+

WO1997043211A1 - Stabilisation de percarbonate alcalin - Google Patents

Stabilisation de percarbonate alcalin Download PDF

Info

Publication number
WO1997043211A1
WO1997043211A1 PCT/EP1997/002301 EP9702301W WO9743211A1 WO 1997043211 A1 WO1997043211 A1 WO 1997043211A1 EP 9702301 W EP9702301 W EP 9702301W WO 9743211 A1 WO9743211 A1 WO 9743211A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
alkali
weight
acid
percarbonate
Prior art date
Application number
PCT/EP1997/002301
Other languages
German (de)
English (en)
Inventor
Heinz-Manfred Wilsberg
Thomas Merz
Khalil Shamayeli
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP97922976A priority Critical patent/EP0902756A1/fr
Publication of WO1997043211A1 publication Critical patent/WO1997043211A1/fr

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
    • 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
    • C11D3/3937—Stabilising agents
    • C11D3/394—Organic compounds

Definitions

  • the present invention relates to the use of certain salts for stabilizing alkali percarbonates, in particular in washing or cleaning agents.
  • Detergents and cleaning agents which contain peroxidic oxidizing agents, alone or as a bleaching system in the form of a combination of an inorganic peroxide or perhydrate with a bleach activator which forms an organic peroxocarboxylic acid under perhydrolysis conditions, have been known for a long time.
  • the most commonly used bleaching components containing active oxygen respectively
  • Oxidizing agents are the alkali perborates, percarbonates, persulfates and persilicates.
  • bleach activators use is generally made of those compounds which split off carboxylic acids or percarboxylic acids under hydrolysis or perhydrolysis conditions, the predominant use being made of those compounds which deliver peracetic acid in the presence of the peroxidic oxidizing agents. Since the reaction of the activator with the peroxygen compound, which is to take place only under the mostly aqueous conditions of use of the agents, can also take place during the preparation and in particular the storage of such agents, as a result of which the availability of the peroxygen compound for the actual intended use decreases, has been going on for a long time Time searched for stabilizers for these peroxygen compounds.
  • the coating of the activator component or the oxidizing agent component or both with fatty acids has been proposed.
  • certain stabilizers for example magnesium silicate
  • the problem of inadequate storage stability is particularly difficult to solve for percarbonate-containing bleaching systems, since this perhydrate is extremely susceptible to hydrolysis and is quickly decomposed by normal atmospheric humidity and also disintegrates in agents which are stored in water-impermeable packaging with the loss of active oxygen.
  • the perhydrates if they are anhydrous, can explode explosively.
  • a certain amount of water is usually present, or stabilizers are added as described above.
  • German patent application DE 31 41 745 describes an enzyme-containing bleaching agent composition which contains an inorganic peroxide which is effective for bleaching fabrics and 0.01 to 5% by weight, based on the total mass of the enzymes, hydrolase, transferase, oxyreductase, lyase , Isomerase, ligase, protease, lipase, cellulase or amylase with an optimal action temperature of 10 ° C to 80 ° C at an optimal pH of 4 to 12, and at least 0.1 to 20 wt .-%, based on the Contains the total mass of an anhydrous salt from the series of anhydrous sodium citrate, anhydrous magnesium sulfate, anhydrous calcium chloride and anhydrous zinc sulfate.
  • the water content of the total mass of the composition described is less than 2% by weight.
  • European patent application EP 0 407 045 describes a stabilized sodium percarbonate composition which, in addition to sodium percarbonate, contains 2.5 to 35% by weight of at least one compound from the group consisting of urea, urea derivatives, acetates, amino acids with no more than seven Contains carbon atoms or their salts, triazine compounds and guanidine compounds as stabilizers.
  • Usual bleaching, washing and cleaning agents generally contain builder substances and surfactants in addition to peroxidic oxidizing agents such as alkali percarbonate.
  • the builder substances and surfactants can be obtained by spray drying aqueous slurries in powder form. This product obtained from the spray tower still contains more or less large amounts of water. If the spray-dried product is mixed with other substances contained therein to produce a bleach and detergent composition, such as, for example, with alkali percarbonate, there is a risk that the water contained in the spray-dried product will decompose the alkali percarbonate and the bleaching action of the composition after a short time Storage time is reduced to a very low value.
  • the object of the present invention was to improve the shelf life of alkali percarbonates, especially when used in detergents and cleaning agents. To improve so that such agents do not have the above disadvantages and they can also contain certain amounts of water.
  • the present invention relates to the use of water-soluble salts which can accumulate water of crystallization for the stabilization of particulate alkali percarbonate.
  • water-soluble salts which can accumulate water of crystallization, for the stabilization of alkali percarbonate in washing or cleaning agents, which can be powder, liquid, paste or block.
  • Block-shaped detergents and cleaning agents also include tablet-shaped agents. These can be produced in particular by the method according to international patent application WO 94/25563 or German patent applications DE 44 29 550 or DE 196 01 840 using microwaves. For use in liquid or pasty compositions, these are preferably anhydrous.
  • the water-soluble salts which can accumulate water of crystallization, surprisingly do not have to be used in their water of crystallization-free form, but rather are able to stabilize alkali percarbonate, even if they are wholly or partially hydrated, i.e. with water in the Crystal lattice.
  • the spatial proximity of alkali percarbonate and water-soluble salt, which can accumulate water of crystallization is necessary.
  • the use according to the invention can be carried out by mixing alkali percarbonate and water-soluble salt which can accumulate water of crystallization with one another in particle or powder form or by coating or coating the alkali percarbonate in a manner known in principle with the water-soluble salt which can accumulate water of crystallization.
  • the water-soluble salt capable of binding water of crystallization is preferably used in a weight ratio of 1: 1 to 1:12, in particular 1: 2 to 1:10, based on alkali percarbonate.
  • the water-soluble salts to be used according to the invention are preferably selected from the alkali metal acetates, the alkali metal citrate dihydrates and their mixtures.
  • Preferred alkali metal in such alkali salts as well as in the alkali percarbonate to be stabilized is sodium.
  • Alkali perborates such as the so-called sodium perborate monohydrate and the so-called sodium perborate tetrahydrate can also be stabilized by the water-soluble salt to be used according to the invention.
  • the alkali percarbonate is preferably stabilized in the presence of a bleach activator which forms an organic peroxocarboxylic acid under perhydrolysis conditions.
  • the bleach activators optionally contained in the compositions include, in particular, compounds which, under perhydrolysis conditions, give substituted or unsubstituted perbenzoic acid and / or peroxocarboxylic acids having 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms.
  • Particularly suitable are substances which have O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine, are preferred (DADHT), acylated phenol sulfonates, especially nonanoyl or isononanoyloxybenzenesulfonate, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, as well as acetylated sorbitol and mannitol, and acylated sugar derivatives, especially pentaacetyl glucose, especially pentaacetyl glucose , Tetraacetylxylose and Octaace
  • the bleach activator combinations known from German patent application DE 44 43 177 can also be used.
  • salts or complexes of super- transition metals which include in particular Mn, Co, Fe and / or Cu, are used, such as those from German patent applications DE 44 16 438, DE 195 29 905, DE 195 36 082 or DE 196 05 688 or the European patent applications EP 0 392 592, EP 0 443 651, EP 0458 397, EP 0 544 490, EP 0 549 271, EP 0 630 964 or EP 0693 550 are known.
  • the bleach activator, detergents and cleaning agents can contain all the ingredients customary in such agents, in particular builder substances, surface-active surfactants, additional organic and / or in particular inorganic peroxygen compounds, water-miscible organic solvents , Enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators, silver corrosion inhibitors, abrasives and colorants and fragrances.
  • the surfactants in question include, in particular, anionic surfactants, non-ionic surfactants and mixtures thereof.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups.
  • Corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical, can also be used.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Usable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized.
  • the useful surfactants of the sulfate type include the salts of the sulfuric acid semiesters of fatty alcohols with 12 to 18 carbon atoms and the sulfa- Tation products of the nonionic surfactants mentioned with a low degree of ethoxylation.
  • the surfactants of the sulfonate type that can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and also olefin sulfonates with 12 to 18 carbon atoms, which are used in the reaction of corresponding mono-olefins arise with sulfur trioxide, as well as alpha-sulfofatty acid esters, which arise in the sulfonation of fatty acid methyl or ethyl esters.
  • Such surfactants are present in the cleaning or washing agents in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight.
  • the specified lower limits can be undershot; the surfactant content in such agents is preferably 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight.
  • Organic peracids, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the conditions of use are particularly suitable as additional bleaching agents based on peroxygen, if desired.
  • additional bleaching agents based on peroxygen, if desired.
  • solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle.
  • Alkali perborate monohydrate is preferably used as an additional bleaching agent. If the washing or cleaning agent contains additional peroxygen compounds, these, including the alkali carbonate, are present in amounts of preferably 5% by weight to 30% by weight, in particular 10% by weight to 25% by weight, these amounts including the alkali percarbonate.
  • the washing and cleaning agents can contain water-soluble and / or water-insoluble, organic and / or inorganic builders.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid, and also polyaspartic acid, polyphosphonic acids, in particular aminotris (methylene phosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application WO 93/161 10 or the one accessible by oxidation of polysaccharides international patent application WO 92/18542 or European patent EP 0 232 202, polymeric acrylic acids, methacrylic
  • the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Polymers of this type can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular weight of between 1,000 and 200,000. Further preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
  • the organic builder substances can, in particular for position liquid or pasty agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts. Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts close to the upper limit mentioned are preferably used in pasty or liquid compositions.
  • Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate.
  • crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid compositions in particular from 1% by weight to 5% by weight. , used.
  • the detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X are preferred. Amounts close to the above upper limit are preferably used in solid, particulate compositions.
  • Suitable aluminosilicates in particular have no particles with a grain size above 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m.
  • Their calcium binding capacity which can be determined according to the information in German patent DE 24 12 837, is generally in the range from 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates.
  • the alkali silicates which can be used as builders in the compositions preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 0: SiO 2 molar ratio of 1: 2 to 1: 2.8.
  • Those with a Na 2 O: SiO 2 molar ratio of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0425 427.
  • Crystalline sheet silicates of the general formula Na 2 Si x O 2x + 1 y H 2 O are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates, in which x, the so-called module, is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514.
  • Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned.
  • both ⁇ - and ⁇ -sodium disilicate are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in the international patent application WO 91/08171 is.
  • ⁇ -sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238 809 or JP 04/260610.
  • Practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can also be prepared from amorphous alkali silicates, as in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 452 428, can be used in detergents and cleaning agents.
  • a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0436 835.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of such agents.
  • alkali aluminosilicate in particular zeolite
  • the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances is preferably 1:10 to 10: 1.
  • the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • Builder substances are preferably contained in the washing or cleaning agents in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight, while disinfectants are preferably free of the builder substances which only complex the components of the water hardness are and preferably not more than 20% by weight, in particular containing from 0.1% by weight to 5% by weight of heavy metal complexing substances, preferably from the group comprising aminopolycarboxylic acids, aminopolyphosphonic acids and hydroxypolyphosphonic acids and their water-soluble salts and mixtures thereof,
  • Enzymes which can be used in detergents and cleaning agents are those from the class of proteases, lipases, cutinases, amylases, pullulanases, cellulases, hemicellulases, xylanases, oxidases and peroxidases and mixtures thereof. Enzymes obtained from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia are particularly suitable.
  • the optionally used enzymes can, as described, for example, in international patent applications WO 92/11347 or WO 94/23005, be adsorbed on carriers and / or be embedded in coating substances in order to protect them against premature inactivation. They are contained in detergents and cleaning agents in amounts of preferably up to 2% by weight, in particular from 0.2% by weight to 1.5% by weight.
  • Organic solvents which can be used in detergents and cleaning agents, in particular if they are in liquid or pasty form include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 C atoms, especially ethylene glycol and propylene glycol, as well as their mixtures and the ethers that can be derived from the compound classes mentioned.
  • Such water-miscible solvents are preferably not more than 30% by weight, in particular from 6% by weight to 20% by weight, in detergents, cleaning agents and disinfectants.
  • such agents can, however, system and environmentally compatible acids, in particular tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid also mineral acids, in particular Sulfuric acid, or bases, especially ammonium or alkali hydroxides, contain.
  • Such pH regulators are preferably not contained in the compositions above 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • Color transfer inhibitors that are suitable for use in detergents for washing textiles include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.
  • Graying inhibitors have the task of keeping the dirt detached from the hard surface and in particular of the textile fiber suspended in the liquor and thus to support the builder or co-builder.
  • water-soluble colloids of mostly organic nature are suitable, for example glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Starch products other than those mentioned above can also be used, for example aldehyde starches.
  • Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably used .
  • the agents can contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-mo ⁇ holino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which are used instead of morpholino - Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyrylene type may also be present, for example the alkali salts of 4,4'-bis (2-suIfostyryI) diphenyl, 4,4'-bis (4-chloro-3-suIfostyryl) diphenyl, or 4 - (4- Chlorostyryl) -4 , - (2-sulfostyryl) diphenyl. Mixtures of the aforementioned optical brighteners can also be used.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and also paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkyl diamides. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

Landscapes

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

Abstract

L'object de l'invention est d'améliorer la stabilité au stockage de percarbonates alcalins sous forme de particules, en particulier lorsqu'ils sont utilisés dans des produits de lavage et de nettoyage et également en présence d'activateurs de blanchiment. Cet objectif est atteint essentiellement grâce à l'utilisation de sels hydrosolubles qui peuvent fixer par addition l'eau de cristallisation.
PCT/EP1997/002301 1996-05-15 1997-05-06 Stabilisation de percarbonate alcalin WO1997043211A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP97922976A EP0902756A1 (fr) 1996-05-15 1997-05-06 Stabilisation de percarbonate alcalin

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19619646.9 1996-05-15
DE1996119646 DE19619646A1 (de) 1996-05-15 1996-05-15 Stabilisierung von Alkalipercarbonat

Publications (1)

Publication Number Publication Date
WO1997043211A1 true WO1997043211A1 (fr) 1997-11-20

Family

ID=7794436

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/002301 WO1997043211A1 (fr) 1996-05-15 1997-05-06 Stabilisation de percarbonate alcalin

Country Status (3)

Country Link
EP (1) EP0902756A1 (fr)
DE (1) DE19619646A1 (fr)
WO (1) WO1997043211A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000050557A1 (fr) * 1999-02-25 2000-08-31 Henkel Kommanditgesellschaft Auf Aktien Corps moules de produits de lavage et de nettoyage stables au stockage
US7435714B2 (en) 2002-12-20 2008-10-14 Evonik Degussa Gmbh Liquid detergent and cleaning agent composition comprising a multi-coated bleach particle
US7588697B2 (en) 2003-05-07 2009-09-15 Evonik Degussa Gmbh Coated sodium percarbonate granules with improved storage stability
US7718592B2 (en) 2004-11-11 2010-05-18 Degussa, Gmbh Sodium percarbonate particles having a shell layer comprising thiosulfate

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10032177A1 (de) * 2000-07-01 2002-01-10 Henkel Kgaa Coatingverfahren für basiche teilchenförmige Verbindungen
DE102004060011A1 (de) * 2004-12-14 2006-07-06 Degussa Ag Verpresste Formkörper enthaltend umhüllte Natriumpercarbonatpartikel

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2229766A1 (fr) * 1973-05-14 1974-12-13 Procter & Gamble
DD140140A1 (de) * 1978-11-28 1980-02-13 Rainer Windisch Verfahren zur herstellung eines stabilen natriumkarbonat-perhydrats
EP0268170A2 (fr) * 1986-11-15 1988-05-25 Henkel Kommanditgesellschaft auf Aktien Composition de blanchiment stable dans le magasin avec une puissance de solution améliorée
EP0546815A1 (fr) * 1991-12-11 1993-06-16 Unilever Plc Percabonate de sodium
DE4324104A1 (de) * 1993-07-17 1995-01-19 Degussa Umhüllte Natriumpercarbonatpartikel, Verfahren zu deren Herstellung und deren Verwendung
WO1995002670A1 (fr) * 1993-07-14 1995-01-26 The Procter & Gamble Company Compositions de detergent a lessive granuleux contenant des particules blanchissantes de percarbonate stabilise
DE4424005A1 (de) * 1994-07-07 1996-01-11 Henkel Kgaa Pulverförmiges Bleich- und Waschmittel

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2229766A1 (fr) * 1973-05-14 1974-12-13 Procter & Gamble
DD140140A1 (de) * 1978-11-28 1980-02-13 Rainer Windisch Verfahren zur herstellung eines stabilen natriumkarbonat-perhydrats
EP0268170A2 (fr) * 1986-11-15 1988-05-25 Henkel Kommanditgesellschaft auf Aktien Composition de blanchiment stable dans le magasin avec une puissance de solution améliorée
EP0546815A1 (fr) * 1991-12-11 1993-06-16 Unilever Plc Percabonate de sodium
WO1995002670A1 (fr) * 1993-07-14 1995-01-26 The Procter & Gamble Company Compositions de detergent a lessive granuleux contenant des particules blanchissantes de percarbonate stabilise
DE4324104A1 (de) * 1993-07-17 1995-01-19 Degussa Umhüllte Natriumpercarbonatpartikel, Verfahren zu deren Herstellung und deren Verwendung
DE4424005A1 (de) * 1994-07-07 1996-01-11 Henkel Kgaa Pulverförmiges Bleich- und Waschmittel

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000050557A1 (fr) * 1999-02-25 2000-08-31 Henkel Kommanditgesellschaft Auf Aktien Corps moules de produits de lavage et de nettoyage stables au stockage
US7435714B2 (en) 2002-12-20 2008-10-14 Evonik Degussa Gmbh Liquid detergent and cleaning agent composition comprising a multi-coated bleach particle
US7588697B2 (en) 2003-05-07 2009-09-15 Evonik Degussa Gmbh Coated sodium percarbonate granules with improved storage stability
US7718592B2 (en) 2004-11-11 2010-05-18 Degussa, Gmbh Sodium percarbonate particles having a shell layer comprising thiosulfate

Also Published As

Publication number Publication date
DE19619646A1 (de) 1997-11-20
EP0902756A1 (fr) 1999-03-24

Similar Documents

Publication Publication Date Title
WO1997041196A1 (fr) Acylacetals s'utilisant comme activateurs de blanchiment pour detergents et nettoyants
WO1997041202A1 (fr) Acyllactames s'utilisant comme activateurs de blanchiment pour detergents et nettoyants
WO1997041200A1 (fr) Activateurs de blanchiment pour detergents et nettoyants
EP0845027B1 (fr) Complexes d'activateurs a action catalytique pour composes peroxygene
EP2440641B1 (fr) Dioxyde de manganèse nanoparticulaire
EP0874890B1 (fr) Detergents avec certains oligosaccharides oxydes
WO1997041201A1 (fr) Esters d'enol s'utilisant comme activateurs de blanchiment pour detergents et nettoyants
WO1996017920A1 (fr) Melanges activateurs pour composes peroxy inorganiques
DE102009001691A1 (de) Wasch- oder Reinigungsmittel mit gegebenenfalls in situ erzeugtem bleichverstärkendem Übergangsmetallkomplex
EP0876463B1 (fr) Agents de blanchiment et de lavage avec systeme de blanchiment enzymatique
DE102009001692A1 (de) Wasch- oder Reinigungsmittel mit gegebenenfalls in situ erzeugtem bleichverstärkendem Übergangsmetallkomplex
DE19620267A1 (de) Katalytisch wirksame Aktivatorkomplexe mit N¶4¶-Liganden für Persauerstoffverbindungen
DE19613103A1 (de) Übergangsmetallkomplex-haltige Systeme als Aktivatoren für Persauerstoffverbindungen
EP2714877A1 (fr) Systèmes activateurs pour composés peroxygénés
DE19754290A1 (de) Enolester als Bleichaktivatoren für Wasch- und Reinigungsmittel
EP0902756A1 (fr) Stabilisation de percarbonate alcalin
EP1749084B1 (fr) Combinaison de renforcement d'agents de blanchiment a utiliser dans des produits de lavage et de nettoyage
EP3415593B1 (fr) Renforcement de l'effet de blanchiment lors du lavage et du nettoyage
DE10162646A1 (de) Bleichaktivatorkombination für den Einsatz in Wasch-und Reinigungsmitteln
EP0879875A2 (fr) Oxa-esters d'acides carboxyliques comme activateurs de blanchiment pour compositions détergentes
DE19628809A1 (de) Katalytisch wirksame Aktivatorkomplexe mit N¶4¶-Liganden vom Diimin-Typ für Persauerstoffverbindungen
DE19650954A1 (de) Stabilisierung von Alkalipercarbonat in Wasch- und Reinigungsmitteln
DE19858661A1 (de) Bisdiacylacetale als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19545727A1 (de) Alkalipercarbonathaltiges Waschmittel
DE19613880A1 (de) Waschmittel mit speziellem Buildersystem

Legal Events

Date Code Title Description
AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1997922976

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1997922976

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1997922976

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载