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WO1992006167A1 - Percarbonate-containing washing agent - Google Patents

Percarbonate-containing washing agent Download PDF

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Publication number
WO1992006167A1
WO1992006167A1 PCT/EP1991/001872 EP9101872W WO9206167A1 WO 1992006167 A1 WO1992006167 A1 WO 1992006167A1 EP 9101872 W EP9101872 W EP 9101872W WO 9206167 A1 WO9206167 A1 WO 9206167A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
component
water
percarbonate
bleaching
Prior art date
Application number
PCT/EP1991/001872
Other languages
German (de)
French (fr)
Inventor
Heinz-Manfred Wilsberg
Rolf Puchta
Rainer Salz
Peter Krings
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6415871&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1992006167(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to DE59106781T priority Critical patent/DE59106781D1/en
Priority to EP91917296A priority patent/EP0552193B1/en
Priority to JP3515475A priority patent/JPH06501723A/en
Publication of WO1992006167A1 publication Critical patent/WO1992006167A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds

Definitions

  • the invention relates to a powdered bleach and detergent for use in household laundry, which can be added to the wash liquor as the sole active cleaning agent or which enhances the cleaning action of a conventional detergent.
  • Bleaching agents which contain a combination of an inorganic peroxide or perhydrate as a bleaching system with a bleach activator which forms an organic peracid under washing conditions have been known for a long time.
  • the most frequently used bleaching components containing active oxygen are the alkali perborates, percarbonates, persulfates and persilicates, among which sodium perborate, which is used as tetra- or monohydrate, occupies a dominant position.
  • activators those compounds are generally used which, under hydrolysis or perhydrolysis conditions, split off carboxylic acids or percarboxylic acids, the majority of those compounds being used which deliver peracetic acid in the presence of the oxidizing agents mentioned.
  • the invention is a storage-stable, essentially phosphate-free powdery bleach and detergent mixture containing alkali percarbonate, bleach activator, surfactant and builder, which is characterized in that it contains 3 powder-form components , wherein component A is a powder produced by spray drying, containing anionic surfactant, water-soluble and / or insoluble builder and less than 3% by weight of water, component B contains the alkali carbonate and component C contains the activator for the percarbonate with which Provided that there are 10% by weight to 93% by weight, preferably 20% by weight to 85% by weight and in particular 40% by weight to 80% by weight of component A, 5% by weight.
  • % to 70% by weight preferably 13% to 60% by weight and in particular 18% by weight to 50% by weight of component B and 2% by weight to 20% by weight, preferably Contains 2 wt .-% to 10 wt .-% of component C.
  • the amounts of water of the powder components specified in the context of the present invention relate to water which can be expelled when heated to a temperature of 200.degree.
  • the phrase "essentially free” means that the substance or component mentioned consists for the most part of the substance or substances mentioned and that no additives of which they are added are added during the preparation of the agents according to the invention should be essentially free.
  • certain starting substances may contain small amounts of other substances due to the manufacturing process, but these do not have a negative effect in the context of the present invention.
  • commercially available sodium percarbonate can contain small amounts, usually below 5% by weight, of phosphate.
  • the agent according to the invention preferably has a bulk density of not more than 800 grams per liter, in particular from 300 to 800 grams per liter and particularly preferably from 400 to 700 grams per liter. It will preferably used as an additive to detergent-containing liquors, in particular in the temperature range from 30 ° C. to 60 ° C., to enhance the bleaching effect (bleach booster), but can also be used to clean contaminated textiles, especially if only with relatively small amounts of non-bleachable soiling are to be used as the sole active cleaning component of the wash liquor.
  • the builder contained in component A is a water-soluble or a water-insoluble compound or a mixture of two or more of such compounds.
  • Zen suitable Bui ldersubstan- are in particular those from the classes of Polycarbonklarp * 1, more particularly sondere polymeric acrylic acids, methacrylic acids, maleic acids and upolymere from these, layered silicates, in particular bentonites, aluminum osilikate, ins ⁇ particular zeolites, alkali ikate, especially sodium silicate, and Alkali carbonates, especially sodium carbonate.
  • the aforementioned polycarboxylic acids are usually used in the form of their alkali salts, in particular their sodium or potassium salts.
  • the zeolites which are preferably incorporated are in particular those of the NaA or NaX type or mixtures thereof.
  • alkali silicates those with molar ratios of SiO 2 to alkali oxide in the range from 1.5 to 3.0 are preferred.
  • Such builder substances are preferably present in component A in amounts from 20% by weight to 90% by weight, in particular from 40% by weight to 80% by weight.
  • Suitable anionic surfactants are in particular those of the sulfate or sulfonate type, but other types such as soaps, long-chain N-acyl sarcosinates, salts of fatty acid cyanamides or salts of ether carboxylic acids, such as those obtainable from long-chain alkyl or alkylphenyl polyglycol ethers and chloroacetic acid, can also be used are used.
  • the anionic surfactants are preferably used in the form of the sodium salts. Such surfactants are contained in component A preferably in amounts of 2% by weight to 30% by weight, in particular 5% by weight to 20% by weight.
  • Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of long-chain primary alcohols of natural and synthetic origin with 10 to 20 carbon atoms, that is to say of fatty alcohols such as, for example, coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the CQ- to C20-0 alcohols and those of secondary alcohols of these chain lengths.
  • the sulfuric acid monoesters of the aliphatic primary alcohols, secondary alcohols or alkylphenols ethoxylated with 1 to 6 moles of ethylene oxide are suitable.
  • Sulfated fatty acid alkanols and sulfated fatty acid monoglycerides are also suitable.
  • the surfactants of the sulfonate type are primarily the alkylbenzenesulfonates with Cg to C ⁇ alkyl groups, sulfosuccinic acid onoesters and diesters with 6 to 22 C atoms in the alcohol parts and the esters of ⁇ -sulfofatty acids , for example the ⁇ -sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • alkanesulfonates which can be obtained from C 1 -C 2 -cig-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins
  • olefinsulfonates that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from long-chain monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkylbenzenesulfonates with linear Cg to C15 alkyl groups the fatty alcohol sulfates with 12 to 18 C atoms and mixtures of these surfactants are particularly preferred.
  • powder component A can contain inorganic filler salt, preferably in amounts not exceeding 50% by weight, in particular 1% by weight to 30% by weight.
  • filling salts include, in particular, the alkali chlorides and alkali sulfates.
  • Component A of the bleaching and washing agent according to the invention which contains builder and surfactant, is prepared in a manner known in principle by spray drying an aqueous suspension or slurry. Care should be taken to ensure that drying takes place in such a way that component A contains no more than 3% by weight of water.
  • a suspension of the containing about 30 wt .-% to 65 wt .-% water Ingredients of powder component A heated to temperatures of about 40 ° C to 100 ° C and sprayed by means of nozzles under an atomizing pressure of about 20 to 120 bar, in particular from 30 to 60 bar, in a falling roughness, in the cocurrent or preferably in the countercurrent Drying gases are introduced, which have inlet temperatures of about 150 ° C to about 350 ° C, in particular from 200 ° C to 250 ° C.
  • the powders produced in this way normally contain less than 5% of constituents with grain sizes of less than 0.1 mm; any higher dust particles that may occur can be removed by simple sieving and returned to the production process.
  • the powder component A thus produced preferably has a bulk density of 250 grams per liter to 750 grams per liter.
  • Component B contains alkali percarbonate, which is preferably the sole constituent of this component.
  • Sodium percarbonate is particularly suitable, which, due to the production process, can contain small amounts, usually below 5% by weight, based on alkali percarbonate, of phosphate and, if appropriate, further salts.
  • Component B can be present as a crystallized or, optionally with the aid of granulation aids, granulated powder.
  • Suitable activator component C is any powder-formable compound that provides organic peracid under perhydrolysis conditions.
  • These include, in particular, N- or 0-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, N-acylated triazines, in particular 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine, acylated glycolurils , in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, brazoles, diketopiperazines, sulphylamides and cyanurates, moreover carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentacylateda
  • the bleach activator can be coated with coating substances in a known manner or, if appropriate using granulation aids, granulated and, if desired, contain further additives, for example dye.
  • the powder component C preferably contains more than 65% by weight, in particular more than 90% by weight of bleach activator.
  • a bleach activator is used which forms peracetic acid under the washing conditions.
  • TAED tetraacetylethylenediamine
  • TAED tetraacetylethylenediamine
  • the washing and bleaching agent according to the invention can contain water-soluble salts as a further powdery component which do not give off water of crystallization in the range from 1 ° C. to 45 ° C. and whose melting point is above 45 ° C.
  • water-soluble salts include in particular sodium chloride, anhydrous sodium carbonate, sodium nitrate, sodium acetate and mixtures thereof.
  • Such powdery components are preferably not contained in the compositions according to the invention in excess of 30% by weight, in particular from 5% by weight to 20% by weight.
  • the agent according to the invention can contain, in addition to the previously mentioned components, complexing agents for heavy metals, which increase both the storage stability, in particular the percarbonate component, and the bleaching action of the bleaching agent according to the invention under conditions of use.
  • Suitable complexing agents include amino polycarboxylic acids, in particular nitrilotriacetic acid, ethylenediaminetetraacetic acid, polyphosphonic acids, in particular aminotri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, and in particular their alkali metal salts, in particular their Sodium salts.
  • Such complexing agents are preferably present in amounts not exceeding 10% by weight, in particular from 0.1% by weight to 2% by weight, based on the finished product. They can be part of component A, B or C and are preferably incorporated into the spray-dried powder (component A), in which they can be present in particular in amounts from 0.1% by weight to 10% by weight.
  • the washing and bleaching agent according to the invention can additionally, preferably in amounts not exceeding 10% by weight, in particular from 2% by weight to 6% by weight, based on the finished composition, contain nonionic surfactant, which may be present as part of the spray-dried component A or may have been sprayed onto the optionally available powdered water-soluble salt. If it is present as part of component A, in which it can preferably be present in amounts of not more than 10% by weight, in particular from 2% by weight to 6% by weight, the nonionic surfactant can be present as part of the aqueous Slurry also sprayed or sprayed onto the powder in a manner known in principle after the spray-drying of the remaining constituents.
  • the nonionic surfactants in question include alkyl polyglycosides with 10 to 22 carbon atoms in the alkyl part and the alkoxylates, in particular the ethoxylates and / or propoxylates of linear or branched-chain alcohols with 10 to 22 carbon atoms, preferably 12 to 18 C atoms.
  • the degree of alkoxylation of the alcohols is between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
  • the derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used.
  • the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful.
  • Corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxylic acid amides which correspond to the alcohols mentioned with regard to the alkyl part and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical can also be used.
  • the agent according to the invention can moreover contain further additives customary in bleaching and washing agents, such as enzymes, dyes and / or fragrances.
  • These constituents are preferably present in amounts of not more than 1% by weight, in particular from 0.05 to 0.5% by weight, based on the total agent. They can be part of one or more powder components or can be distributed more or less homogeneously over all powdery components.
  • the preparation of the agents according to the invention does not require any major technical effort.
  • simple mixing devices such as shovel or drum mixer in which the powdery components can be mixed.
  • the use of automatically operating belt scales in combination with free-fall mixers is also possible and is preferred for continuous production of the agents according to the invention.
  • the mixture can be carried out with simultaneous spraying of colorants and / or fragrances or liquid enzyme preparations.
  • Table 2 Composition of agents according to the invention [% by weight]
  • the detergents and bleaches Ml to M6 were free-flowing, non-clumping powders with bulk densities of about 560 to 620 grams per liter. They were stored at temperatures from 20 ° C. to 40 ° C. over a period of 24 weeks without any noticeable loss of activity, while similar formulations, the powder component A of which contained more than 3% by weight of water, showed clear decreases in theirs after only a few weeks Showed active oxygen content. In all cases, the bleaching performance of the detergents according to the invention was at least not worse than that of agents produced for comparison purposes, which contained sodium perborate instead of sodium percarbonate.

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Abstract

The bleaching and washing agent contains 3 powdered components, whereby component A is a powder produced by spray-drying, containing in particular 2 to 40 % wt. of anionic tenside, especially 20 to 90 % wt. of water-soluble and/or insoluble builders, not more than 50 % wt. inorganic filler salt, not more than 10 % wt. complex formers, not over 10 % wt. non-ionic tenside and less than 3 % wt. water, component B is alkaline percarbonate and component C contains an activator for the percarbonate, with the proviso that it contains 10 to 93 % wt. of component A, 5 to 70 % wt. of component B and 2 to 20 % wt. of component C.

Description

'Percarbonathaltiges Waschmittel' 'Percarbonate detergent'
Die Erfindung betrifft ein pulverförmiges Bleich- und Waschmittel zur An¬ wendung in der Haushaltswäsche, das als alleiniges reinigungsaktives Mit¬ tel der Waschlauge zugesetzt werden kann oder die Reinigungswirkung eines üblichen Waschmittels verstärkt.The invention relates to a powdered bleach and detergent for use in household laundry, which can be added to the wash liquor as the sole active cleaning agent or which enhances the cleaning action of a conventional detergent.
Bleichmittel, die als Bleichsystem eine Kombination eines anorganischen Peroxids oder Perhydrats mit einem Bleichaktivator, der unter Waschbedin¬ gungen eine organische Persäure bildet, enthalten, sind seit langer Zeit bekannt. Die am häufigsten eingesetzten aktivsauerstoffhaltigen Bleich¬ komponenten sind die Alkaliperborate, -percarbonate, -persulfate und - persilikate, unter denen Natriumperborat, das als Tetra- oder Monohydrat verwendet wird, eine dominierende Position einnimmt. Als Aktivatoren wer¬ den in der Regel solche Verbindungen verwendet, die unter Hydrolyse- be¬ ziehungsweise Perhydrolysebedingungen Carbonsäuren beziehungsweise Per- carbonsäuren abspalten, wobei in überwiegendem Maße solche Verbindungen eingesetzt werden, die in Gegenwart der erwähnten Oxidationsmittel Per¬ essigsäure liefern. Da die Reaktion des Aktivators mit der Perverbindung, die erst unter den wäßrigen Waschbedingungen erfolgen soll, auch bei der Herstellung und insbesondere der Lagerung derartiger Mittel ablaufen kann, wodurch die Verfügbarkeit der Perverbindung für den eigentlichen Anwen¬ dungszweck zurückgeht, wird seit langer Ze'it nach Stabilisatoren für die erwähnten Bleichsysteme gesucht. So ist zum Beispiel die Umhüllung der Aktivator- oder der Oxidationskomponente oder beider mit Fettsäuren vor¬ geschlagen worden. Auch die Zugabe bestimmter Stabilisatoren, beispiels¬ weise Magnesiumsilikat, ist bekannt. Für Percarbonat-haltige Bleichsysteme ist das Problem der mangelhaften Lagerstabilität besonders schwer zu lö¬ sen, da dieses Perhydrat extrem hydrolyseanfällig ist und sowohl von der normalen Luftfeuchtigkeit rasch zersetzt wird als auch in Bleichmitteln, die in wasserundurchlässigen Verpackungen gelagert werden, unter Verlust von Aktivsauerstoff zerfällt.Bleaching agents which contain a combination of an inorganic peroxide or perhydrate as a bleaching system with a bleach activator which forms an organic peracid under washing conditions have been known for a long time. The most frequently used bleaching components containing active oxygen are the alkali perborates, percarbonates, persulfates and persilicates, among which sodium perborate, which is used as tetra- or monohydrate, occupies a dominant position. As activators, those compounds are generally used which, under hydrolysis or perhydrolysis conditions, split off carboxylic acids or percarboxylic acids, the majority of those compounds being used which deliver peracetic acid in the presence of the oxidizing agents mentioned. Since the reaction of the activator with the per-compound, which is only to take place under the aqueous washing conditions, can also take place during the preparation and in particular the storage of such agents, as a result of which the availability of the per-compound for the actual purpose of use decreases, it has been a long time searched for stabilizers for the bleaching systems mentioned. For example, the coating of the activator component or the oxidation component or both with fatty acids has been proposed. The addition of certain stabilizers, for example magnesium silicate, is also known. For bleaching systems containing percarbonate, the problem of inadequate storage stability is particularly difficult to solve, since this perhydrate is extremely susceptible to hydrolysis and from both normal atmospheric moisture is rapidly decomposed and also in bleaches, which are stored in water-impermeable packaging, disintegrates with the loss of active oxygen.
Gegenstand der Erfindung, mit der diese Nachteile vermieden werden können, ist ein lagerstabiles, im wesentlichen phosphatfreies pulverförmiges Bleich- und Waschmittelgemisch, enthaltend Alkalipercarbonat, Bleichakti¬ vator, Tensid und Builder, das dadurch gekennzeichnet ist, daß es 3 pul- verför ige Komponenten enthält, wobei Komponente A ein durch Sprühtrocknen hergestelltes Pulver ist, enthaltend Aniontensid, wasserlöslichen und/oder unlöslichen Builder und weniger als 3 Gew.-% Wasser, Komponente B das Al¬ kalipercarbonat und Komponente C den Aktivator für das Percarbonat ent¬ hält, mit der Maßgabe, daß es 10 Gew.-% bis 93 Gew.-%, vorzugsweise 20 Gew.-% bis 85 Gew.-% und insbesondere 40 Gew.-% bis 80 Gew.-% der Kom¬ ponente A, 5 Gew.-% bis 70 Gew.-%, vorzugsweise 13 Gew.- bis 60 Gew.-% und insbesondere 18 Gew.-% bis 50 Gew.-% der Komponente B und 2 Gew.-% bis 20 Gew.-%, vorzugsweise 2 Gew.-% bis 10 Gew.-% der Komponente C enthält.The invention, with which these disadvantages can be avoided, is a storage-stable, essentially phosphate-free powdery bleach and detergent mixture containing alkali percarbonate, bleach activator, surfactant and builder, which is characterized in that it contains 3 powder-form components , wherein component A is a powder produced by spray drying, containing anionic surfactant, water-soluble and / or insoluble builder and less than 3% by weight of water, component B contains the alkali carbonate and component C contains the activator for the percarbonate with which Provided that there are 10% by weight to 93% by weight, preferably 20% by weight to 85% by weight and in particular 40% by weight to 80% by weight of component A, 5% by weight. % to 70% by weight, preferably 13% to 60% by weight and in particular 18% by weight to 50% by weight of component B and 2% by weight to 20% by weight, preferably Contains 2 wt .-% to 10 wt .-% of component C.
Die im Rahmen der vorliegenden Erfindung angegebenen Wassermengen der Pulverkomponenten beziehen sich auf Wasser, das bei Erhitzen auf eine Temperatur von 200 °C ausgetrieben werden kann.The amounts of water of the powder components specified in the context of the present invention relate to water which can be expelled when heated to a temperature of 200.degree.
Die Formulierung "im wesenlichen frei" bedeutet im Rahmen des vorliegenden Textes, daß die angesprochene Substanz oder Komponente zum weitaus über¬ wiegenden Teil aus dem genannten Stoff oder den genannten Stoffen besteht und während der Herstellung der erfindungsgemäßen Mittel keine Zusätze hinzugegeben werden, von der sie im wesentlichen frei sein soll. Aller¬ dings können bestimmte Ausgangssubstanzen herstellungsbedingt geringe Mengen anderer Stoffe enthalten, die sich im Rahmen der vorliegenden Er¬ findung jedoch nicht negativ auswirken. So kann zum Beispiel handels¬ übliches Natriumpercarbonat geringe Mengen, in der Regel unter 5 Gew.-%, Phosphat enthalten.In the context of the present text, the phrase "essentially free" means that the substance or component mentioned consists for the most part of the substance or substances mentioned and that no additives of which they are added are added during the preparation of the agents according to the invention should be essentially free. However, certain starting substances may contain small amounts of other substances due to the manufacturing process, but these do not have a negative effect in the context of the present invention. For example, commercially available sodium percarbonate can contain small amounts, usually below 5% by weight, of phosphate.
Das erfindungsgemäße Mittel weist vorzugsweise ein Schüttgewicht von nicht über 800 Gramm pro Liter, insbesondere von 300 bis 800 Gramm pro Liter und besonders bevorzugt von 400 bis 700 Gramm pro Liter auf. Es wird vorzugsweise als Zusatz zu wasch ittelhaltigen Flotten, insbesondere im Temperaturbereich von 30 °C bis 60 °C, zur Verstärkung der Bleichwirkung (Bleichbooster) eingesetzt, kann allerdings auch, insbesondere wenn nur mit relativ geringen Mengen an nicht-bleichbaren Anschmutzungen verunrei¬ nigte Textilien gereinigt werden sollen, als alleinige reinigungsaktive Komponente der Waschflotte verwendet werden.The agent according to the invention preferably has a bulk density of not more than 800 grams per liter, in particular from 300 to 800 grams per liter and particularly preferably from 400 to 700 grams per liter. It will preferably used as an additive to detergent-containing liquors, in particular in the temperature range from 30 ° C. to 60 ° C., to enhance the bleaching effect (bleach booster), but can also be used to clean contaminated textiles, especially if only with relatively small amounts of non-bleachable soiling are to be used as the sole active cleaning component of the wash liquor.
Bei dem in der Komponente A enthaltenen Builder handelt es sich um eine wasserlösliche oder eine wasserunlösliche Verbindung oder um ein Gemisch aus zwei oder mehreren derartiger Verbindungen. Geeignete Bui ldersubstan- zen sind insbesondere solche aus den Klassen der Polycarbonsäurp*1, insbe¬ sondere polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und upolymere aus diesen, Schichtsilikate, insbesondere Bentonite, Alu osilikate, ins¬ besondere Zeolithe, Alkalis ikate, insbesondere Natriumsilikat, und Alkalicarbonate, insbesondere Natriumcarbonat. Die vorgenannten Polycarbonsäuren werden üblicherweise in Form ihrer Alkal salze, insbe¬ sondere ihrer Natrium- oder Kaliumsalze eingesetzt. Die vorzugsweise ein¬ gearbeiteten Zeolithe sind insbesondere solche des NaA- oder NaX-Typs oder deren Gemische. Unter den Alkalisil katen sind solche mit MolVerhältnissen von SiÜ2 zu Alkalioxid im Bereich von 1,5 bis 3,0 bevorzugt. Derartige Buildersubstanzen sind in Komponente A vorzugsweise in Mengen von 20 Gew.-% bis 90 Gew.-%, insbesondere von 40 Gew.-% bis 80 Gew.-% enthalten.The builder contained in component A is a water-soluble or a water-insoluble compound or a mixture of two or more of such compounds. Zen suitable Bui ldersubstan- are in particular those from the classes of Polycarbonsäurp * 1, more particularly sondere polymeric acrylic acids, methacrylic acids, maleic acids and upolymere from these, layered silicates, in particular bentonites, aluminum osilikate, ins¬ particular zeolites, alkali ikate, especially sodium silicate, and Alkali carbonates, especially sodium carbonate. The aforementioned polycarboxylic acids are usually used in the form of their alkali salts, in particular their sodium or potassium salts. The zeolites which are preferably incorporated are in particular those of the NaA or NaX type or mixtures thereof. Among the alkali silicates, those with molar ratios of SiO 2 to alkali oxide in the range from 1.5 to 3.0 are preferred. Such builder substances are preferably present in component A in amounts from 20% by weight to 90% by weight, in particular from 40% by weight to 80% by weight.
Geeignete anionische Tenside sind insbesondere solche vom Sulfat- oder Sulfonattyp, doch können auch andere Typen wie Seifen, langkettige N- Acylsarkosinate, Salze von Fettsäurecyanamiden oder Salze von Ethercar- bonsäuren, wie sie aus langkettigen Alkyl- oder Alkylphenyl-Polyglykol- ethern und Chloressigsäure zugänglich sind, verwendet werden. Die anio¬ nischen Tenside werden vorzugsweise in Form der Natriumsalze verwendet. Derartige Tenside sind in Komponente A vorzugsweise in Mengen von 2 Gew.-% bis 30 Gew.-%, insbesondere von 5 Gew.-% bis 20 Gew.- enthalten.Suitable anionic surfactants are in particular those of the sulfate or sulfonate type, but other types such as soaps, long-chain N-acyl sarcosinates, salts of fatty acid cyanamides or salts of ether carboxylic acids, such as those obtainable from long-chain alkyl or alkylphenyl polyglycol ethers and chloroacetic acid, can also be used are used. The anionic surfactants are preferably used in the form of the sodium salts. Such surfactants are contained in component A preferably in amounts of 2% by weight to 30% by weight, in particular 5% by weight to 20% by weight.
Besonders geeignete Tenside vom Sulfattyp sind die Schwefelsäuremonoester von langkettigen primären Alkoholen natürlichen und synthetischen Ur¬ sprungs mit 10 bis 20 C-Atomen, das heißt von Fettalkoholen wie zum Bei¬ spiel Kokosfettalkoholen, Taigfettalkoholen, Oleylalkohol, oder den C Q- bis C20-0χoalkoholen und solche von sekundären Alkoholen dieser Ketten¬ längen. Daneben kommen die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten aliphatischen primären Alkohole, sekundären Al¬ kohole oder Alkylphenole in Betracht. Ferner eignen sich sulfatierte Fettsäurealkanola ide und sulfatierte Fettsäuremonoglyceride.Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of long-chain primary alcohols of natural and synthetic origin with 10 to 20 carbon atoms, that is to say of fatty alcohols such as, for example, coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the CQ- to C20-0 alcohols and those of secondary alcohols of these chain lengths. In addition, the sulfuric acid monoesters of the aliphatic primary alcohols, secondary alcohols or alkylphenols ethoxylated with 1 to 6 moles of ethylene oxide are suitable. Sulfated fatty acid alkanols and sulfated fatty acid monoglycerides are also suitable.
Bei den Tensiden vom Sulfonattyp handelt es sich in erster Linie um die Alkylbenzolsulfonate mit Cg- bis C^-Alkylgruppen, um Sulfobernstein- säure ono- und -diester mit 6 bis 22 C-Atomen in den Alkoholteilen und um die Ester von α-Sulfofettsäuren, beispeilsweise die α-sulfonierten Methyl¬ oder Ethylester der hydrierten Kokos-, Palmkern- oder Taigfettsäuren. Weitere brauchbare Tenside vom Sulfonattyp sind die Alkansulfonate, die aus Ci2~ bis Cig-Alkanen durch Sulfochlorierung oder Sulfoxidation und anschließende Hydrolyse bzw. Neutralisation oder durch Bisulfitaddition an Olefine erhältlich sind, sowie die Olefinsulfonate, das heißt Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie zum Beispiel aus langkettigen Monoolefinen mit end- oder innenständiger Dop¬ pelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und an¬ schließender alkalischer oder saurer Hydrolyse der Sulfonierungsprodukte erhält.The surfactants of the sulfonate type are primarily the alkylbenzenesulfonates with Cg to C ^ alkyl groups, sulfosuccinic acid onoesters and diesters with 6 to 22 C atoms in the alcohol parts and the esters of α-sulfofatty acids , for example the α-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Other useful surfactants of the sulfonate type are the alkanesulfonates which can be obtained from C 1 -C 2 -cig-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the olefinsulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from long-chain monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
Besonders bevorzugt werden die Alkylbenzolsulfonate mit linearen Cg- bis Ci5-Alkylgruppen, die Fettalkoholsulfate mit 12 bis 18 C-Atomen und Ge¬ mische dieser Tenside verwendet.The alkylbenzenesulfonates with linear Cg to C15 alkyl groups, the fatty alcohol sulfates with 12 to 18 C atoms and mixtures of these surfactants are particularly preferred.
Zusätzlich kann die Pulverkomponente A anorganisches Füllsalz, vorzugs¬ weise in Mengen nicht über 50 Gew.-%, insbesondere 1 Gew.-% bis 30 Gew.-% enthalten. Zu derartigen Füllsalzen gehören insbesondere die Alkalichlo¬ ride und Alkal sulfate.In addition, powder component A can contain inorganic filler salt, preferably in amounts not exceeding 50% by weight, in particular 1% by weight to 30% by weight. Such filling salts include, in particular, the alkali chlorides and alkali sulfates.
Die Builder- und Tensid-haltige Komponente A des erfindungsgemäßen Bleich- und Waschmittels wird in im Prinzip bekannter Weise durch Sprühtrocknen einer wäßrigen Suspension oder Aufschlämmung hergestellt. Dabei ist darauf zu achten, daß die Trocknung derart erfolgt, daß Komponente A nicht mehr als 3 Gew.-% Wasser enthält. Vorzugsweise geht man daher so vor, daß eine etwa 30 Gew.-% bis 65 Gew.-% Wasser enthaltende Suspension der Inhaltsstoffe der Pulverkomponente A auf Temperaturen von etwa 40 °C bis 100 °C erwärmt und mittels Düsen unter einem Zerstäubungsdruck von etwa 20 bis 120 bar, insbesondere von 30 bis 60 bar, in einen Fallrau gesprüht wird, in den im Gleichstrom oder vorzugsweise im Gegenstrom Trocknungsgase eingeleitet werden, die Eingangstemperaturen von etwa 150 °C bis etwa 350 °C, insbesondere von 200 °C bis 250 °C aufweisen. Die auf diese Weise erzeugten Pulver enthalten normalerweise weniger als 5 % Bestandteile mit Korngrößen unter 0,1 mm, eventuell auftretende höhere Staubaπteile können durch einfaches Aussieben entfernt und in den Herstellungspi ozeß zurück¬ geführt werden. Vorzugsweise weist die derart hergestellte Pulverkompo¬ nente A ein Schüttgewicht von 250 Gramm pro Liter bis 750 Gramm pro Liter auf.Component A of the bleaching and washing agent according to the invention, which contains builder and surfactant, is prepared in a manner known in principle by spray drying an aqueous suspension or slurry. Care should be taken to ensure that drying takes place in such a way that component A contains no more than 3% by weight of water. It is therefore preferred to proceed in such a way that a suspension of the containing about 30 wt .-% to 65 wt .-% water Ingredients of powder component A heated to temperatures of about 40 ° C to 100 ° C and sprayed by means of nozzles under an atomizing pressure of about 20 to 120 bar, in particular from 30 to 60 bar, in a falling roughness, in the cocurrent or preferably in the countercurrent Drying gases are introduced, which have inlet temperatures of about 150 ° C to about 350 ° C, in particular from 200 ° C to 250 ° C. The powders produced in this way normally contain less than 5% of constituents with grain sizes of less than 0.1 mm; any higher dust particles that may occur can be removed by simple sieving and returned to the production process. The powder component A thus produced preferably has a bulk density of 250 grams per liter to 750 grams per liter.
Komponente B enthält Alkalipercarbonat, das vorzugsweise der alleinige Bestandteil dieser Komponente ist. In Frage kommt insbesondere Natrium- percarbonat, das bedingt durch das Herstellungsverfahren geringe Mengen, normalerweise unter 5 Gew.-% bezogen auf Alkalipercarbonat, an Phosphat sowie gegebenenfalls weitere Salze enthalten kann. Komponente B kann als kristallisiertes oder, gegebenenfalls mit Hilfe von Granulationshilfsmit¬ teln, granuliertes Pulver vorliegen.Component B contains alkali percarbonate, which is preferably the sole constituent of this component. Sodium percarbonate is particularly suitable, which, due to the production process, can contain small amounts, usually below 5% by weight, based on alkali percarbonate, of phosphate and, if appropriate, further salts. Component B can be present as a crystallized or, optionally with the aid of granulation aids, granulated powder.
Als Aktivatorkomponente C ist jede pulverförmig konfektionierbare, unter Perhydrolysebedingungen organische Persäure liefernde Verbindung geeignet. Zu diesen gehören insbesondere N- oder 0-AcylVerbindungen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendia in, N-acylierte Triazine, insbesondere l,5-Diacetyl-2,4-dioxo-hexahydro-l,3,5- triazin, acylierte Glykolurile, insbesondere Tetraacetylglykoluril , N- acylierte Hydantoine, Hydrazide, Triazole, brazole, Diketopiperazine, Sul- furylamide und Cyanurate, außerdem Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, Carbonsäureester, insbesondere Natrium-isononanoyl- phenolsulfonat,und acylierte Zuckerderivate, insbesondere Pentaacetyl- glukose. Der Bleichaktivator kann in bekannter Weise mit Hüllsubstanzen überzogen oder, gegebenenfalls unter Einsatz von Granulierhilfs ittlen, granuliert worden sein und gewünschtenfalls weitere Zusatzstoffe, beispiels¬ weise Farbstoff, enthalten. Vorzugsweise enthält die Pulverkomponente C über 65 Gew.-%, insbesondere über 90 Gew.- Bleichaktivator. Vorzugsweise wird ein Bleichaktivator eingesetzt, der unter den Waschbedingungen Per¬ essigsäure bildet. Unter diesen ist mit Hilfe von Carboxy ethylcellulose granuliertes Tetraacetylethylendiamin (TAED) mit mittleren Korngrößen von 0,01 mm bis 0,8 mm, wie es nach dem in der europäischen Patentschrift EP 037026 beschriebenen Verfahren hergestellt werden kann, besonders bevorzugt. TAED ist vorzugsweise in Mengen von 94 Gew.-% bis 99 Gew.-% in der Pulverkomponente C enthalten.Suitable activator component C is any powder-formable compound that provides organic peracid under perhydrolysis conditions. These include, in particular, N- or 0-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, N-acylated triazines, in particular 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine, acylated glycolurils , in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, brazoles, diketopiperazines, sulphylamides and cyanurates, moreover carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentacylatedacetate derivatives. The bleach activator can be coated with coating substances in a known manner or, if appropriate using granulation aids, granulated and, if desired, contain further additives, for example dye. The powder component C preferably contains more than 65% by weight, in particular more than 90% by weight of bleach activator. Preferably a bleach activator is used which forms peracetic acid under the washing conditions. Among these, tetraacetylethylenediamine (TAED) granulated with carboxyethylcellulose and having average grain sizes of 0.01 mm to 0.8 mm, as can be prepared by the process described in European Patent EP 037026, is particularly preferred. TAED is preferably contained in the powder component C in amounts of 94% by weight to 99% by weight.
Zusätzlich zu den Komponenten A, B und C kann das erfindungsgemäße Wasch- und Bleichmittel als weitere pulverför ige Komponente wasserlösliche Salze enthalten, die im Bereich von 1 °C bis 45 °C kein Kristallwasser abgeben und deren Schmelzpunkt über 45 °C liegt. Zu diesen gehören insbesondere Natriumchlorid, wasserfreies Natriu carbonat, Natriumnitrat, Natriumacetat und deren Gemische. Derartige pulverförmige Komponenten sind in den er¬ findungsgemäßen Mitteln vorzugsweise nicht über 30 Gew.-%, insbesondere von 5 Gew.-% bis 20 Gew.-% enthalten.In addition to components A, B and C, the washing and bleaching agent according to the invention can contain water-soluble salts as a further powdery component which do not give off water of crystallization in the range from 1 ° C. to 45 ° C. and whose melting point is above 45 ° C. These include in particular sodium chloride, anhydrous sodium carbonate, sodium nitrate, sodium acetate and mixtures thereof. Such powdery components are preferably not contained in the compositions according to the invention in excess of 30% by weight, in particular from 5% by weight to 20% by weight.
Das erfindungsgemäße Mittel kann zusätzlich zu den bisher genannten Be¬ standteilen Komplexbildner für Schwermetalle enthalten, die sowohl die Lagerstabilität, insbesondere der Percarbonat-Komponente, wie auch die Bleichwirkung des erfindungsgemäßen Bleichmittels unter Anwendungsbedin¬ gungen erhöhen. Zu den geeigneten Ko plexierungs itteln gehören Amino- polycarbonsäuren, insbesondere Nitrilotriessigsäure, Ethylendiamintetra- essigsäure, Polyphosphonsäuren, insbesondere Aminotri-(methylenphosphon- säure), Ethylendiamintetra-(methylenphosphonsäure) und 1-Hydroxyethan- 1,1-diphosphonsäure sowie deren Alkalisalze, insbesondere deren Natrium¬ salze. Derartige Komplexbildner sind vorzugsweise in Mengen nicht über 10 Gew.-%, insbesondere von 0,1 Gew.-% bis 2 Gew.-%, bezogen auf das fer¬ tige Mittel, vorhanden. Sie können Teil der Komponente A, B oder C sein und werden vorzugsweise in das sprühgetrocknete Pulver (Komponente A) eingearbeitet, in dem sie insbesondere in Mengen von 0,1 Gew.-% bis 10 Gew.-% vorhanden sein können.The agent according to the invention can contain, in addition to the previously mentioned components, complexing agents for heavy metals, which increase both the storage stability, in particular the percarbonate component, and the bleaching action of the bleaching agent according to the invention under conditions of use. Suitable complexing agents include amino polycarboxylic acids, in particular nitrilotriacetic acid, ethylenediaminetetraacetic acid, polyphosphonic acids, in particular aminotri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, and in particular their alkali metal salts, in particular their Sodium salts. Such complexing agents are preferably present in amounts not exceeding 10% by weight, in particular from 0.1% by weight to 2% by weight, based on the finished product. They can be part of component A, B or C and are preferably incorporated into the spray-dried powder (component A), in which they can be present in particular in amounts from 0.1% by weight to 10% by weight.
Weiterhin kann das erfindungsgemäße Wasch- und Bleichmittel zusätzlich, vorzugsweise in Mengen nicht über 10 Gew.-%, insbesondere von 2 Gew.-% bis 6 Gew.-%, bezogen auf das fertige Mittel, nichtionisches Tensid enthalten, das als Teil der sprühgetrockneten Komponente A vorliegen oder auf das fakultativ vorhandene pulverförmige wasserlösliche Salz aufgedüst worden sein kann. Falls es als Teil der Komponente A, in der es vorzugsweise in Mengen nicht über 10 Gew.-%, insbesondere von 2 Gew.- bis 6 Gew.-% ent¬ halten sein kann, vorliegt, kann das nichtionische Tensid als Teil der wäßrigen Aufschlämmung mitversprüht oder nach dem Sprühtrocknen der übri¬ gen Bestandteile in im Prinzip bekannter Weise auf das Pulver aufgedüst werden. Zu den in Frage kommenden nichtionischen Tensiden gehören Alkyl- polyglykoside mit 10 bis 22 C-Atomen im Alkylteil und die Alkoxylate, ins¬ besondere die Ethoxylate und/oder Propoxylate von linearen oder verzweigt- kettigen Alkoholen mit 10 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Ato¬ men. Der Alkoxylierungsgrad der Alkohole liegt dabei zwischen 1 und 20, vorzugsweise zwischen 3 und 10. Sie können in bekannter Weise durch Um¬ setzung der entsprechenden Alkohole mit den entsprechenden Alkylenoxiden hergestellt werden. Geeignet sind insbesondere die Derivate der Fettalko¬ hole, obwohl auch deren verzweigtkettige Isomere, insbesondere sogenannte Oxoalkohole, zur Herstellung verwendbarer Alkoxylate eingesetzt werden können. Brauchbar sind demgemäß insbesondere die Ethoxylate primärer Alko¬ hole mit linearen Dodecyl-, Tetradecyl-, Hexadecyl- oder Octadecylresten sowie deren Gemische. Außerdem sind entsprechende Ethoxylierungs- und/oder Propoxylierungsprodukte von Alkylaminen, vicinalen Diolen und Carbonsäure- amiden, die hinsichtlich des Alkylteils den genannten Alkoholen entsprechen sowie von Alkylphenolen mit 5 bis 12 C-Atomen im Alkylrest verwendbar.Furthermore, the washing and bleaching agent according to the invention can additionally, preferably in amounts not exceeding 10% by weight, in particular from 2% by weight to 6% by weight, based on the finished composition, contain nonionic surfactant, which may be present as part of the spray-dried component A or may have been sprayed onto the optionally available powdered water-soluble salt. If it is present as part of component A, in which it can preferably be present in amounts of not more than 10% by weight, in particular from 2% by weight to 6% by weight, the nonionic surfactant can be present as part of the aqueous Slurry also sprayed or sprayed onto the powder in a manner known in principle after the spray-drying of the remaining constituents. The nonionic surfactants in question include alkyl polyglycosides with 10 to 22 carbon atoms in the alkyl part and the alkoxylates, in particular the ethoxylates and / or propoxylates of linear or branched-chain alcohols with 10 to 22 carbon atoms, preferably 12 to 18 C atoms. The degree of alkoxylation of the alcohols is between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. The derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used. Accordingly, the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxylic acid amides which correspond to the alcohols mentioned with regard to the alkyl part and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical can also be used.
Das erfindungsgemäße Mittel kann darüberhinaus weitere in Bleich- und Waschmitteln übliche Zusatzstoffe, wie Enzyme, Farbstoffe und/oder Duft¬ stoffe, enthalten. Diese Bestandteile sind vorzugsweise in Mengen nicht über 1 Gew.-%, insbesondere von 0,05 bis 0,5 Gew.-%, bezogen auf das ge¬ samte Mittel, vorhanden. Sie können Teil einer oder mehrerer Pulverkom¬ ponenten sein oder mehr oder weniger homogen auf alle pulverförmigen Be¬ standteile verteilt sein.The agent according to the invention can moreover contain further additives customary in bleaching and washing agents, such as enzymes, dyes and / or fragrances. These constituents are preferably present in amounts of not more than 1% by weight, in particular from 0.05 to 0.5% by weight, based on the total agent. They can be part of one or more powder components or can be distributed more or less homogeneously over all powdery components.
Die Herstellung der erfindungsgemäßen Mittel erfordert keinen größeren technischen Aufwand. Meist sind einfache Mischapparaturen, wie Schaufel- oder Trommelmischer geeignet, in denen die pulverförmigen Komponenten ge¬ mischt werden können. Auch die Verwendung automatisch arbeitender Band¬ waagen in Kombination mit Freifallmischern ist möglich und wird für eine kontiniuerliche Produktion der erfindungsgemäßen Mittel bevorzugt. Gege¬ benenfalls kann die Mischung unter gleichzeitigem Aufdüsen von Farb- und/oder Duftstoffen beziehungsweise flüssigen Enzymzubereitungen erfol¬ gen.The preparation of the agents according to the invention does not require any major technical effort. Usually, simple mixing devices, such as shovel or drum mixer in which the powdery components can be mixed. The use of automatically operating belt scales in combination with free-fall mixers is also possible and is preferred for continuous production of the agents according to the invention. If necessary, the mixture can be carried out with simultaneous spraying of colorants and / or fragrances or liquid enzyme preparations.
BeispieleExamples
Beispiel 1example 1
Durch Versprühen von etwa 35 Gew.-% Wasser enthaltenden Aufschlämmungen, die auf 60 °C bis 70 °C erwärmt worden waren, unter einem Druck von etwa 60 bar und Temperaturen des Trocknungsgases von 220 °C bis 230 °C wurden die in der nachfolgenden Tabelle 1 durch ihre Zusammensetzung charakteri¬ sierten Pulver (Komponente A) hergestellt. Diese wiesen Schüttdichten von etwa 450 Gramm pro Liter auf.By spraying slurries containing about 35% by weight of water, which had been heated to 60 ° C to 70 ° C, under a pressure of about 60 bar and temperatures of the drying gas of 220 ° C to 230 ° C, those in the following Table 1 produced powder characterized by their composition (component A). These had bulk densities of around 450 grams per liter.
Tabelle 1; Zusammensetzung der Pulverkomponente A [Gew.-%]Table 1; Composition of powder component A [% by weight]
Figure imgf000010_0001
a) Tetra-Na-hydroxyethan-l,l-diphosphonat (Hersteller Henkel) b) Acrylsäure/Maleinsäure-Copolymer (30:70), Natriumsalz (Hersteller BASF) c) 3- bis 5-fach ethoxylierte C-^-lS^-^talkohole (Hersteller Henkel) Durch Vermischen der in der nachfolgenden Tabelle 2 angegebenen Pulver¬ komponenten in einem Freifall ischer unter gleichzeitigem Aufdüsen eines oxidationsstabilen Parfüms wurden die durch ihre Zusammensetzung charak¬ terisierten erfindungsgemäßen Bleichmittel Ml bis M6 hergestellt.
Figure imgf000010_0001
a ) Tetra-Na-hydroxyethane-l, l-diphosphonate (manufacturer Henkel) b) acrylic acid / maleic acid copolymer (30:70), sodium salt (manufacturer BASF) c ) 3- to 5-fold ethoxylated C - ^ - lS ^ - ^ talkohole (manufacturer Henkel) The bleaching agents M1 to M6 according to the invention characterized by their composition were prepared by mixing the powder components listed in Table 2 below in a free fall with simultaneous spraying on of an oxidation-stable perfume.
Tabelle 2: Zusammensetzung erfindungsgemäßer Mittel [Gew.-%]Table 2: Composition of agents according to the invention [% by weight]
Figure imgf000011_0001
a) Aktivsauerstoffgehalt 14 % (Hersteller Interox) b) Granulat gemäß EP 037026, 94-prozentig c) Dehydol(R) LST (20 Gew.-Teile) auf Natriumcarbonat (80 Gew.-Teile) aufgedüst
Figure imgf000011_0001
a ) Active oxygen content 14% (manufacturer Interox) b ) Granules according to EP 037026, 94 percent c ) Dehydol ( R ) LST (20 parts by weight) sprayed onto sodium carbonate (80 parts by weight)
Die Wasch- und Bleichmittel Ml bis M6 waren freifließende, nicht Klumpende Pulver mit Schüttdichten von etwa 560 bis 620 Gramm pro Liter. Sie wurden bei Temperaturen von 20 °C bis 40 °C über einen Zeitraum von 24 Wochen ohne nennenswerten Aktivitätsverlust gelagert, während gleichartige For¬ mulierungen, deren Pulverkomponente A über 3 Gew.-% Wasser enthielt, schon nach Lagerungszeiten von wenigen Wochen deutliche Abnahmen ihres Aktiv- sauerstoffgehaltes zeigten. Die Bleichleistung der erfindungsgemäßen Waschmittel war in allen Fällen zumindest nicht schlechter als die von zu Vergleichszwecken hergestellten Mitteln, die statt Natriumpercarbonat Na¬ triumperborat enthielten. The detergents and bleaches Ml to M6 were free-flowing, non-clumping powders with bulk densities of about 560 to 620 grams per liter. They were stored at temperatures from 20 ° C. to 40 ° C. over a period of 24 weeks without any noticeable loss of activity, while similar formulations, the powder component A of which contained more than 3% by weight of water, showed clear decreases in theirs after only a few weeks Showed active oxygen content. In all cases, the bleaching performance of the detergents according to the invention was at least not worse than that of agents produced for comparison purposes, which contained sodium perborate instead of sodium percarbonate.

Claims

Patentansprüche Claims
1. Im wesentlichen phosphatfreies pulverförmiges Bleich- und Waschmittel, enthaltend Alkalipercarbonat, Bleichaktivator, Tensid und Builder, da¬ durch gekennzeichnet, daß es 3 pulverförmige Komponenten enthält, wobei Komponente A ein durch Sprühtrocknen hergestelltes Pulver ist, enthal¬ tend Aniontensid, wasserlöslichen und/oder unlöslichen Builder und we¬ niger als 3 Gew.-% Wasser, Komponente B das Alkalipercarbonat und Kom¬ ponente C einen Aktivator für das Percarbonat enthält, mit der Maßgabe, daß es 10 Gew.-% bis 93 Gew.-% der Komponente A, 5 Gew.-% bis 70 Gew.-% der Komponente B und 2 Gew.-% bis 20 Gew.-% der Komponente C enthält.1. Essentially phosphate-free powdered bleaching and washing agent, containing alkali percarbonate, bleach activator, surfactant and builder, characterized in that it contains 3 powdery components, component A being a powder produced by spray drying, containing anionic surfactant, water-soluble and / or insoluble builder and less than 3% by weight of water, component B which contains alkali percarbonate and component C an activator for the percarbonate, with the proviso that it contains 10% by weight to 93% by weight of the component A, 5 wt .-% to 70 wt .-% of component B and 2 wt .-% to 20 wt .-% of component C.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß es 20 Gew.-% bis 85 Gew.-%, insbesondere 40 Gew.-% bis 80 Gew.-% Komponente A, 13 Gew.-% bis 60 Gew.-%, insbesondere 18 Gew.-% bis 50 Gew.-% Komponente B und 2 Gew.-% bis 20 Gew.-%, insbesondere 2 Gew.-% bis 10 Gew.-% Komponen¬ te C enthält.2. Composition according to claim 1, characterized in that it is 20 wt .-% to 85 wt .-%, in particular 40 wt .-% to 80 wt .-% component A, 13 wt .-% to 60 wt .-% , in particular 18% by weight to 50% by weight of component B and 2% by weight to 20% by weight, in particular 2% by weight to 10% by weight of component C.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß Komponente A 2 Gew.-% bis 40 Gew.-%, insbesondere 5 Gew.-% bis 20 Gew.-% anionisches Tensid, 20 Gew.-% bis 90 Gew.-%, insbesondere 40 Gew.-% bis 80 Gew.-% Builder, nicht über 50 Gew.-%, insbesondere 1 Gew.-% bis 30 Gew.-% an¬ organisches Füllsalz, nicht über 10 Gew.- , insbesondere 0,1 Gew.-% bis 2 Gew.-% Komplexbildner und nicht über 10 Gew.-%, insbesondere 2 Gew.-% bis 6 Gew.-% nichtionisches Tensid enthält.3. Composition according to claim 1 or 2, characterized in that component A 2 wt .-% to 40 wt .-%, in particular 5 wt .-% to 20 wt .-% anionic surfactant, 20 wt .-% to 90 wt %, in particular 40% by weight to 80% by weight, builder, not more than 50% by weight, in particular 1% by weight to 30% by weight of inorganic filler salt, not more than 10% by weight, contains in particular 0.1% by weight to 2% by weight of complexing agent and not more than 10% by weight, in particular 2% by weight to 6% by weight, of nonionic surfactant.
4. Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der in Komponente C enthaltene Bleichaktivator eine unter Waschbedin¬ gungen Peressigsäure bildende Verbindung ist.4. Agent according to one of claims 1 to 3, characterized in that the bleach activator contained in component C is a peracetic acid-forming compound under Waschbedin¬ conditions.
5. Mittel nach Anspruch 4, dadurch gekennzeichnet, daß der Bleichaktivator N,N,N' ,N'-Tetraacetylethylendiamin l,5-Diacetyl-2,4-dioxo-hexahydro- 1,3,5-triazin, Tetraacetylglykoluril und/oder Pentaacetylglucose ist.5. Composition according to claim 4, characterized in that the bleach activator N, N, N ', N'-tetraacetylethylenediamine l, 5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine, tetraacetylglycoluril and / or Is pentaacetyl glucose.
6. Bleichmittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es als zusätzliche Komponente nicht über 30 Gew.-%, insbesondere 5 Gew.-% bis 20 Gew.-% eines wasserlöslichen Salzes in Pulverform ent¬ hält, das im Bereich von 1 °C bis 45 °C kein Kristallwasser abgibt und dessen Schmelzpunkt über 45 °C liegt.6. Bleaching agent according to one of claims 1 to 5, characterized in that it as an additional component not more than 30 wt .-%, in particular Contains 5% by weight to 20% by weight of a water-soluble salt in powder form which does not give off water of crystallization in the range from 1 ° C. to 45 ° C. and whose melting point is above 45 ° C.
7. Bleichmittel nach Anspruch 6, dadurch gekennzeichnet, daß das wasser¬ lösliche Salz aus der Gruppe umfassend Natriumchlorid, wasserfreies Natriumcarbonat, Natriumnitrat, Natriu acetat und deren Gemische aus¬ gewählt wird.7. Bleaching agent according to claim 6, characterized in that the water-soluble salt is selected from the group comprising sodium chloride, anhydrous sodium carbonate, sodium nitrate, sodium acetate and mixtures thereof.
8. Bleichmittel nach Anspruch 6 oder 7, dadurch gekennzeichnet, daß das wasserlösliche Salz nicht über 10 Gew.-%, insbesondere 2 Gew.-% bis 10 Gew.-%, bezogen auf das gesamte Mittel, nichtionisches Tensid trägt.8. Bleaching agent according to claim 6 or 7, characterized in that the water-soluble salt does not carry more than 10% by weight, in particular 2% by weight to 10% by weight, based on the total agent, of nonionic surfactant.
9. Bleichmittel nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß es eine Schüttdichte unter 800 Gramm pro Liter, vorzugsweise von 300 bis 800 Gramm pro Liter und insbesondere von 400 bis 700 Gramm pro Liter aufweist. 9. Bleaching agent according to one of claims 1 to 8, characterized in that it has a bulk density below 800 grams per liter, preferably from 300 to 800 grams per liter and in particular from 400 to 700 grams per liter.
PCT/EP1991/001872 1990-10-08 1991-09-30 Percarbonate-containing washing agent WO1992006167A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE59106781T DE59106781D1 (en) 1990-10-08 1991-09-30 PERCARBONATE DETERGENT.
EP91917296A EP0552193B1 (en) 1990-10-08 1991-09-30 Percarbonate-containing washing agent
JP3515475A JPH06501723A (en) 1990-10-08 1991-09-30 Detergents containing percarbonates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4031910.5 1990-10-08
DE4031910A DE4031910A1 (en) 1990-10-08 1990-10-08 PERCARBONATE DETERGENT

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WO1992006167A1 true WO1992006167A1 (en) 1992-04-16

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JP (1) JPH06501723A (en)
AT (1) ATE129521T1 (en)
DE (2) DE4031910A1 (en)
ES (1) ES2079678T3 (en)
WO (1) WO1992006167A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996001887A1 (en) * 1994-07-07 1996-01-25 Henkel Kommanditgesellschaft Auf Aktien Powdered bleaching and washing agent
WO1996008554A1 (en) * 1994-09-16 1996-03-21 Henkel Kommanditgesellschaft Auf Aktien Enzyme-containing washing and bleaching agent in powder form
WO1996022355A1 (en) * 1995-01-17 1996-07-25 Henkel Kommanditgesellschaft Auf Aktien Granular bleaching washing and cleaning agent
US5565422A (en) * 1995-06-23 1996-10-15 The Procter & Gamble Company Process for preparing a free-flowing particulate detergent composition having improved solubility
WO2000077159A1 (en) * 1999-06-16 2000-12-21 Kao Corporation Particles for detergent addition
US7179892B2 (en) 2000-12-06 2007-02-20 Neuralab Limited Humanized antibodies that recognize beta amyloid peptide

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GB9021761D0 (en) * 1990-10-06 1990-11-21 Procter & Gamble Detergent compositions
CA3213769A1 (en) 2021-04-01 2022-10-06 Sterilex, Llc Quat-free powdered disinfectant/sanitizer

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996001887A1 (en) * 1994-07-07 1996-01-25 Henkel Kommanditgesellschaft Auf Aktien Powdered bleaching and washing agent
WO1996008554A1 (en) * 1994-09-16 1996-03-21 Henkel Kommanditgesellschaft Auf Aktien Enzyme-containing washing and bleaching agent in powder form
WO1996022355A1 (en) * 1995-01-17 1996-07-25 Henkel Kommanditgesellschaft Auf Aktien Granular bleaching washing and cleaning agent
US5565422A (en) * 1995-06-23 1996-10-15 The Procter & Gamble Company Process for preparing a free-flowing particulate detergent composition having improved solubility
WO2000077159A1 (en) * 1999-06-16 2000-12-21 Kao Corporation Particles for detergent addition
US7179892B2 (en) 2000-12-06 2007-02-20 Neuralab Limited Humanized antibodies that recognize beta amyloid peptide

Also Published As

Publication number Publication date
EP0552193A1 (en) 1993-07-28
ATE129521T1 (en) 1995-11-15
JPH06501723A (en) 1994-02-24
DE4031910A1 (en) 1992-04-09
ES2079678T3 (en) 1996-01-16
DE59106781D1 (en) 1995-11-30
EP0552193B1 (en) 1995-10-25

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