can be found no teaching, such as
  • Sodium percarbonate particles must be coated so that they are sufficiently stable in the stored molded bodies and have no increased loss of active oxygen content.
  • WO 97/45524 discloses detergent compositions containing a sustained-release alkaline component. These detergent formulations may contain, as bleaching component, organic peracids or inorganic perhydrates, sodium perborate and sodium percarbonate being mentioned as preferred inorganic perhydrates.
  • the inorganic perhydrates are preferably used in a sustained release form, with the delayed form being preferred for sodium percarbonate
  • the detergent compositions described in this document may take the form of granules, tablets, blocks or liquids. However, the document does not disclose how sodium percarbonate particles have to be coated so that they are sufficiently stable in storage in compressed moldings and have no increased loss of active oxygen content.
  • WO 97/03177 discloses machine-dish cleaners in tablet form containing sodium perborate as a bleaching agent. Instead of sodium perborate, it is also possible to use sodium percarbonate, preferably in coated form. The document can be found but no teaching, such as the wrapping of
  • Sodium percarbonate particles must be constructed so that tablets containing these sodium percarbonate particles have sufficient storage stability with a low loss of active oxygen content.
  • EP-A-0 992 575 discloses sodium percarbonate particles containing an alkali metal silicate having a molar ratio SiO 2 to alkali metal oxide of more than 3 and less than 5. The particles can do this
  • Alkali metal silicate contained both in the core and in a cladding layer. The described
  • Sodium percarbonate particles are preferably coated with one or more cladding layers, wherein as suitable constituents of the cladding layers in addition to the
  • Alkali metal silicate also water-soluble organic stabilizers, water-soluble magnesium compounds and alkali metal carbonates, bicarbonates and sulfates are called.
  • the document also discloses compositions suitable as detergents, dishwashing detergents or bleaches which contain such sodium percarbonate particles and which may take the form of free-flowing particles or the form of tablets for a wash cycle.
  • the document does not disclose any teaching of how the coating layer of sodium percarbonate particles must be structured, so that compressed molded articles containing such sodium percarbonate particles have sufficient storage stability with a low loss of active oxygen content.
  • EP-A 0 737 738 discloses bleach tablets which contain 45 to 85% by weight of coated sodium percarbonate and 1 to 50% by weight of phyllosilicate or alkali metal silicate having a composition SiO 2 : Na 2 O in the range from 1 to 3.5, and have a high storage stability.
  • the composition of the coating layer is disclosed in this document only by two exemplified products, one of which has a boron-containing coating layer and the other a coating layer based on sulfate and sodium carbonate.
  • the document teaches on page 2 in lines 25 to 28 that in the production of tablets, the coating layer of sodium percarbonate is partially or completely destroyed by the high pressure used for tableting and that this leads to a strong loss of the protective effect of the cladding layer.
  • the document does not indicate that the composition of the coating layer of the sodium percarbonate particles has an influence on the storage stability of the tablets.
  • WO 00/71666 discloses laundry detergent tablets containing coated sodium percarbonate particles wherein the wrapper is made of a water-soluble material.
  • Suitable shell materials include sodium sulfate, sodium carbonate, sodium chloride and sodium borate, as well as mixtures of these materials.
  • the document gives no indication that the composition of the coating layer of the sodium percarbonate particles has an influence on the storage stability of the tablets.
  • WO 01/34759 discloses laundry detergent tablets containing a bleaching agent.
  • Perborates, percarboxylic acids and peroxygen compounds are mentioned as bleaching agents, preferred being the peroxygen compound
  • Sodium percarbonate is called.
  • the sodium percarbonate may be coated with silicate, borate or water-soluble surfactants.
  • the document gives no indication that the composition of the coating layer of the sodium percarbonate particles has an influence on the storage stability of the tablets.
  • WO 2004/056954 discloses coated sodium percarbonate particles having two cladding layers.
  • the inner shell layer contains at least one hydrate-forming inorganic salt and constitutes from 2 to 20% by weight of the particles.
  • these sodium percarbonate particles in a powdery detergent formulation have a higher storage stability and a lower loss of active oxygen than sodium percarbonate particles which lack the outer coating layer.
  • the document gives no indication that these sodium percarbonate particles can be used in compressed moldings and how the pressing process affects the stability of the sodium percarbonate particles.
  • the object of providing compressed moldings with coated sodium percarbonate particles contained therein which have improved storage stability with a lower loss of active oxygen content, can be achieved if the coating of the sodium percarbonate particles has an inner coating layer with at least one water-soluble hydrate-forming salt and an outer shell layer with an alkali metal silicate.
  • the invention relates to compressed moldings containing coated sodium percarbonate particles, characterized in that the coating of the sodium percarbonate particles has an inner shell layer containing one or more water-soluble hydrate-forming salts and an overlying outer shell layer containing an alkali metal silicate.
  • the invention also encompasses the use of the compressed shaped bodies according to the invention in detergents or cleaners, and the use of compressed shaped bodies according to the invention which additionally contain at least one surfactant as detergent or cleaning agent.
  • the invention furthermore relates to a process for the production of shaped bodies containing coated sodium percarbonate particles, characterized in that a pulverulent mixture containing coated sodium percarbonate particles is compacted by tabletting or briquetting, wherein the coated sodium percarbonate particles comprise an envelope with an inner shell layer containing one or more water-soluble hydrate-forming salts and an overlying outer shell layer containing an alkali metal silicate.
  • the coated sodium percarbonate particles contained in the moldings according to the invention comprise a core consisting essentially of sodium carbonate perhydrate of the composition 2Na 2 CO 3 .3H 2 O 2 .
  • they can still small amounts of known
  • Stabilizers for peroxygen compounds such as magnesium salts, silicates, phosphates and / or chelating agents.
  • the proportion of sodium percarbonate in the core of the sodium percarbonate particles according to the invention is preferably more than 95% by weight and more preferably more than 98% by weight.
  • the proportion of organic carbon compounds in the core is preferably less than 1 wt .-%, more preferably less than 0.1 wt .-%.
  • the core contains small amounts of additives which have a stabilizing effect on the active oxygen content, wherein the proportion of stabilizing additives in the core is preferably less than 2% by weight.
  • additives which have a stabilizing effect on the active oxygen content, wherein the proportion of stabilizing additives in the core is preferably less than 2% by weight.
  • stability-increasing additives magnesium salts, water glass, stannates, pyrophosphates, polyphosphates and Chelatkomplextruckner from the series of hydroxycarboxylic acids, aminocarboxylic acids, aminophosphonic acids, phosphonocarboxylic acids and hydroxyphosphonic acids and their alkali metal, ammonium or magnesium salts are preferably used.
  • the core contains as stabilizing additive an alkali metal silicate, preferably water glass with a Si0 2 / Na 2 0 modulus in the range of 1 to 3, in an amount of 0.1 to 1 wt .-%.
  • the core in addition to this amount of alkali metal silicate, the core also contains a magnesium compound in an amount of 50 to 2000 ppm
  • the core of the coated sodium percarbonate particles can be produced according to one of the known production processes for sodium percarbonate.
  • a suitable production process for sodium percarbonate is the crystallization of sodium percarbonate from aqueous
  • Sodium percarbonate particles prepared by the crystallization process in the presence of a salting-out agent may still contain small amounts of the salting-out agent used, e.g. Contain sodium chloride.
  • the fluidized bed build-up granulation by spraying aqueous hydrogen peroxide solution and aqueous sodium carbonate solution on sodium percarbonate nuclei in a fluidized bed with simultaneous evaporation of water by way of example, reference is made to WO 95/06615.
  • the core of the coated sodium percarbonate particles is obtained by fluidized bed granulation.
  • Coated sodium percarbonate particles whose core has been produced by fluidized bed build-up granulation exhibit improved storage stability in the pressed molded bodies according to the invention compared to particles whose core has been produced by a different process.
  • the coated sodium percarbonate particles contained in the Porm bodies according to the invention comprise, in addition to the core of sodium percarbonate, an inner shell layer which contains a water-soluble, hydrate-forming salt and an outer shell layer which contains an alkali metal silicate.
  • the inner shell layer contains one or more inorganic hydrate-forming salts.
  • Inorganic, hydrate-forming salts in the context of the invention are salts which can bind water in the crystal lattice, contain no organic radicals and are not oxidized by sodium percarbonate.
  • the coated sodium percarbonate particles may also contain one or more further cladding layers, which may be arranged both between the core and the inner cladding layer, and between the inner and outer cladding layers and outside the outer cladding layer.
  • transitional zone will be formed between the individual cladding layers and between the innermost cladding layer and the core, which in each case contains the components of both adjoining layers.
  • Such transition zones are formed, for example, by the application of a coating layer in the form of an aqueous solution, wherein at the beginning of the
  • a portion of the underlying layer is dissolved, so that a transition zone is formed, which contains the components of both layers.
  • a transitional layer can form, the sodium percarbonate,
  • the cladding layer may similarly form a transition layer containing the water-soluble hydrate-forming salt of the inner cladding layer and the alkali metal silicate of the outer cladding layer.
  • Inner cladding layer and outer cladding layer are preferably formed to cover the underlying material more than 95%, preferably more than 98%, and more preferably completely.
  • sodium percarbonate particles preferably contain one or more hydrate-forming salts of an alkali metal and / or
  • the water-soluble hydrate-forming salt is selected from the series sodium sulfate, sodium carbonate, sodium bicarbonate or magnesium sulfate. Also suitable are mixtures and mixed salts of these compounds.
  • the inner shell layer contains sodium sulfate as an inorganic hydrate-forming salt.
  • the proportion of water-soluble, hydrate-forming salt in the material of the inner shell layer is preferably at least 50% by weight, particularly preferably at least 90% by weight.
  • the proportion of the inner shell layer of the coated sodium percarbonate particles is preferably in the range of 1 to 10 wt .-%, particularly preferably in the range of 2 to 7 wt .-%.
  • the inner shell layer consists essentially of sodium sulfate.
  • the application of the inner shell layer is preferably carried out by spraying an aqueous solution in which at least one hydrate-forming salt is dissolved.
  • the aqueous solution preferably contains no further dissolved components in addition to the dissolved hydrate-forming salt
  • the inner shell layer is applied by spraying on an aqueous sodium sulfate solution.
  • the spraying of the aqueous solution preferably the largest part of the water contained therein, in particular more than 90% of the water contained in the aqueous solution, is evaporated by supplying heat, so that only a small part of the core material is dissolved again during the application of the inner shell layer and already during the spraying forms a solid shell layer containing the hydrate-forming salt.
  • the application of the inner shell layer is preferably carried out by spraying an aqueous solution containing the hydrate-forming salt in a fluidized bed, and more preferably according to the method described in EP-A 0 970 917, with which a dense shell layer can be achieved even with small amounts of shell layer material.
  • the application of the inner shell layer in a fluidized bed is preferably carried out by supplying a drying gas to the fluidized bed, so that a temperature in the range of 30 to 90 0 C sets in the fluidized bed.
  • Sodium percarbonate particles contains an alkali metal silicate, which preferably has a modulus SiO 2 to alkali metal oxide of more than 2.5 and more preferably a modulus in the range of 3 to 5, wherein the modulus of the molar ratio of SiO 2 to alkali metal oxide.
  • the proportion of alkali metal silicate in the material of the outer shell layer is preferably at least 50% by weight, particularly preferably at least 90% by weight.
  • the amount of alkali metal silicate contained in the outer shell layer is preferably from 0.2 to 3% by weight and preferably from 0.3 to 1% by weight, based on the total amount of sodium percarbonate particles coated.
  • the alkali metal silicate is preferably a sodium silicate and more preferably a soda water glass.
  • the application of the outer shell layer is preferably carried out by spraying an alkali metal silicate-containing aqueous solution.
  • an aqueous solution with a concentration of alkali metal silicate in the range of 2 to 20 wt .-%, particularly preferably 3 to 15 wt .-% and in particular 5 to 10 wt .-% is used.
  • a so-called water glass solution is preferably sprayed on.
  • the spraying of the alkali metal silicate-containing aqueous solution is preferably already the majority of the water contained therein, in particular more than 90% of the water contained in the aqueous solution, evaporated by supplying heat, so that during the application of the outer shell layer only a small part of underlying material is redissolved and already formed during spraying a solid alkali metal silicate-containing shell layer.
  • the application of the outer shell layer is preferably carried out by spraying the aqueous alkali metal silicate-containing
  • Solution in a fluidized bed and particularly preferably according to the method described in EP-A 0 970 917, with which even with small amounts of coating layer material, a dense coating layer can be achieved.
  • the application of the outer shell layer takes place in a fluidized bed preferably with the supply of a drying gas to the fluidized bed, so that a temperature in the range of 30 to 90 0 C sets in the fluidized bed.
  • Coating layer containing an alkali metal silicate with a modulus SiO 2 to alkali metal oxide of more than 2.5 show an increased dissolution time when dissolved in water, especially when the outer shell layer by spraying an aqueous solution having a concentration of alkali metal silicate in the range of 2 to 20 wt. -% was applied.
  • Moldings according to the invention containing such coated sodium percarbonate particles with increased dissolution time together with one or more enzymes show an improved effectiveness as detergent or
  • the increased dissolution time of the coated sodium percarbonate particles causes a sustained release of hydrogen peroxide, so that the enzymes can act for a longer period of time before it comes to deactivation of the enzymes by hydrogen peroxide or denaturation of enzymatically degradable proteins by hydrogen peroxide.
  • the sodium percarbonate particles contained in the moldings according to the invention preferably have an average particle size in the range from 0.2 to 5 mm and particularly preferably in the range from 0.5 to 2 mm.
  • the shaped bodies according to the invention preferably contain sodium percarbonate particles with a low fines content, preferably with a fraction of less than 10% by weight of particles smaller than 0.2 mm and particularly preferably less than 10% by weight of particles having a particle size of less than 0.3 mm.
  • the sodium percarbonate particles contained in the moldings according to the invention preferably have a substantially 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 less than 5% of the particle diameter.
  • Particle shape of the sodium percarbonate particles the storage stability of the shaped body according to the invention can be further improved.
  • the compressed shaped bodies according to the invention preferably contain between 1 and 90% by weight and more preferably between 5 and 40% by weight of the above-described coated sodium percarbonate particles.
  • the pressed molded bodies according to the invention preferably also contain at least one surfactant in addition to the coated sodium percarbonate particles, surfactants which are suitable for detergents and cleaning agents preferably being selected.
  • the pressed molded bodies according to the invention may also contain further ingredients suitable for detergents and cleaning agents, preferably those from the series of builders, alkaline components, bleach activators, enzymes, chelating complexing agents, grayness inhibitors, foam inhibitors, optical agents
  • Brightener, silver corrosion inhibitors, fragrances and dyes are especially suitable for the compressed molded bodies according to the invention.
  • Suitable anionic surfactants are, for example, surfactants with sulfonate groups, preferably alkylbenzenesulfonates, alkanesulfonates, alpha-olefinsulfonates, alpha-sulfofatty acid esters or sulfosuccinates.
  • alkylbenzenesulfonates those having a straight-chain or branched alkyl group having 8 to 20 carbon atoms, more preferably 10 to 16 carbon atoms are preferred.
  • Preferred alkanesulfonates are those having straight-chain alkyl chains of 12 to 18 carbon atoms.
  • alpha-olefin sulfonates the reaction products of the sulfonation of alpha-olefins having 12 to 18 carbon atoms are preferably used.
  • the alpha-sulfofatty acid esters imitation products of fatty acid esters of fatty acids having 12 to 18 carbon atoms and short-chain alcohols having 1 to 3 carbon atoms are preferred.
  • anionic surfactants are surfactants having a sulfate group in the molecule, preferably alkyl sulfates and ether sulfates.
  • Preferred alkyl sulfates are those having straight chain alkyl radicals of 12 to 18 carbon atoms.
  • ether sulfates are the alkyl ether sulfates obtained by ethoxylation of linear alcohols having 12 to 18 carbon atoms with 2 to 6 ethylene oxide units followed by sulfation.
  • anionic surfactants it is also possible to use soaps, such as, for example, alkali metal salts of lauric acid, myristic acid, palmitic acid, stearic acid and / or natural ones Fatty acid mixtures, such as coconut, palm kernel or tallow fatty acids.
  • Suitable nonionic surfactants are, for example, alkoxylated compounds, in particular ethoxylated and propoxylated compounds. Particularly suitable are condensation products of alkylphenols or fatty alcohols with 1 to 50 mol, preferably 1 to 10 mol of ethylene oxide and / or propylene oxide. Also suitable are polyhydroxy fatty acid amides in which the amide nitrogen is bonded to an organic radical having one or more hydroxyl groups, which may also be alkoxylated. Also suitable as nonionic surfactants are alkyl glycosides having a straight-chain or branched alkyl group having 8 to 22 carbon atoms, in particular having 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 C 6 - to C 6 -alkyl radical bonded to the nitrogen and one or two hydroxyalkyl groups.
  • the molded compacts of the invention may also contain builders capable of binding calcium and magnesium ions dissolved in the water when used. Suitable builders are alkali metal phosphates and alkali metal polyphosphates, especially pentasodium triphosphate; water-soluble and water-insoluble sodium silicates, in particular phyllosilicates of the formula Wa 5 Si 2 Os; Zeolites of structures A, X and / or P; and trisodium citrate. In addition to the Builders may also organic cobuilders, such as polyacrylic acid, polyaspartic acid and / or acrylic acid copolymers with methacrylic acid, acrolein or sulfonated onklare restroomn vinyl monomers, and their alkali metal salts are used.
  • organic cobuilders such as polyacrylic acid, polyaspartic acid and / or acrylic acid copolymers with methacrylic acid, acrolein or sulfonated onklare restroomn vinyl monomers, and their alkali metal
  • the pressed molded bodies according to the invention may contain, in addition to the coated sodium percarbonate particles contained therein, further alkaline components which, when used as intended in a washing liquor or an aqueous cleaning agent solution, have a pH in the range from 8 to 12.
  • alkaline components especially sodium carbonate, sodium sesquicarbonate, sodium metasilicate and other soluble alkali metal silicates are suitable.
  • the pressed moldings according to the invention can furthermore also contain bleach activators.
  • bleach activators are compounds with one or more perhydrolysis, to nitrogen or
  • Oxygen-bonded acyl groups which react with the hydrogen peroxide released from the sodium percarbonate particles in a wash liquor or an aqueous cleaning agent solution to give peroxycarboxylic acids. Examples of such
  • Compounds are polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED); acylated triazine derivatives, in particular 1, 5-diacetyl-2, 4-dioxohexahydro-l, 3, 5-triazine (DADHT); acylated glycolurils, especially tetraacetylglycoluril (TAGU); N-acylimides, especially N-nonanoylsuccinimide (NOSI); acylated Phenolsulf onate, in particular n-nonanoyl or iso-Nonanoyloxybenzolsulf onat (n- or iso-NOBS); Carboxylic acid anhydrides, such as phthalic anhydride; acylated polyhydric alcohols such as ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, acetylated sorbito
  • bleach activators are amino-functionalized nitriles and their salts (nitrile quats), which are described, for example, in the journal Surfactants Surf. Det. 1997, 34 (6), pages 404-409.
  • bleach activators also transition metal complexes can be used, the
  • Suitable transition metal complexes are known, for example, 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,
  • the compressed shaped bodies according to the invention can furthermore contain enzymes which enhance the cleaning action, in particular lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and / or peroxidases.
  • the enzymes can be adsorbed on carriers or in
  • the compressed molded bodies according to the invention may also contain chelating complexing agents for transition metals, with which a catalytic decomposition of active oxygen compounds in a wash liquor, or an aqueous
  • Suitable examples are phosphonates, such as hydroxyethane-1, 1-disphosphonate, nitrilotrimethylene phosphonate, diethylene triamine penta (methylene phosphonate), ethylenediamine tetra (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) and their alkali metal salts.
  • nitrilotriacetic acid and polyaminocarboxylic acids in particular ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N, N'-disuccinic acid, methylglycinediacetic acid and polyaspartates, and also their alkali metal and ammonium salts.
  • polybasic carboxylic acids and in particular hydroxycarboxylic acids, in particular tartaric acid and citric acid are also suitable as chelating complexing agents.
  • the compressed molded articles according to the invention can additionally contain graying inhibitors for use in detergents or as detergents, which keep the dirt removed from fibers suspended and prevent the dirt from being re-applied to the fibers.
  • Suitable graying inhibitors are, for example, cellulose ethers such as carboxymethylcellulose and its alkali metal salts, methylcellulose, hydroxyethylcellulose and hydroxypropylcellulose. Also suitable is polyvinylpyrrolidone.
  • the pressed moldings according to the invention may furthermore also contain foam inhibitors which reduce the foaming in a wash liquor. Suitable foam inhibitors are, for example, organopolysiloxanes such as polydimethylsiloxane, paraffins and / or waxes, and mixtures thereof with finely divided silicic acids.
  • the compressed molded articles according to the invention may optionally contain optical brighteners for use in detergents or as detergents, which are applied to fibers, absorb light in the UV region and fluoresce blue, in order to compensate for yellowing of the fibers.
  • Suitable optical brighteners are, for example derivatives of diaminostilbenedisulfonic acid, such as alkali metal salts of 4, 4 ⁇ -bis- (2-anilino-4-morpholino-l, 3, 5-triazinyl-6-amino) - stilbene-2, 2 '-disulfonic acid or substituted diphenyl, such as alkali metal salts of 4,4 X-bis- (2-sulfostyrlyl) -diphenyl.
  • the pressed molded articles according to the invention may also contain, for use as machine dishwashing detergents, silver corrosion inhibitors which prevent or reduce the tarnishing of non-ferrous metals, in particular silver, during machine cleaning with the machine-dishwashing detergent.
  • the silver corrosion inhibitors used are preferably one or more compounds from the series of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles and alkylaminotriazoles.
  • the compounds of the substance classes mentioned may also have substituents, such as linear or branched alkyl groups having 1 to 20 carbon atoms, as well as vinyl, hydroxy, thiol or halogen radicals.
  • a particularly preferred silver corrosion inhibitor is tolyltriazole.
  • compressed molded bodies according to the invention may also contain fragrances and dyes.
  • the compressed molded articles according to the invention preferably have the form of pellets, briquettes or tablets, but are in principle not limited in their shape. Particularly preferably, the shaped bodies have the form of round or rectangular tablets.
  • the size of the pressed molded bodies according to the invention is also basically not limited and is preferably in the range of 5 to 50 g. In the case of compressed molded articles which, in addition to sodium percarbonate, also contain at least one surfactant and further ingredients suitable for detergents and cleaning agents, the size of the shaped bodies is preferably selected such that a shaped body contains the amount of washing-active substances required for a washing cycle in a washing machine or a dishwashing machine.
  • the pressed molded bodies according to the invention can be prepared by pressing agglomeration processes, in particular by hole pressing, roll compacting or tabletting, starting from pulverulent feedstocks or starting materials Granules are produced.
  • the pressed molded bodies according to the invention may additionally contain one or more binders which give the shaped bodies a higher strength during press agglomeration.
  • one or more detergent-active ingredients for use in detergents or cleaners, for example, nonionic surfactants perform the function of the binder.
  • the pressed molded bodies according to the invention have a better stability during storage than moldings containing sodium percarbonate particles with a coating layer not constructed according to the invention.
  • the compressed molded bodies according to the invention show a significantly lower loss of active oxygen content.
  • the pressed molded bodies according to the invention also exhibit an improved combination of the strength of the shaped bodies and the dissolution rate of the shaped bodies in water, since the pressed molded bodies according to the invention have a higher strength than molded bodies produced under the same pressing conditions and contain sodium percarbonate particles with a differently structured coating layer.
  • the invention also provides a process for the production of the compressed molded bodies according to the invention, in which a pulverulent mixture containing coated sodium percarbonate particles is compacted by tabletting or briquetting, the enveloped ones
  • Sodium percarbonate particles an enclosure having an inner shell layer containing one or more water-soluble hydrate-forming salts and an overlying outer shell layer containing an alkali metal silicate.
  • the term pulverulent mixture also includes mixtures which contain granules with particle dimensions of up to 2 mm.
  • the shaped bodies are obtained without the addition of water, so that a dissolution of the coating layer of the sodium percarbonate particles during the shaping process is avoided.
  • the pressed moldings produced by the process according to the invention simultaneously have a high strength of the moldings and a high dissolution rate of the moldings in water.
  • the pressed molded bodies according to the invention can be used advantageously in detergents and cleaning agents.
  • the pressed molded bodies according to the invention can be formulated as mixtures with further granules or shaped bodies to ready-to-use detergents or cleaning agents.
  • Such mixtures have the advantage that, when stored with sodium percarbonate, incompatible constituents of the mixture can be contained in the further granules or shaped bodies and thus the shelf life of the formulated detergent or cleaning agent can be further improved.
  • compressed molded bodies according to the invention which contain other detergent ingredients in addition to sodium percarbonate, in combination with other granules or moldings, the densities of the granules or moldings contained in such a mixture can be coordinated so that a separation of the components of the formulation can be avoided can.
  • the pressed molded bodies according to the invention can also be used in detergents and cleaning agents in a further embodiment in which an inventive Shaped body is used as a portioned Bleachitiittelkomponente together with a ready-formulated detergent or cleaning agent containing no bleach.
  • Compressed molded articles according to the invention which additionally contain at least one surfactant and optionally further substances from the series of builders, alkaline components, bleach activators, enzymes, chelating complexing agents, grayness inhibitors, foam inhibitors, optical
  • Brightener, fragrances and dyes included can also be used advantageously on its own as a detergent or cleaning agent.
  • the size and composition of the compressed molded bodies according to the invention is preferably selected such that a shaped body contains all the washing-active substances required for a washing operation or cleaning process.
  • sodium percarbonate particles were used which were prepared by fluidized bed granulation from aqueous hydrogen peroxide solution and aqueous sodium carbonate solution according to the method described in WO 95/06615 and have an average particle diameter x 50 of 0.65 mm and a Fine grain content of less than 0.2 mm of less than 2 wt .-% had.
  • the coating layers were applied to these particles by the method described in EP-B 0 863 842 in section [0021] by spraying aqueous solutions of the coating materials in a fluidized bed at a
  • Sodium sulfate was sprayed on as a 20% by weight aqueous solution.
  • Water glass was used as a 10 wt .-% aqueous solution of sodium water glass with a module siue 2: Na 2 O of 3.3 sprayed. The in the
  • Examples in percentages by weight of coated amounts refer to the amount of coating agent sprayed, calculated without water of crystallization, relative to the total amount of sodium percarbonate particles used and sprayed-on coating substances.
  • the heat release by decomposition of sodium percarbonate was determined by microcalorimetric determination of the heat release of samples when stored at 40 ° C. using a TAM® Thermal Activity Monitor from Thermometric AB, Järsocila (SE).
  • the specified TAM values are the measured values determined after storage after 48 h.
  • Enveloped sodium percarbonate particles were mixed in a tumble mixer with a commercially available
  • Dishwashing powder mixed containing 2.2 wt.% TAED, but no bleach, leaving the mixture
  • Cardboard box (dimensions 14 x 14 x 6 cm), which was closed with hot glue, stored for 14 days at 50 0 C. After storage, the active oxygen content was determined iodometrically and the retention of the active oxygen content (Oa recovery) was determined in percent.
  • Sodium detergent particles were prepared as described above dishwashing tablets, as well as the mixture of dishwashing detergent powder and
  • Example 3 show a higher storage stability with lower loss of active oxygen than the tablets from Examples 1 and 3, which contain sodium percarbonate with only one of the coating layers, or the tablets from Example 4, the sodium percarbonate with two Coating layers of the same amount and composition contained in a reversed order.
  • the coated sodium percarbonate particles of Examples 3 and 4 showed approximately the same before compression in admixture with the other components of the tablet

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des corps moulés comprimés contenant des particules de percarbonate de sodium enrobées, présentant une couche d'enrobage intérieure contenant un ou plusieurs sels solubles dans l'eau, formant un hydrate, et une couche d'enrobage extérieure située sur celle-ci, contenant un silicate de métal alcalin. Lesdits corps moulés présentent une meilleure stabilité au stockage ainsi que des pertes en oxygène actif réduites. Lesdits corps moulés contiennent par ailleurs de préférence au moins un tensioactif et éventuellement d'autres agents détergents. Lesdits corps moulés peuvent être fabriqués par mise en tablettes ou briquettes d'un mélange pulvérulent. Lesdits corps moulés peuvent être employés dans des lessives ou des détergents.
EP05810720A 2004-12-14 2005-11-24 Corps moules comprimes contenant des particules de percarbonate de sodium enrobees Withdrawn EP1824783A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004060011A DE102004060011A1 (de) 2004-12-14 2004-12-14 Verpresste Formkörper enthaltend umhüllte Natriumpercarbonatpartikel
PCT/EP2005/012597 WO2006063668A1 (fr) 2004-12-14 2005-11-24 Corps moules comprimes contenant des particules de percarbonate de sodium enrobees

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EP1824783A1 true EP1824783A1 (fr) 2007-08-29

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US (1) US20060154841A1 (fr)
EP (1) EP1824783A1 (fr)
JP (1) JP2008522945A (fr)
CN (1) CN101061063A (fr)
CA (1) CA2583830C (fr)
DE (1) DE102004060011A1 (fr)
MY (1) MY142234A (fr)
WO (1) WO2006063668A1 (fr)

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US8946141B2 (en) * 2009-05-14 2015-02-03 Ecolab Usa Inc. Compositions, systems and method for in situ generation of alkalinity
EP2584028B1 (fr) * 2011-10-19 2017-05-10 The Procter & Gamble Company Particule
CA2895328A1 (fr) * 2012-12-20 2014-06-26 The Procter & Gamble Company Composition de detergent ayant un agent de blanchiment revetu par du silicate
DE102013211093A1 (de) 2013-06-14 2014-12-18 Evonik Treibacher Gmbh Umhüllte Natriumpercarbonatpartikel
EP3039113B1 (fr) * 2013-08-28 2019-12-04 Novozymes A/S Granulés enzymatiques avec agent de blanchiment fluorescent
CN106811336A (zh) * 2015-11-30 2017-06-09 常州西品科技有限公司 家用清洁剂
CN106811315A (zh) * 2015-11-30 2017-06-09 常州西品科技有限公司 家用清洁片
US10626350B2 (en) 2015-12-08 2020-04-21 Ecolab Usa Inc. Pressed manual dish detergent
CN105505622A (zh) * 2015-12-15 2016-04-20 濮阳宏业环保新材料股份有限公司 可染色过碳酸钠及该过碳酸钠的染色方法
CN105331459A (zh) * 2015-12-15 2016-02-17 濮阳宏业环保新材料股份有限公司 一种染色过碳酸钠及其制备方法
CN106544181A (zh) * 2016-10-27 2017-03-29 陆腾蛟 一种洗洁产品及生产设备及工艺
WO2019241629A1 (fr) * 2018-06-15 2019-12-19 Ecolab Usa Inc. Stabilité améliorée du peroxygène à l'aide d'acide gras dans un solide peroxygéné contenant un agent d'activation de blanchiment
CN112742381B (zh) * 2019-10-29 2023-03-10 中国石油化工股份有限公司 壳层分布型催化剂及其制备方法和应用

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Publication number Publication date
WO2006063668A1 (fr) 2006-06-22
US20060154841A1 (en) 2006-07-13
CA2583830A1 (fr) 2006-06-22
JP2008522945A (ja) 2008-07-03
DE102004060011A1 (de) 2006-07-06
MY142234A (en) 2010-11-15
CN101061063A (zh) 2007-10-24
CA2583830C (fr) 2010-08-24

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