WO1997043211A1 - Stabilisation of alkali percarbonate - Google Patents

Stabilisation of alkali percarbonate Download PDF

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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
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WIPO (PCT)
Prior art keywords
water
alkali
weight
acid
percarbonate
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PCT/EP1997/002301
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German (de)
French (fr)
Inventor
Heinz-Manfred Wilsberg
Thomas Merz
Khalil Shamayeli
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to EP97922976A priority Critical patent/EP0902756A1/en
Publication of WO1997043211A1 publication Critical patent/WO1997043211A1/en

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    • 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.

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Abstract

The invention proposes to improve the storage life of particulate alkali percarbonates, in particular, when used in washing and cleaning agents and also in the presence of bleaching activators substantially by the use of water-soluble salts which can absorb water of crystallization.

Description

Stabilisierung von Alkalipercarhonat Stabilization of alkali percarhonate
Die vorliegende Erfindung betrifft die Verwendung bestimmter Salze zur Stabilisierung von Alkalipercarbonaten, insbesondere in Wasch- oder Reinigungsmitteln.The present invention relates to the use of certain salts for stabilizing alkali percarbonates, in particular in washing or cleaning agents.
Wasch- und Reinigungsmittel, die peroxidische Oxidationsmittel, allein oder als Bleichsystem in Form einer Kombination eines anorganischen Peroxids oder Perhydrats mit einem Bleichaktivator, der unter Perhydrolysebedingungen eine organische Peroxocarbonsäure bildet, enthalten, sind seit langer Zeit bekannt. Die am häufigsten eingesetzten aktivsauerstoffhaltigen Bleichkomponenten beziehungsweiseDetergents 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
Oxidationsmittel sind die Alkaliperborate,- percarbonate,- persulfate und -persilikate. Als Bleichaktivatoren werden in der Regel solche Verbindungen verwendet, die unter Hydrolyse- beziehungsweise Perhydrolysebedingungen Carbonsäuren beziehungsweise Percarbonsäuren abspalten, wobei in überwiegendem Maße solche Verbindungen ein¬ gesetzt werden, die in Gegenwart der peroxidischen Oxidationsmittel Peressigsäure lie¬ fern. Da die Reaktion des Aktivators mit der Persauerstoffverbindung, die erst unter den meist wäßrigen Anwendungsbedingungen der Mittel erfolgen soll, auch bei der Herstellung und insbesondere der Lagerung derartiger Mittel ablaufen kann, wodurch die Verfügbarkeit der Persauerstoffverbindung für den eigentlichen Anwendungszweck zu¬ rückgeht, wird seit langer Zeit nach Stabilisatoren für diese Persauerstoffverbindungen gesucht. So ist zum Beispiel die Umhüllung der Aktivator- oder der Oxidationsmittelkom- ponente oder beider mit Fettsäuren vorgeschlagen worden. Auch die Zugabe bestimmter Stabilisatoren, beispielsweise Magnesiumsilikat, ist bekannt. Für percarbonathaltige Bleichsysteme ist das Problem der mangelhaften Lagerstabilität besonders schwer zu lösen, da dieses Perhydrat extrem hydrolyseanfällig ist und sowohl von der normalen Luftfeuchtigkeit rasch zersetzt wird als auch in Mitteln, die in wasserundurchlässigen Verpackungen gelagert werden, unter Verlust von Aktivsauerstoff zerfällt. Auf der anderen Seite besteht das Problem, daß sich die Perhydrate, wenn sie wasserfrei vorliegen, explosionsartig zersetzen können. Um diese Perhydrate zu stabilisieren, liegt in der Regel ein gewisser Wasseranteil vor, oder es werden wie oben beschrieben Stabili¬ satoren zugesetzt. In der deutschen Patentanmeldung DE 31 41 745 wird zum Beispiel eine enzymhaltige Bleichmittelzusammensetzung beschrieben, die ein zum Bleichen von Geweben wirksames anorganisches Peroxid sowie 0,01 bis 5 Gew.-%, bezogen auf die Gesamtmasse der Enzyme, Hydrolase, Transferase, Oxyreductase, Lyase, Isomerase, Ligase, Protease, Lipase, Cellulase oder Amylase mit einer optimalen Wirkungstemperatur von 10 °C bis 80 °C bei einem optimalen pH- Wert von 4 bis 12, sowie mindestens 0,1 bis 20 Gew.-%, bezogen auf die Gesamtmasse eines wasserfreien Salzes aus der Reihe wasserfreies Natriumeitrat, wasserfreies Magnesiumsulfat, wasserfreies Calciumchlorid und wasserfreies Zinksulfat enthält. Der Wassergehalt der Gesamtmasse der beschriebenen Zusammensetzung beträgt weniger als 2 Gew.-%.Oxidizing agents are the alkali perborates, percarbonates, persulfates and persilicates. As 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. For example, the coating of the activator component or the oxidizing agent component or both with fatty acids has been proposed. The addition of certain stabilizers, for example magnesium silicate, is also known. 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. On the other hand, there is the problem that the perhydrates, if they are anhydrous, can explode explosively. In order to stabilize these perhydrates, a certain amount of water is usually present, or stabilizers are added as described above. German patent application DE 31 41 745, for example, 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.
In der europäischen Patentanmeldung EP 0 407 045 wird eine stabilisierte Natriumpercar- bonatzusammensetzung beschrieben, die neben Natriumpercarbonat 2,5 bis 35 Gew.-% mindestens einer Verbindung aus der Gruppe bestehend aus Harnstoff, Harn¬ stoffderivaten, Acetaten, Aminosäuren mit nicht mehr als sieben Kohlenstoffatomen oder deren Salzen, Triazinverbindungen und Guanidinverbindungen als Stabilisatoren enthält.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.
Übliche Bleich-, Wasch- und Reinigungsmittel enthalten in der Regel neben peroxidischen Oxidationsmitteln wie Alkalipercarbonat auch Buildersubstanzen und Ten- side. Die Buildersubstanzen und Tenside können durch Sprühtrocknung wäßriger Aufschlämmungen in Pulverform erhalten werden. Dieses aus dem Sprühturm erhaltene Produkt enthält noch mehr oder weniger große Wassermengen. Wenn das sprühgetrocknete Produkt zur Herstellung einer Bleich- und Waschmittel¬ zusammensetzung mit anderen darin enthaltenden Substanzen vermischt wird, wie zum Beispiel mit Alkalipercarbonat, besteht die Gefahr, daß das in dem sprühgetrockneten Produkt enthaltene Wasser das Alkalipercarbonat zersetzt und die Bleichwirkung der Zusammensetzung bereits nach kurzer Lagerzeit auf einen sehr geringen Wert erniedrigt wird.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.
Aufgabe der vorliegenden Erfindung war es, die Lagerbeständigkeit von Alkalipercarbonaten, insbesondere in bei deren Einsatz in Wasch- und Reinigungsmitteln, so zu verbessern, daß derartige Mittel die obigen Nachteile nicht aufweisen und sie auch gewisse Wassermengen enthalten können.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.
Überraschenderweise wurde gefunden, daß dies durch die Verwendung bestimmter wasserlöslicher Salze erreicht werden kann.Surprisingly, it has been found that this can be achieved using certain water-soluble salts.
Gegenstand der vorliegenden Erfindung ist die Verwendung wasserlöslicher Salze, die Kristallwasser anlagern können, zur Stabilisierung von teilchenförmigem Alkalipercarbonat.The present invention relates to the use of water-soluble salts which can accumulate water of crystallization for the stabilization of particulate alkali percarbonate.
Weitere Gegenstände der Erfindung sind die Verwendung wasserlöslicher Salze, die Kristallwasser anlagern können, zur Stabilisierung von Alkalipercarbonat in Wasch- oder Reinigungsmitteln, die pulverförmig, flüssig, pastenförmig oder blockförmig sein können. Zu den blockförmigen Wasch- und Reinigungsmitteln gehören auch tablettenförmige Mittel. Diese können insbesondere nach dem Verfahren gemäß der internationalen Patent¬ anmeldung WO 94/25563 oder der deutschen Patentanmeldungen DE 44 29 550 beziehungsweise DE 196 01 840 unter Einsatz von Mikrowellen hergestellt werden. Zur Verwendung in flüssigen oder pastenförmigen Mitteln sind diese bevorzugt wasserfrei.Further objects of the invention are the use of 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.
Um erfindungsgemäß verwendet werden zu können, müssen die wasserlöslichen Salze, die Kristallwasser anlagern können, überraschenderweise nicht in ihrer kristallwasserfreien Form eingesetzt werden, sondern sind durchaus in der Lage, Alkalipercarbonat zu stabilisieren, auch wenn sie ganz oder teilweise hydratisiert, das heißt mit Wasser im Kristallgitter, vorliegen.In order to be able to be used according to the invention, 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.
Um den der Erfindung zugrundeliegenden Effekt zu erzielen, ist die räumliche Nähe von Alkalipercarbonat und wasserlöslichem Salz, das Kristallwasser anlagern kann, erforderlich. Die erfindungsgemäße Verwendung kann dadurch vorgenommen werden, daß man Alkalipercarbonat und wasserlösliches Salz, das Kristallwasser anlagern kann, in Teilchen- beziehungsweise Pulverform miteinander vermischt oder das Alkalipercarbonat in im Prinzip bekannter Weise mit dem wasserlöslichen Salz, das Kristallwasser anlagern kann, umhüllt beziehungsweise coatet. Vorzugsweise wird das wasserlösliche, zur Kristallwasserbindung fähige Salz im Ge¬ wichtsverhältnis 1 :1 bis 1 :12, insbesondere 1 :2 bis 1 : 10, bezogen auf Alkalipercarbonat, eingesetzt.In order to achieve the effect on which the invention is based, 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.
Die erfindungsgemäß zu verwendenden wasserlöslichen Salze werden vorzugsweise aus den Alkaliacetaten, den Alkalitricitrat-dihydraten und deren Mischungen ausgewählt. Be¬ vorzugtes Alkalimetall in derartigen Alkalisalzen wie auch im zu stabilisierenden Alkalipercarbonat ist Natrium. Auch Alkaliperborate wie das sogenannte Natriumperborat-Monohydrat und das sogenannte Natriumperborat-Tetrahydrat können durch das erfindungsgemäß zu verwendende wasserlösliche Salz stabilisiert werden.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.
Insbesondere bei der erfindungsgemäßen Verwendung in Wasch- und Reinigungsmitteln findet die Stabilisierung des Alkalipercarbonats vorzugsweise in Gegenwart eines Bleich¬ aktivators statt, der unter Perhydrolysebedingungen eine organische Peroxocarbonsäure bildet. Zu den gegebenenfalls in den Mitteln enthaltenen Bleichaktivatoren gehören insbesondere Verbindungen, die unter Perhydrolysebedingungen gegebenenfalls substi¬ tuierte Perbenzoesäure und/oder Peroxocarbonsäuren mit 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen ergeben. Geeignet sind insbesondere Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituier¬ te Benzoylgruppen aufweisen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbe¬ sondere Tetraacetylethylendiamin (TAED), acylierte Glykolurile, insbesondere Tetraace- tylglykoluril (TAGU), acylierte Triazinderivate, insbesondere l,5-Diacetyl-2,4-dioxo- hexahydro-l,3,5-triazin (DADHT), acylierte Phenolsulfonate, insbesondere Nonanoyl- oder Isononanoyloxybenzolsulfonat, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat und 2,5-Diacetoxy-2,5-dihydrofuran sowie acetyliertes Sorbit und Mannit, und acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton. Auch die aus der deutschen Patentanmeldung DE 44 43 177 bekannten Bleichaktivatorkombinationen können eingesetzt werden. Zusätzlich oder anstatt derartiger Bleichaktivatoren können als sogenannte Bleichkatalysatoren bekannte Salze beziehungsweise Komplexe von Über- gangsmetallen, zu denen insbesondere Mn, Co, Fe und/oder Cu gehören, eingesetzt werden, wie sie beispielsweise aus den deutschen Patentanmeldungen DE 44 16 438, DE 195 29 905, DE 195 36 082 oder DE 196 05 688 oder den europäischen Patentanmel¬ dungen EP 0 392 592, EP 0 443 651, EP 0458 397, EP 0 544 490, EP 0 549 271 , EP 0 630 964 oder EP 0693 550 bekannt sind.Particularly when used in detergents and cleaning agents 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 Octaacetyllactose as well as acetylated, optionally N-alkylated Glucamin and Gluconolacton. The bleach activator combinations known from German patent application DE 44 43 177 can also be used. In addition to or instead of such bleach activators, 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.
Wasch- und Reinigungsmittel können außer Alkalipercarbonat und dem erfindungsgemäß zu verwendenden wasserlöslichen Salz sowie gegebenenfalls dem Bleichaktivator alle in derartigen Mitteln gebräuchliche Inhaltsstoffe enthalten, zu denen insbesondere Builder¬ substanzen, oberflächenaktive Tenside, zusätzliche organische und/oder insbesondere an¬ organische Persauerstoffverbindungen, wassermischbare organische Lösungsmittel, En¬ zyme, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren und weitere Hilfsstoffe, wie optische Aufheller, Vergrauungsinhibitoren, Farbübertragungsinhibitoren, Schaumregula¬ toren, Silberkorrosionsinhibitoren, Abrasivmittel sowie Färb- und Duftstoffe gehören.In addition to alkali percarbonate and the water-soluble salt to be used according to the invention and, if appropriate, 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.
Zu den in Frage kommenden Tensiden gehören insbesondere anionische Tenside, nicht¬ ionische Tenside und deren Gemische. Geeignete nichtionische Tenside sind insbesondere Alkylglykoside und Ethoxylierungs- und/oder Propoxylierungsprodukte von Alkyl - glykosiden oder linearen oder verzweigten Alkoholen mit jeweils 12 bis 18 C-Atomen im Alkylteil und 3 bis 20, vorzugsweise 4 bis 10 Alkylethergruppen. Weiterhin sind entspre¬ chende Ethoxylierungs- und/oder Propoxylierungsprodukte von N-Alkyl-aminen, vicinalen Diolen, Fettsäureestern und Fettsäureamiden, die hinsichtlich des Alkylteils den genannten langkettigen Alkoholderivaten entsprechen, sowie von Alkylphenolen mit 5 bis 12 C-Atomen im Alkylrest brauchbar.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.
Geeignete anionische Tenside sind insbesondere Seifen und solche, die Sulfat- oder Sulfonat-Gruppen mit bevorzugt Alkaliionen als Kationen enthalten. Verwendbare Seifen sind bevorzugt die Alkalisalze der gesättigten oder ungesättigten Fettsäuren mit 12 bis 18 C-Atomen. Derartige Fettsäuren können auch in nicht vollständig neutralisierter Form eingesetzt werden. Zu den brauchbaren Tensiden des Sulfat-Typs gehören die Salze der Schwefelsäurehalbester von Fettalkoholen mit 12 bis 18 C-Atomen und die Sulfa- tierungsprodukte der genannten nichtionischen Tenside mit niedrigem Ethoxy- lierungsgrad. Zu den verwendbaren Tensiden vom Sulfonat-Typ gehören lineare Alkyl- benzolsulfonate mit 9 bis 14 C-Atomen im Alkylteil, Alkansulfonate mit 12 bis 18 C- Atomen, sowie Olefinsulfonate mit 12 bis 18 C-Atomen, die bei der Umsetzung entspre¬ chender Monoolefme mit Schwefeltrioxid entstehen, sowie alpha-Sulfofettsäureester, die bei der Sulfonierung von Fettsäuremethyl- oder -ethylestern entstehen.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.
Derartige Tenside sind in den Reinigungs- oder Waschmitteln in Mengenanteilen von vorzugsweise 5 Gew.-% bis 50 Gew.-%, insbesondere von 8 Gew.-% bis 30 Gew.-%, ent¬ halten. In Mitteln für die Reinigung von Geschirr können die genannten Untergrenzen jedoch unterschritten werden; der Tensidgehalt in derartigen Mitteln liegt vorzugsweise bei 0,1 Gew.-% bis 20 Gew.-%, insbesondere 0,2 Gew.-% bis 5 Gew.-%.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. In agents for cleaning dishes, however, 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.
Als gewünschtenfalls vorhandene zusätzliche Bleichmittel auf Persauerstoffbasis kommen insbesondere organische Persäuren, Wasserstoffperoxid und unter den Anwendungsbe¬ dingungen Wasserstoffperoxid abgebende anorganische Salze, wie Perborat, Persulfat und/oder Persilikat, in Betracht. Sofern feste Persauerstoffverbindungen eingesetzt werden sollen, können diese in Form von Pulvern oder Granulaten verwendet werden, die auch in im Prinzip bekannter Weise umhüllt sein können. Bevorzugt wird als zusätzliches Bleichmittel Alkaliperborat-Monohydrat eingesetzt. Falls das Wasch- oder Reinigungs¬ mittel zusätzliche Persauerstoffverbindungen enthält, sind diese einschließlich des Alkalicarbonats in Mengen von vorzugsweise 5 Gew.-% bis 30 Gew.-%, insbesondere 10 Gew.-% bis 25 Gew.-% vorhanden, wobei diese Mengen einschließlich des Alkalipercarbonats zu verstehen sind.Organic peracids, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the conditions of use, such as perborate, persulfate and / or persilicate, are particularly suitable as additional bleaching agents based on peroxygen, if desired. If 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.
Außerdem können die Wasch- und Reinigungsmittel wasserlöslichen und/oder wasser¬ unlöslichen, organischen und/oder anorganischen Builder enthalten. Zu den wasserlös¬ lichen organischen Buildersubstanzen gehören Polycarbonsäuren, insbesondere Citronensäure und Zuckersäuren, monomere und polymere Aminopolycarbonsäuren, ins¬ besondere Methylglycindiessigsäure, Nitrilotriessigsäure und Ethylendiamintetraessig- säure sowie Polyasparaginsäure, Polyphosphonsäuren, insbesondere Aminotris(methylen- phosphonsäure), Ethylendiamintetrakis(methylenphosphonsäure) und 1 -Hydroxyethan- 1,1-diphosphonsäure, polymere Hydroxyverbindungen wie Dextrin sowie polymere (Poly-)carbonsäuren, insbesondere die durch Oxidation von Polysacchariden zugäng¬ lichen Polycarboxylate der internationalen Patentanmeldung WO 93/161 10 beziehungsweise der internationalen Patentanmeldung WO 92/18542 oder der europäischen Patentschrift EP 0 232 202, polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Die relative Molekülmasse der Homopolymeren ungesättiger Carbonsäuren liegt im allge¬ meinen zwischen 5 000 und 200 000, die der Copolymeren zwischen 2 000 und 200 000, vorzugsweise 50 000 bis 120 000, jeweils bezogen auf freie Säure. Ein besonders be¬ vorzugtes Acrylsäure-Maleinsäure-Copolymer weist eine relative Molekülmasse von 50 000 bis 100 000 auf. Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copolymere der Acrylsäure oder Methacrylsäure mit Vinylethern, wie Vinyl- methylethern, Vinylester, Ethylen, Propylen und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-% beträgt. Als wasserlösliche organische Buildersubstanzen können auch Terpolymere eingesetzt werden, die als Monomere zwei ungesättigte Säuren und/oder deren Salze sowie als drittes Monomer Vinylalkohol und/oder einem veresterten Vinylalkohol oder ein Kohlenhydrat enthalten. Das erste saure Monomer beziehungsweise dessen Salz leitet sich von einer monoethylenisch ungesättigten C3-C8-Carbonsäure und vorzugsweise von einer C3-C4-Monocarbonsäure, insbesondere von (Meth)-acrylsäure ab. Das zweite saure Monomer beziehungsweise dessen Salz kann ein Derivat einer C4-C8- Dicarbonsäure, wobei Maleinsäure besonders bevorzugt ist, und/oder ein Derivat einer Allylsulfonsäure, die in 2-Stellung mit einem Alkyl- oder Arylrest substituiert ist, sein. Derartige Polymere lassen sich insbesondere nach Verfahren herstellen, die in der deutschen Patentschrift DE 42 21 381 und der deutschen Patentanmeldung DE 43 00 772 beschrieben sind, und weisen im allgemeinen eine relative Molekülmasse zwischen 1 000 und 200 000 auf. Weitere bevorzugte Copolymere sind solche, die in den deutschen Patentanmeldungen DE 43 03 320 und DE 44 17 734 beschrieben werden und als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäuresalze beziehungsweise Vinylacetat aufweisen. Die organischen Buildersubstanzen können, insbesondere zur Her- stellung flüssiger oder pastenförmiger Mittel, in Form wäßriger Lösungen, vorzugsweise in Form 30- bis 50-gewichtsprozentiger wäßriger Lösungen eingesetzt werden. Alle ge¬ nannten Säuren werden in der Regel in Form ihrer wasserlöslichen Salze, insbesondere ihre Alkalisalze, eingesetzt. Derartige organische Buildersubstanzen können gewünschtenfalls in Mengen bis zu 40 Gew.-%, insbesondere bis zu 25 Gew.-% und vorzugsweise von 1 Gew.-% bis 8 Gew.-% enthalten sein. Mengen nahe der genannten Obergrenze werden vorzugsweise in pastenförmigen oder flüssigen Mitteln eingesetzt.In addition, 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 acids, maleic acids and copolymers of these, which may also contain small amounts of polymerizable substances in copolymerized form without carboxylic acid functionality. 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.
Als wasserlösliche anorganische Buildermaterialien kommen insbesondere Polyphos- phate, vorzugsweise Natriumtriphosphat, in Betracht. Als wasserunlösliche, wasserdisper- gierbare anorganische Buildermaterialien werden insbesondere kristalline oder amorphe Alkalialumosilikate, in Mengen von bis zu 50 Gew.-%, vorzugsweise nicht über 40 Gew - % und in flüssigen Mitteln insbesondere von 1 Gew.-% bis 5 Gew.-%, eingesetzt. Unter diesen sind die kristallinen Natriumalumosilikate in Waschmittelqualität, insbesondere Zeolith A, P und gegebenenfalls X, bevorzugt. Mengen nahe der genannten Obergrenze werden vorzugsweise in festen, teilchenförmigen Mitteln eingesetzt. Geeignete Alumosi- likate weisen insbesondere keine Teilchen mit einer Korngröße über 30 μm auf und bestehen vorzugsweise zu wenigstens 80 Gew.-% aus Teilchen mit einer Größe unter 10 μm. Ihr Calciumbindevermögen, das nach den Angaben der deutschen Patentschrift DE 24 12 837 bestimmt werden kann, liegt in der Regel im Bereich von 100 bis 200 mg CaO pro Gramm. Geeignete Substitute beziehungsweise Teilsubstitute für das genannte Alumosilikat sind kristalline Alkalisilikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können. Die in den Mitteln als Gerüststoffe brauchbaren Alkalisilikate weisen vorzugsweise ein molares Verhältnis von Alkalioxid zu SiO2 unter 0,95, insbesondere von 1 :1,1 bis 1 :12 auf und können amorph oder kristallin vorliegen. Be¬ vorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amorphen Natriumsili¬ kate, mit einem molaren Verhältnis Na20:SiO2 von 1 :2 bis 1:2,8. Solche mit einem molaren Verhältnis Na2O:SiO2 von 1 :1,9 bis 1 :2,8 können nach dem Verfahren der europäischen Patentanmeldung EP 0425 427 hergestellt werden. Als kristalline Silikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können, werden vorzugs¬ weise kristalline Schichtsilikate der allgemeinen Formel Na2SixO2x+1 y H2O eingesetzt, in der x, das sogenannte Modul, eine Zahl von 1 ,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Kristalline Schichtsilikate, die unter diese allgemeine Formel fallen, werden beispielsweise in der europäischen Patentanmeldung EP 0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate sind solche, bei denen x in der genannten allgemeinen Formel die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch δ-Natriumdisilikate (Na2Si2O5 y H2O) bevorzugt, wobei ß-Natriumdi- silikat beispielsweise nach dem Verfahren erhalten werden kann, das in der interna¬ tionalen Patentanmeldung WO 91/08171 beschrieben ist. δ-Natriumsilikate mit einem Modul zwischen 1,9 und 3,2 können gemäß den japanischen Patentanmeldungen JP 04/238 809 oder JP 04/260610 hergestellt werden. Auch aus amorphen Alkalisilikaten hergestellte, praktisch wasserfreie kristalline Alkali Silikate der obengenannten allgemeinen Formel, in der x eine Zahl von 1,9 bis 2,1 bedeutet, herstellbar wie in den europäischen Patentanmeldungen EP 0 548 599, EP 0 502 325 und EP 0 452 428 beschrieben, können in Wasch- und Reinigungsmitteln eingesetzt werden. In einer weiteren bevorzugten Ausfuhrungsform von Mitteln, in denen die erfindungsgemäße Verwendung stattfindet, wird ein kristallines Natriumschichtsilikat mit einem Modul von 2 bis 3 eingesetzt, wie es nach dem Verfahren der europäischen Patentanmeldung EP 0436 835 aus Sand und Soda hergestellt werden kann. Kristalline Natriumsilikate mit einem Modul im Bereich von 1,9 bis 3,5, wie sie nach den Verfahren der europäischen Patentschriften EP 0 164 552 und/oder EP 0 293 753 erhältlich sind, werden in einer weiteren bevorzugten Ausführungsform solcher Mittel eingesetzt. Falls als Buildersub- stanz auch Alkalialumosilikat, insbesondere Zeolith, vorhanden ist, beträgt das Gewichtsverhältnis Alumosilikat zu Silikat, jeweils bezogen auf wasserfreie Aktivsubstanzen, vorzugsweise 1:10 bis 10:1. In Mitteln, die sowohl amorphe als auch kristalline Alkalisilikate enthalten, beträgt das Gewichtsverhältnis von amorphem Alkali¬ silikat zu kristallinem Alkalisilikat vorzugsweise 1:2 bis 2:1 und insbesondere 1:1 bis 2:1.Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate. In particular, 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. Among these, 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 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. 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. In particular, both β- and δ-sodium disilicate (Na 2 Si 2 O 5 y H 2 O) are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in the international patent application WO 91/08171 is. δ-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. In a further preferred embodiment of agents in which the use according to the invention takes place, 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, as can be obtained by the processes of European patent EP 0 164 552 and / or EP 0 293 753, are used in a further preferred embodiment of such agents. If alkali aluminosilicate, in particular zeolite, is also present as the builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In compositions which contain both amorphous and crystalline alkali silicates, 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.
Buildersubstanzen sind in den Wasch- oder Reinigungsmitteln vorzugsweise in Mengen bis zu 60 Gew.-%, insbesondere von 5 Gew.-% bis 40 Gew.-%, enthalten, während Desin¬ fektionsmittel vorzugsweise frei von den lediglich die Komponenten der Wasserhärte komplexierenden Buildersubstanzen sind und bevorzugt nicht über 20 Gew.-%, insbeson- dere von 0,1 Gew.-% bis 5 Gew.-%, an schwermetallkomplexierenden Stoffen, vorzugsweise aus der Gruppe umfassend Aminopolycarbonsäuren, Aminopolyphosphon- säuren und Hydroxypolyphosphonsäuren und deren wasserlösliche Salze sowie deren Gemische, enthalten,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,
Als in Wasch- und Reinigungsmitteln verwendbare Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Cutinasen, Amylasen, Pullulanasen, Cellulasen, Hemicellulasen, Xylanasen, Oxidasen und Peroxidasen sowie deren Gemische in Frage. Besonders geeignet sind aus Pilzen oder Bakterien, wie Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes oder Pseudomonas cepacia gewonnene enzymatische Wirkstoffe. Die gegebenenfalls verwendeten Enzyme können, wie zum Beispiel in den internationalen Patentanmeldungen WO 92/11347 oder WO 94/23005 beschrieben, an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vor¬ zeitige Inaktivierung zu schützen. Sie sind in Wasch- und Reinigungsmitteln in Mengen von vorzugsweise bis zu 2 Gew.-%, insbesondere von 0,2 Gew.-% bis l,5 Gew.-%, enthalten.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.
Zu den in Wasch- und Reinigungsmitteln, insbesondere wenn sie in flüssiger oder pastö- ser Form vorliegen, verwendbaren organischen Lösungsmitteln gehören Alkohole mit 1 bis 4 C-Atomen, insbesondere Methanol, Ethanol, Isopropanol und tert.-Butanol, Diole mit 2 bis 4 C-Atomen, insbesondere Ethylenglykol und Propylenglykol, sowie deren Ge¬ mische und die aus den genannten Verbindungsklassen ableitbaren Ether. Derartige was¬ sermischbare Lösungsmittel sind in Wasch-, Reinigungs- und Desinfektionsmitteln vorzugsweise nicht über 30 Gew.-%, insbesondere von 6 Gew.-% bis 20 Gew.-%, vorhan¬ den.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.
Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH-Werts können derartige Mittel system- und umwelt¬ verträgliche Säuren, insbesondere Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bern¬ steinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure, oder Basen, insbesondere Ammonium- oder Alkalihydroxide, enthalten. Derartige pH-Regulatoren sind in den Mitteln vorzugsweise nicht über 20 Gew.-%, insbe¬ sondere von 1 ,2 Gew.-% bis 17 Gew.-%, enthalten.To set a desired pH value which does not result from the mixture of the other components, 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.
Zu den für den Einsatz in Waschmitteln für die Wäsche von Textilen in Frage kommenden Farbübertragungsinhibitoren gehören insbesondere Polyvinylpyrrolidone, Polyvinylimidazole, polymere N-Oxide wie Poly-(vinylpyridin-N-oxid) und Copolymere von Vinylpyrrolidon mit Vinylimidazol.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.
Vergrauungsinhibitoren haben die Aufgabe, den von der harten Oberfläche und insbesondere von der Textilfaser abgelösten Schmutz in der Flotte suspendiert zu halten und so den Builder beziehungsweise Co-Builder zu unterstützen. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise Leim, Gelatine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich andere als die obengenannten Stärkeprodukte verwenden, zum Beispiel Aldehydstärken. Bevorzugt werden Celluloseether, wie Carboxymethylcellulose (Na- Salz), Methylcellulose, Hydroxyalkylcellulose und Mischether, wie Methylhydroxyethylcellulose, Methylhydroxypropylcellulose, Methylcarboxymethyl- cellulose und deren Gemische, beispielsweise in Mengen von 0, 1 bis 5 Gew.-%, bezogen auf die Mittel, eingesetzt.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. For this purpose, 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 .
Die Mittel können als optische Aufheller zum Beispiel Derivate der Diaminostilbendisul- fonsäure beziehungsweise deren Alkalimetallsalze enthalten. Geeignet sind zum Beispiel Salze der 4,4'-Bis(2-anilino-4-moφholino-l,3,5-triazinyl-6-amino)stilben-2,2'- disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino- Gruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle anwesend sein, zum Beispiel die Alkalisalze des 4,4'- Bis(2-suIfostyryI)-diphenyls, 4,4'-Bis(4-chlor-3-suIfostyryl)-diphenyls, oder 4-(4- Chlorstyryl)-4,-(2-sulfostyryl)-diphenyls. Auch Gemische der vorgenannten optischen Aufheller können verwendet werden.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-moφholino-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.
Insbesondere beim Einsatz in maschinellen Wasch- und Reinigungsverfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Als Schauminhibitoren eignen sich beispielsweise Seifen natürlicher oder synthetischer Herkunft, die einen hohen Anteil an C18-C24-Fettsäuren aufweisen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure oder Bisfettsäurealkylendiamiden. Mit Vorteilen werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, zum Beispiel solche aus Silikonen, Paraffinen oder Wachsen. Vorzugsweise sind die Schauminhibitoren, insbesondere Silikon- und/oder Paraffin-haltige Schauminhibitoren, an eine granuläre, in Wasser lösliche beziehungsweise dispergierbare Trägersubstanz gebunden. Insbesondere sind dabei Mischungen aus Paraffinen und Bistearylethylendiamiden bevorzugt.In particular when used in machine washing and cleaning processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and 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.
Die Herstellung fester Mittel bietet keine Schwierigkeiten und kann auf bekannte Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei Persauerstoffverbin¬ dungen, insbesondere das Alkalipercarbonat, und sonstige thermisch empfindliche Inhaltsstoffe gegebenenfalls später separat zugesetzt werden. Zur Herstellung von Mitteln mit erhöhtem Schüttgewicht, insbesondere im Bereich von 650 g/1 bis 950 g/1, ist ein aus der europäischen Patentschrift EP 0 486 592 bekanntes, einen Extrusionschritt aufweisen¬ des Verfahren bevorzugt. Flüssige beziehungsweise pastöse Wasch- oder Reinigungsmit¬ tel in Form von übliche Lösungsmittel enthaltenden Lösungen werden in der Regel durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automa¬ tischen Mischer gegeben werden können, hergestellt. The preparation of solid agents presents no difficulties and can be carried out in a known manner, for example by spray drying or granulation, with peroxygen compounds, in particular the alkali percarbonate, and other thermally sensitive ingredients optionally being added separately later. For the production of agents with increased bulk density, in particular in the range from 650 g / 1 to 950 g / 1, a method known from European Patent EP 0 486 592 and having an extrusion step is preferred. Liquid or pasty detergents or cleaning agents in the form of solutions containing customary solvents are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.

Claims

Patentansprüche claims
1. Verwendung wasserlöslicher Salze, die Kristallwasser anlagern können, zur Stabili¬ sierung von teilchenförmigem Alkalipercarbonat.1. Use of water-soluble salts which can accumulate water of crystallization for the stabilization of particulate alkali percarbonate.
2. Verwendung wasserlöslicher Salze, die Kristallwasser anlagern können, zur Stabili¬ sierung von Alkalipercarbonat in pulverförmigen Wasch- oder Reinigungsmitteln.2. Use of water-soluble salts, which can accumulate water of crystallization, for stabilizing alkali percarbonate in powdered detergents or cleaning agents.
3. Verwendung wasserlöslicher Salze, die Kristallwasser anlagern können, zur Stabili¬ sierung von Alkalipercarbonat in flüssigen Wasch- oder Reinigungsmitteln.3. Use of water-soluble salts, which can accumulate water of crystallization, for the stabilization of alkali percarbonate in liquid washing or cleaning agents.
4. Verwendung wasserlöslicher Salze, die Kristallwasser anlagern können, zur Stabili¬ sierung von Alkalipercarbonat in pastenfbrmigen Wasch- oder Reinigungsmitteln.4. Use of water-soluble salts which can accumulate water of crystallization for the stabilization of alkali percarbonate in paste-like detergents or cleaning agents.
5. Verwendung nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß das flüssige oder pastenfbrmige Mittel wasserfrei ist.5. Use according to claim 3 or 4, characterized in that the liquid or paste-like agent is anhydrous.
6. Verwendung wasserlöslicher Salze, die Kristallwasser anlagern können, zur Stabili¬ sierung von Alkalipercarbonat in blockförmigen, insbesondere tablettenfbrmigen Wasch- oder Reinigungsmitteln.6. Use of water-soluble salts, which can accumulate water of crystallization, for the stabilization of alkali percarbonate in block-shaped, in particular tablet-shaped detergents or cleaning agents.
7. Verwendung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die wasserlöslichen Salze aus den Alkaliacetaten, den Alkalitricitrat-dihydraten und deren Mischungen ausgewählt werden.7. Use according to one of claims 1 to 6, characterized in that the water-soluble salts are selected from the alkali metal acetates, the alkali metal citrate dihydrates and mixtures thereof.
8. Verwendung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das wasserlösliche Salz ein Natriumsalz ist.8. Use according to one of claims 1 to 7, characterized in that the water-soluble salt is a sodium salt.
9. Verwendung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das Alkalipercarbonat Natriumpercarbonat ist.9. Use according to one of claims 1 to 8, characterized in that the alkali percarbonate is sodium percarbonate.
10. Verwendung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die Stabilisierung in Gegenwart eines Bleichaktivators stattfindet, der unter Perhydrolyse- bedingungen eine organische Peroxocarbonsäure bildet. 10. Use according to one of claims 1 to 9, characterized in that the stabilization takes place in the presence of a bleach activator which with perhydrolysis conditions forms an organic peroxocarboxylic acid.
PCT/EP1997/002301 1996-05-15 1997-05-06 Stabilisation of alkali percarbonate WO1997043211A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP97922976A EP0902756A1 (en) 1996-05-15 1997-05-06 Stabilisation of alkali percarbonate

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DE1996119646 DE19619646A1 (en) 1996-05-15 1996-05-15 Stabilization of alkali percarbonate
DE19619646.9 1996-05-15

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
WO2000050557A1 (en) * 1999-02-25 2000-08-31 Henkel Kommanditgesellschaft Auf Aktien Washing and cleaning agent shaped bodies which are stable in storage
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
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DE10032177A1 (en) * 2000-07-01 2002-01-10 Henkel Kgaa Coating process for basic particulate compounds
DE102004060011A1 (en) * 2004-12-14 2006-07-06 Degussa Ag Pressed shaped bodies containing coated sodium percarbonate particles

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FR2229766A1 (en) * 1973-05-14 1974-12-13 Procter & Gamble
DD140140A1 (en) * 1978-11-28 1980-02-13 Rainer Windisch METHOD FOR PRODUCING A STABLE SODIUM CARBONATE PERHYDRATE
EP0268170A2 (en) * 1986-11-15 1988-05-25 Henkel Kommanditgesellschaft auf Aktien Bleaching composition with a constant shelf-life and with improved solution ability
EP0546815A1 (en) * 1991-12-11 1993-06-16 Unilever Plc Sodium percarbonate
DE4324104A1 (en) * 1993-07-17 1995-01-19 Degussa Coated sodium percarbonate particles, process for their production and their use
WO1995002670A1 (en) * 1993-07-14 1995-01-26 The Procter & Gamble Company Granular laundry detergent compositions containing stabilised percarbonate bleach particles
DE4424005A1 (en) * 1994-07-07 1996-01-11 Henkel Kgaa Powdery bleach and detergent

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2229766A1 (en) * 1973-05-14 1974-12-13 Procter & Gamble
DD140140A1 (en) * 1978-11-28 1980-02-13 Rainer Windisch METHOD FOR PRODUCING A STABLE SODIUM CARBONATE PERHYDRATE
EP0268170A2 (en) * 1986-11-15 1988-05-25 Henkel Kommanditgesellschaft auf Aktien Bleaching composition with a constant shelf-life and with improved solution ability
EP0546815A1 (en) * 1991-12-11 1993-06-16 Unilever Plc Sodium percarbonate
WO1995002670A1 (en) * 1993-07-14 1995-01-26 The Procter & Gamble Company Granular laundry detergent compositions containing stabilised percarbonate bleach particles
DE4324104A1 (en) * 1993-07-17 1995-01-19 Degussa Coated sodium percarbonate particles, process for their production and their use
DE4424005A1 (en) * 1994-07-07 1996-01-11 Henkel Kgaa Powdery bleach and detergent

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000050557A1 (en) * 1999-02-25 2000-08-31 Henkel Kommanditgesellschaft Auf Aktien Washing and cleaning agent shaped bodies which are stable in storage
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

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EP0902756A1 (en) 1999-03-24
DE19619646A1 (en) 1997-11-20

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