EP0241962B1 - Phosphatfreie, granulierte Reinigungs- und Bleichmittelzusammensetzungen - Google Patents

Phosphatfreie, granulierte Reinigungs- und Bleichmittelzusammensetzungen Download PDF

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Publication number
EP0241962B1
EP0241962B1 EP87200469A EP87200469A EP0241962B1 EP 0241962 B1 EP0241962 B1 EP 0241962B1 EP 87200469 A EP87200469 A EP 87200469A EP 87200469 A EP87200469 A EP 87200469A EP 0241962 B1 EP0241962 B1 EP 0241962B1
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EP
European Patent Office
Prior art keywords
weight
water
carbonate
bleach activator
soluble
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EP87200469A
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English (en)
French (fr)
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EP0241962A2 (de
EP0241962A3 (en
Inventor
James Gavin De Bernat
Ian Donald Robb
Raymond John Wilde
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Publication of EP0241962A2 publication Critical patent/EP0241962A2/de
Publication of EP0241962A3 publication Critical patent/EP0241962A3/en
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Classifications

    • 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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1233—Carbonates, e.g. calcite or dolomite
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof

Definitions

  • This invention relates to granular non-phosphorus bleach activator containing detergent bleach compositions. Particularly it pertains to granular compositions containing activators for peroxygen bleaching agents in the form of organic peroxyacid bleach precursors usable in phosphorus-free granular detergent bleach compositions.
  • Granular detergent compositions which contain organic bleach activators in addition to the usual detergent substances having a cleaning action, builders and peroxygen bleaching agents are known in the art.
  • the peroxygen bleaching agents commonly used are those which release hydrogen peroxide in aqueous solution, such as alkali metal perborates, persilicates, percarbonates, perphosphates and urea peroxide. These peroxygen bleaching agents will hereinafter also be referred to as "persalts".
  • the most commonly used persalt in detergent compositions is alkali metal perborate, particularly sodium perborate, tetrahydrate or monohydrate.
  • the organic bleach activators referred to herein are generally organic N-acyl or O-acyl compounds, or carbonic or pyrocarbonic esters, which react with hydrogen peroxide (e.g. from the persalts) in solution forming a peroxy acid or percarbonic acid, a bleaching species which, unlike the persalts, is effective in bleaching at lower temperatures, e.g. from ambient to 60 ° C.
  • bleach activators are amply described in literature, for example in a series of articles by Allan H. Gilbert in Detergent Age, June 1967, pages 18-20, July 1967, pages 30-33, and August 1967, pages 26, 27 and 67, andfurther in British Patent Specifications 836,988; 855,735; 907,356; 907,358; 970,950; 1,003,310 and 1,246,339; US Patent Specifications 3,332,882, 3,277,750, 4,128,494 and 4,412,934.
  • bleach activator compounds are generally hydrolysable materials, they need to be protected from the surrounding media when incorporated in detergent compositions.
  • any proper method of protecting the bleach activator from the environment must allow a relatively quick release or dissolution of the activator in the wash liquor. Release of the activator must be achieved at a period well before the end of the wash cycle so as to give time for the activator to react with the persalt forming the peroxyacid. Preferably this should occur as early as possible in the wash cycle for maximum bleaching to occur.
  • bleach activator granules Various compositions and forms of bleach activator granules have been proposed in the art, most of them using a phosphate, particularly sodium triphosphate, as an essential component of the granulating agent because of its typical property of imparting good structure combined with quick dispersion to the granule.
  • a representative example of such bleach activator granule compositions having good storage stability and satisfactory release is that which comprises a mixture of sodium triphosphate and potassium triphosphate as the granulating agent, currently used in the majority of commercial detergent powder formulations.
  • phosphates such as sodium triphosphate
  • non-phosphorus builders especially a mixture of an alkali metal carbonate, such as sodium carbonate, with a water-insoluble calcium carbonate seed material, such as calcite, as disclosed for example in GB Patent Specifications 1,437,950 (Unilever), 1,481,516 (Unilever) and 1,481,685 (Unilever), and it is for use in compositions containing such builders that the present non-phosphorus bleach activator granule composition is particularly designed.
  • Non-phosphorus-containing bleach activator granule compositions are known in the art and various methods of preparing such granules and their use in detergent compositions have been proposed.
  • an organic compound or a mixture of organic compounds were proposed as the binding or coating agent, such as for example nonionic compounds, fatty acids, fatty alcohols, waxes and polymeric materials with or without the optional use of inorganic salts.
  • German DE-OS 2,657,042 discloses a detergent composition comprising tetraacetyl ethylene diamine (TAED) in the form of granules, which consist of said TAED activator and a nonionic surfactant having a melting point of at least 35 ° C as the binding agent.
  • TAED tetraacetyl ethylene diamine
  • European EP-B-0051987 discloses bleach activator granule compositions comprising a bleach activator and a nonionic surfactant having a melting point of not more than 40 ° C as binding agent.
  • nonionics tend to bleed and cause stickiness, giving rise to caking problems, especially urider hot summer temperature conditions.
  • Migration pf nonionics in the formulation would also tend to aid decomposition of bleach-sensitive ingredients owing to interaction with the oxidising bleach system.
  • Higher melting nonionics will have poor dispersing ability, resulting in a poor release of the bleach activator, with the deleterious consequence of the granules sedimenting and being lost in the dead spaces of the washing machines, known as mechanical loss.
  • EP-0070474 and EP-0037026 disclose methods of using water-soluble cellulose ether, starch or starch ether as granulation binder for preparing bleach activator granules having a bleach activator content of from 90-99% by weight. The methods as described here are only viable if coarse particle size bleach activators are used.
  • European Patent Application EP-0075818 discloses water-free activator granules comprising a) 70-99.5% bleach activator and b) 0.5-30% of a swelling agent, prepared by compacting the compounds a) and b) without the addition of water, optionally followed by breaking into smaller particles.
  • swelling agents are mentioned high molecular weight carbohydrates, such as starch, powdered cellulose, wood pulp; cross-linked polyvinyl pyrrolidone (PVP) and also starch ether and carboxymethyl cellulose.
  • PVP polyvinyl pyrrolidone
  • non-phosphorus-containing bleach activator composition which can be used in non-phosphorus granular detergent bleach compositions containing as builders a mixture of an alkali metal carbonate with a water-insoluble particulate carbonate material, which is capable of acting as a seed crystal for the precipitate resulting from the reaction between the calcium hardness ions of the water and the water-soluble carbonate, e.g. a mixture of sodium carbonate and calcite without poisoning the water-insoluble carbonate material, especially calcite, whereby its seed activity is reduced.
  • a finely divided particulate bleach activator is granulated to a size of from about 0.2-2.0 mm, using an inert non-alkaline, non-phosphate inorganic or organic salt and a water-soluble, low- to non- carboxylate containing film-forming polymeric material having average molecular weight of from 500-1, 000, 000, as granulating agent.
  • the granular bleach activator composition of the invention is essentially free of phosphorus materials and comprises:
  • Preferred bleach activators are the N-diacylated and N,N'-tetraacylated amines mentioned under a) above, particularly N,N,N',N'-tetraacetyl ethylene diamine, the esters of carbonic or pyrocarbonic acids mentioned under m) and the reactive phenol esters as described in US Patent Specification 4,412,934 and GB Patent Specifications 836,988 and 864,798.
  • the inert non-alkaline, non-phosphate inorganic or organic salts which can be used in the invention are, for example, sodium sulphate, sodium nitrate, sodium chloride, sodium citrate, calcium sulphate and calcium chloride.
  • a preferred salt is sodium sulphate.
  • the low- to non-carboxylate film-forming polymeric material usable in the invention will be any polymer, both homo- and co-polymers, which have a carboxyl group to polymer weight ratio of less than 1:5. They may be composed of monomers such as vinyl acetate, vinyl pyrrolidone, methyl vinylether, styrene and styrene sulphonate, alkyl acrylates, etc.
  • suitable polymeric materials include polyvinylpyrrolidone, polyvinyl alcohol, co-polymers of polyvinyl alcohol/polyvinyl acetate, carbohydrates and carbohydrate ethers such as carboxymethyl cellulose, and dextrin-modified vinylacetate polymers. Polymers having average molecular weight of less than 500,000, particularly less than 100,000, are preferred.
  • the granular bleach activator composition will comprise:
  • Water may be present in an amount of up to about 5%, preferably up to 4%.
  • the granular bleach activator composition has particular applicability to non-phosphorus detergent compositions containing as builders a mixture of an alkali metal carbonate, such as sodium carbonate, with a water-insoluble carbonate seed material, such as calcium carbonate, e.g. calcite.
  • an alkali metal carbonate such as sodium carbonate
  • a water-insoluble carbonate seed material such as calcium carbonate, e.g. calcite.
  • the invention provides a granular detergent bleach composition which is substantially free of phosphorus-containing material, comprising:
  • the detergent-active material can be anionic, nonionic, cationic or zwitterionic or a mixture of such agents.
  • Nonionic surfactants suitable for use in the present invention include water-soluble compounds produced by the condensation of ethylene oxide with a hydrophobic compound such as an alcohol, alkyl phenol, polypropoxy glycol or polypropoxy ethylene diamine. Also suitable are alkyl amine oxides, alkyl polyglucosides and alkyl methylsulphoxides.
  • Preferred nonionic surfactants are polyethoxy alcohols formed as the condensation products of 1 to 30 moles of ethylene oxide with 1 mole of ethylene oxide with 1 mole of branched- or straight-chain, primary or secondary aliphatic alcohols having from about 8 to about 22 carbon atoms; more especially, 6 to 15 moles of ethylene oxide are condensed with 1 mole of straight- or branched-chain, primary or secondary aliphatic alcohol having from about 10 to about 16 carbon atoms.
  • Certain polyethoxy alcohols are commercially available under the trade-names "Neodol", “Synperonic” and "Tergitol”.
  • Anionic surfactants suitable for use in formulating the detergent bleach compositions of the invention include water-soluble alkali metal alkylbenzenesulphonates, alkyl sulphates, alkylpolyethoxyether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alpha sulphocarboxylates and their esters, alkylglycerylether sulphonates, fatty acid monoglyceride sulphates and sulphonates, alkylphenolpoly- ethoxy ethersulphates, 2-acyloxyalkane-1-sulphonates and beta-alkyloxyalkane sulphonates. Soaps can also be used as anionic surfactants.
  • Preferred anionic surfactants are alkylbenzenesulphonates with about 9 to about 15 carbon atoms in a linear or branched alkyl chain, more especially about 11 to about 13 carbon atoms; alkylsulphates with about 8 to about 22 carbon atoms in the alkyl chain, more especially from about 12 to about 18 carbon atoms; alkylpolyethoxy ethersulphates with about 10 to about 18 carbon atoms in the alkyl chain and an average of about 1 to about 12 -CH z CH 2 0-groups per molecule; linear paraffin sulphonates with about 8 to about 24 carbon atoms, more especially from about 14 to about 18 carbon atoms and alpha-olefin sulphonates with about 10 to about 24 carbon atoms, more especially about 14 to about 16 carbon atoms; and soaps having from 8 to 24, especially 12 to 18 carbon atoms.
  • Cationic surface-active agents suitable for use in the invention include the quaternary ammonium compounds, e.g. cetyltrimethylammonium bromide or chloride and distearyldimethylammonium bromide or chloride, and the fatty alkyl amines.
  • Zwitterionic surfactants that can be used in the present invention include water-soluble derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium cationic compounds in which the aliphatic moieties can be straight or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, especially alkyldimethylammoni- um propanesulphonates and carboxylates (betaines) and alkyldimethylammoniohydroxy propanesulphonates and carboxylates wherein the alkyl group in both types contains from about 8 to 18 carbon atoms.
  • the effective amount of the detergent active compound or compounds used in the composition is generally in the range from 5 to 40% by weight, preferably not more than 30% by weight of the composition.
  • a second essential ingredient of the composition is a water-soluble carbonate material as a builder.
  • This is preferably sodium or potassium carbonate or a mixture thereof, for reasons of cost and efficiency.
  • the carbonate salt is preferably fully neutralised but it may be partially neutralised, for example a sesquicarbonate may be used in partial replacement of the normal carbonate salt; the partial salts tend to be less alkaline and therefore less efficient.
  • the amount of water-soluble carbonate material in the detergent composition can be varied widely, but the amount should be at least 5% by weight, such as from 10% to 40%, preferably 10% to 30% by weight, though an amount of up to 75% could possibly be used, if desired, in special products.
  • the amount of the water-soluble carbonate material is determined on an anhydrous basis, though the salts may be hydrated either before or when incorporated in the detergent composition. It should be mentioned that within the preferred range the higher levels tend to be required under conditions of use at low product concentrations, as is commonly the practice in North America, and the converse applies under conditions of use at higher product concentrations, as tends to occur in Europe. It should be noted that it may also be desirable to limit the carbonate content to a lower level within the range mentioned, so as to decrease the risk of internal damage following any accidental ingestion, for example by children.
  • water-soluble carbonate material it is possible to include minor amounts of other non-phosphorus detergency builders, provided that the total amount of the detergency builders does not exceed 85% by weight, so as to leave room in the detergent composition for other desirable ingredients.
  • a soap is used as a detergent active material, it may be present in such a quantity that it will al - so contribute as an additional builder.
  • the composition further necessarily contains a water-insoluble particulate carbonate material.
  • This material must be capable of acting as a seed crystal for the precipitate which results from the reaction between the calcium hardness ions of the water and the water-soluble carbonate.
  • this water-insoiu- ble particulate material is a seed crystal for calcium carbonate, such as calcium carbonate itself.
  • the water-insoluble particulate carbonate material should be finely divided and should have a surface area of at least 10 0 m2/g, and preferably at least 15 m 2 /g.
  • the particularly preferred material has a surface area from 30-100 m2/g. Insoluble carbonate material with surface areas in excess of 100 m 2 /g may be used if such materials are economically available.
  • the high surface area material be prepared in the absence of poisons, so as to retain its seed activity.
  • the insoluble carbonate material will usually have an average particle size of less than 10 microns, as measured by sieve analysis.
  • any crystalline form thereof may be used or a mixture thereof, but calcite is preferred as aragonite and vaterite are less readily available commercially, and calcite is a little less soluble than aragonite or vaterite at most usual wash temperatures.
  • any aragonite or vaterite is used, it is generally in admixture with calcite.
  • the term 'calcite' is used to mean either calcite itself or any other suitable water-insoluble calcium carbonate seed material.
  • the selected level of calcite in the overall composition depends on the specific surface area as described above.
  • the amount of calcite used in the compositions should be from 5% to 60%, more preferably from 5% to 30%.
  • non-phosphorus detergency builders known in the art and described in a number of patent publications, such as the sodium carboxy methyloxy disuccinates, citric acid, mellitic acid, benzene polycarboxylic acids, and the polyacetalcarboxylates as disclosed in US Patent Specification 4 144 226 may be incorporated in minor amounts to the carbonate system.
  • the amount of peroxygen bleaching agent used in the compositions of the invention will generally be from 5% to 30% by weight, preferably from 7% to 25% by weight.
  • the amount of non-phosphorus bleach activator granules incorporated in the compositions will depend on the bleach activator content of the granule composition and may be from 0.5% to 15% by weight, more preferably from 1.5% to 10% by weight, calculated as pure bleach activator.
  • the bleach activator as used in preparing the granular bleach activator compositions, it is preferred that its particle size should be less than 200 micrometre, more preferably up to 150 micrometre.
  • Suitable bleach activators are those having a major proportion of particle size of between 50 micrometre and 150 micrometre. Particle size distribution as described in US Patent Specification 4 283 302 are especially suitable.
  • the detergent compositions in which the granular non-phosphorus bleach activator compositions are incorporated can optionally contain any of the conventional ingredients in the amounts in which such ingredients are normally employed in fabric washing detergent compositions.
  • One such optional ingredient is an alkali metal silicate, particularly sodium, neutral, alkaline, meta- or orthosilicate.
  • a low level of silicate for example from about 2-10% by weight, is usually advantageous in decreasing the corrosion of metal parts in fabric washing machines and it may give processing benefits. If higher levels of silicate are used up to a practical maximum of 30%, for example from 10% to 20% by weight, there can be a more noticeable improvement in detergency, which may permit some decrease in the water-soluble carbonate material content. This effect appears to be particularly beneficial when the wash liquor is used in water with appreciable levels of magnesium hardness.
  • the amount of silicate can also be used to some extent to control the equilibrium pH of the wash liquor, which is generally within the range of 9-11, preferably 10-11, for an aqueous solution of the composition at the recommended concentration. It should be noted that a higher pH (i.e. over pH 10.5) tends to be more efficient as regards detergency, but it may be less desirable for domestic safety.
  • Sodium silicate is commonly supplied in concentrated aqueous solution or in concentrated powder form, but the amounts are calculated on an anhydrous basis.
  • Examples of other optional ingredients include the lather boosters, such as alkanolamides, particularly the monoethanolamides derived from palmkernel fatty acids and coconut fatty acids, lather depressants, fabric softening agents, inorganic salts, such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes, such as proteases and amylases, germicides and colourants.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palmkernel fatty acids and coconut fatty acids
  • lather depressants such as the lather depressants
  • fabric softening agents such as sodium sulphate
  • fluorescent agents such as sodium sulphate
  • perfumes such as acetylases
  • germicides and colourants particularly when the composition does not contain an anionic detergent active material, it can be beneficial to include an anti-ashing material to reduce the deposition of calcium carbonate on to fabrics.
  • the detergent compositions may be produced by any of the techniques commonly employed in the manufacture of fabric washing detergent compositions, including particularly slurry-making and spray-drying processes for the manufacture of detergent powders.
  • a solid feed consisting of a mixture of 90% TAED (average particle size of 50-150 micrometre) and 10% sodium sulphate was sprayed in a Schugi@ Flexomix 160 apparatus with the proper amount of an aqueous solution consisting of 15% polymer and 85% water.
  • the product was aerated to dry and obtain a product of the above composition with the following properties:
  • TAED granular non-phosphorus bleach activator
  • the product was dried in a fluid bed to yield a product of the above composition with the following properties:
  • the granule made according to the invention has no effect on water softening, whereas a granule containing a poison causes a drastic reduction in the water softening achieved.
  • the two compositions were used to wash 2.5 kg of a soiled fabric load in washing machines having a capacity of 18 litres, the load including a number of bleach-sensitive test cloths. The reflectance of these cloths was measured both before and after the wash and the difference ( ⁇ R 460 *) calculated.
  • the wash conditions were a pre-wash followed by a 35 minute wash cycle heating up from 15 ° C to 60 ° C.
  • the water hardness was 40 ° FH (Ca:Mg molar ratio 4:1).
  • 80 g each composition was used in the pre-wash, 100 g for the main wash.
  • the pH of the wash liquor was measured both before and after the wash. The results were as follows, being averaged over 6 washes:
  • the granular bleach activator granules were used in carbonate/calcite base powder compositions. No poisoning of calcite was observed.

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

Claims (4)

1. Granulierte Detergenz-Bleich-Zusammensetzung, im wesentlichen frei von phosphorhaltigem Material umfassend ein detergenzaktives Material, ein wasserlösliches Carbonatmaterial, das ein Detergenzgerüststoff ist, ein wasserunlösliches, teilchenförmiges Carbonatmaterial, das ein Impfkristall für Calciumcarbonat ist, ein Peroxygen-Bleichmittel und einen Bleichaktivator, dadurch gekennzeichnet, daß der Bleichaktivator in der Form von nicht-phosphorhaltigen Körnchen einer Größe von 0,2-2,0 mm vorhanden ist, umfassend:
(a) von 50-90 Gew.-% fein zerteilter, partikelförmiger Bleichaktivator,
(b) von 5-45 Gew.-% eines inerten, nicht-alkalischen, phosphatfreien, wasserlöslichen, anorganischen oder organischen Salzes, und
(c) von 1-15 Gew.-% eines wasserlöslichen, niedrig- bis nicht-Carboxylat-enthaltenden, filmbildenden polymeren Materials, mit einem Carboxylgruppen zu Polymer Gewichtsverhältnis von weniger als 1:5, eines durchschnittlichen Molekulargewichts von 500-1 000 000.
2. Granulierte Detergenz-Bleich-Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das wasserlösliche Salz Natriumsulfat ist.
3. Granulierte Detergenz-Bleich-Zusammensetzung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das wasserunlösliche Carbonatmaterial Calcit ist.
4. Granulierte Detergenz-Bleich-Zusammensetzung nach Anspruch 3, dadurch gekennzeichnet, daß sie 5-40 Gew.-% detergenzaktives Material, 5-75 Gew.-% wasserlösliches Carbonatmaterial, 5-60 Gew.-% Calcit, 5-30 Gew.-% Peroxygen-Bleichmittel und von 0,5-15 Gew.-% Bleichaktivator umfaßt.
EP87200469A 1986-03-25 1987-03-12 Phosphatfreie, granulierte Reinigungs- und Bleichmittelzusammensetzungen Expired - Lifetime EP0241962B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8607387 1986-03-25
GB868607387A GB8607387D0 (en) 1986-03-25 1986-03-25 Activator compositions

Publications (3)

Publication Number Publication Date
EP0241962A2 EP0241962A2 (de) 1987-10-21
EP0241962A3 EP0241962A3 (en) 1988-06-22
EP0241962B1 true EP0241962B1 (de) 1990-05-16

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EP87200469A Expired - Lifetime EP0241962B1 (de) 1986-03-25 1987-03-12 Phosphatfreie, granulierte Reinigungs- und Bleichmittelzusammensetzungen

Country Status (9)

Country Link
EP (1) EP0241962B1 (de)
JP (1) JPH0645799B2 (de)
AU (1) AU586326B2 (de)
CA (1) CA1288311C (de)
DE (1) DE3762753D1 (de)
ES (1) ES2016615B3 (de)
GB (1) GB8607387D0 (de)
TR (1) TR24351A (de)
ZA (1) ZA872198B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7709434B2 (en) 2007-05-04 2010-05-04 Ecolab Inc. Compositions including Ca and Mg ions and gluconate and methods employing them to reduce corrosion and etch

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5002691A (en) * 1986-11-06 1991-03-26 The Clorox Company Oxidant detergent containing stable bleach activator granules
US5112514A (en) * 1986-11-06 1992-05-12 The Clorox Company Oxidant detergent containing stable bleach activator granules
GB8810630D0 (en) * 1988-05-05 1988-06-08 Unilever Plc Process for preparing bodies containing peroxyacid & compositions comprising said bodies
US5269962A (en) * 1988-10-14 1993-12-14 The Clorox Company Oxidant composition containing stable bleach activator granules
GB8919006D0 (en) * 1989-08-21 1989-10-04 Unilever Plc Granulated bleach activator particles
GB9016504D0 (en) * 1990-07-27 1990-09-12 Warwick Int Ltd Granular bleach activator compositions
DE19605526A1 (de) 1996-02-15 1997-08-21 Hoechst Ag Ammoniumnitrile und deren Verwendung als Bleichaktivatoren
WO1998040457A1 (en) * 1997-03-11 1998-09-17 The Procter & Gamble Company Builder mixture containing crystalline calcium carbonate builder for use in detergent compositions
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US7709434B2 (en) 2007-05-04 2010-05-04 Ecolab Inc. Compositions including Ca and Mg ions and gluconate and methods employing them to reduce corrosion and etch
US7741262B2 (en) 2007-05-04 2010-06-22 Ecolab Inc. Compositions including hardness ions and gluconate and methods employing them to reduce corrosion and etch
US7749329B2 (en) 2007-05-04 2010-07-06 Ecolab Inc. Cleaning compositions containing water soluble magnesium compounds and methods of using them
US7919448B2 (en) 2007-05-04 2011-04-05 Ecolab Usa Inc. Compositions including hardness ions and gluconate and methods employing them to reduce corrosion and etch
US7922827B2 (en) 2007-05-04 2011-04-12 Ecolab Usa Inc. Cleaning compositions containing water soluble magnesium compounds and methods of using them
US7960329B2 (en) 2007-05-04 2011-06-14 Ecolab Usa Inc. Compositions including magnesium ion, calcium ion, and silicate and methods employing them to reduce corrosion and etch
US8021493B2 (en) 2007-05-04 2011-09-20 Ecolab Usa Inc. Method of reducing corrosion using a warewashing composition
US8071528B2 (en) 2007-05-04 2011-12-06 Ecolab Usa Inc. Cleaning compositions with water insoluble conversion agents and methods of making and using them
US8207102B2 (en) 2007-05-04 2012-06-26 Ecolab Usa Inc. Compositions including hardness ion and threshold agent and methods employing them to reduce corrosion and etch

Also Published As

Publication number Publication date
TR24351A (tr) 1991-09-16
JPS62240394A (ja) 1987-10-21
DE3762753D1 (de) 1990-06-21
GB8607387D0 (en) 1986-04-30
EP0241962A2 (de) 1987-10-21
ZA872198B (en) 1988-11-30
CA1288311C (en) 1991-09-03
EP0241962A3 (en) 1988-06-22
JPH0645799B2 (ja) 1994-06-15
AU7050687A (en) 1987-10-01
ES2016615B3 (es) 1990-11-16
AU586326B2 (en) 1989-07-06

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