WO2001012768A1 - Mixed powder or mixed granulate based on glycine-n,n-diacetic acid - Google Patents
Mixed powder or mixed granulate based on glycine-n,n-diacetic acid Download PDFInfo
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- WO2001012768A1 WO2001012768A1 PCT/EP2000/007628 EP0007628W WO0112768A1 WO 2001012768 A1 WO2001012768 A1 WO 2001012768A1 EP 0007628 W EP0007628 W EP 0007628W WO 0112768 A1 WO0112768 A1 WO 0112768A1
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/30—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic using agents to prevent the granules sticking together; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
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- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
Definitions
- the invention relates to a mixed powder or mixed granules based on glycine-N, N-diacetic acid or derivatives thereof.
- Solid or liquid formulations can be selected for the production of detergents, in particular textile detergents or cleaning agents, in particular dish detergents.
- Solid formulations can be present, for example, as powders or granules.
- the preparation of individual powder or granular detergent ingredients or ingredient mixtures can be difficult or impossible depending on the nature of the ingredients.
- the powders or granules must not cake together during the manufacture, mixing and storage of the agents and must not impair the spreadability or flowability of the powder or granules.
- WO 95/29216 relates to detergent powder compositions containing a metal ion chelate complex and an anionic functionalized polymer.
- the detergent powder contains a complex of a chelating agent and a metal ion selected from magnesium, calcium, strontium, zinc and aluminum as well as a polymer which in particular has carboxyl groups.
- the powder is made by spray drying.
- the chelating agents can be selected from a large number of compounds, but no mention is made of glycine-N, N-diacetic acid derivatives.
- the polymers that can be used include polycarboxylates which contain water-soluble salts of homopolymers and copolymers of aliphatic carboxylic acids.
- EP-A-0 618 289 also relates to highly active granular detergent compositions which contain chelates and polymers.
- the composition comprises an anionic surfactant, a chelating agent and a polymer or copolymer.
- the chelating agents can in turn be selected from a large number of compounds. However, glycine-N, N-diacetic acid derivatives are not listed.
- the polymers include, in particular, polycarboxylates such as polyacrylates.
- the object of the present invention is to provide mixed powders or mixed granules containing glycine-N, N-diacetic acid derivatives for use in solid washing and cleaning agents.
- the powders or granules should remain free from debris and flow.
- the object is achieved according to the invention by a mixed powder or mixed granules containing at least 80% by weight of a mixture
- M alkali metal (b) 30 to 95% by weight of at least one polycarboxylate in which up to 40 mol% of the carboxyl groups are neutralized.
- the remaining proportion can be accounted for by other auxiliaries, such as conventional detergent additives or fillers.
- the mixture preferably consists essentially, particularly preferably only of components (a) and (b).
- Glycine-N, N-diacetic acid derivatives which can be used according to the invention are described, for example, in EP-A-0 845 456.
- M denotes an alkali metal, preferably sodium or potassium, in particular sodium.
- R is preferably a -6-alkyl radical, in particular a methyl or ethyl radical.
- Methylglycinediacetic acid (MGDA) is particularly preferably used, preferably as the trisodium salt.
- a polycarboxylate is used as component (b) in which up to 40 mol% of the carboxyl groups are neutralized. It is preferably a homopolymer or copolymer which comprises at least 50% by weight of the monomers
- maleic acid (meth) acrylic acid, itaconic acid, mesaconic acid, fumaric acid, Aconitic acid, citraconic acid and / or methylene malonic acid or their anhydrides is built up.
- Preferred monomers are maleic acid, fumaric acid, acrylic acid and (meth) acrylic acid, in particular maleic acid and acrylic acid.
- Suitable polycarboxylates are described for example in US 3,308,067.
- a polycarboxylate is particularly preferably used which is composed of at least 70% by weight of acrylic acid and maleic acid or their anhydrides.
- a copolymer of acrylic acid and maleic acid is particularly preferred.
- the proportion of acrylic acid is preferably 50 to 80% by weight.
- the molecular weight of the polycarboxylates is preferably 1,500 to 100,000, particularly preferably 2,000 to 80,000, in particular 3,000 to 70,000.
- a derivatized cellulose such as a carboxy-lower alkyl cellulose can also be used as the polycarboxylate.
- carboxymethyl cellulose is particularly preferably used.
- the carboxyl groups are neutralized in the polycarboxylates. This means that the pure acid (0% neutralization) can also be used.
- the neutralization can be carried out with suitable bases such as alkali hydroxides or amines. They can also be present as ammonium salts.
- the proportion of component (a) is 5 to 70% by weight, preferably 10 to 60% by weight.
- Exemplary proportions of component (a) are 30 or 60% by weight.
- component (b) is present in an amount of 30 to 95% by weight, preferably 40 to 90% by weight. Quantities of 40 or 70% by weight are exemplary.
- the mixed powder or mixed granulate according to the invention preferably reacts acidically in aqueous solution.
- An aqueous solution of the mixed powder or mixed granules preferably has a pH of less than 7.
- the mixed powders or mixed granules according to the invention can be prepared by dissolving components (a) and (b) in a solvent and spray-drying the mixture obtained, which can be followed by a granulation step.
- Components (a) and (b) can be dissolved separately, the solutions subsequently being mixed, or a powder mixture of the components can be dissolved in water.
- the mixed powders or mixed granules according to the invention are preferably used for the production of solid washing and cleaning agents, for washing textiles or for cleaning dishes.
- Component (a) can act as a readily biodegradable complexing agent, while component (b) can act as a builder. Both components of the mixed powder or mixed granules thus have an effect in detergents and cleaning agents.
- the mixed powders or mixed granules can be incorporated into powder detergents and cleaning agents without them clumping or baking.
- the invention also relates to a solid detergent comprising a mixed powder or mixed granulate as described above and at least one surfactant.
- Suitable detergent compositions are known and are described, for example, in WO 95/29216 and EP-A-0 618 289.
- the invention further relates to a solid dishwashing detergent which contains a mixed powder or mixed granules as described above and also at least one surfactant.
- the agents are preferably in powder or granule form.
- MGDA in the form of the trisodium salt was used as component (a).
- an acrylic acid / maleic acid copolymer of 70% by weight acrylic acid and 30% by weight maleic acid with a molecular weight of 70,000 was used, which was 40% partially neutralized (sodium salt) (component bl).
- an acrylic acid / maleic acid copolymer with 50% by weight of acrylic acid and 50% by weight of maleic acid in the pure acid form was used (molecular weight 3,000) (component b2).
- Mixture 1 according to the invention was prepared by spray drying an aqueous
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
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Abstract
Description
Mischpulver oder Mischgranulat auf Basis von Glycin-N,N-diessigsäure Mixed powder or mixed granules based on glycine-N, N-diacetic acid
Die Erfindung betrifft ein Mischpulver oder Mischgranulat auf Basis von Glycin- N,N-diessigsäure oder Derivaten davon.The invention relates to a mixed powder or mixed granules based on glycine-N, N-diacetic acid or derivatives thereof.
Zur Herstellung von Waschmitteln, insbesondere Textilwaschmitteln oder Reinigungsmitteln, insbesondere Geschirrreinigungsmitteln können feste oder flüssige Formulierungen gewählt werden. Feste Formulierungen können beispielsweise als Pulver oder Granulate vorliegen. Die Herstellung von einzelnen pulver- oder granulatförmigen Waschmittelbestandteilen oder Bestandteilsgemischen kann je nach Art der Bestandteile schwierig oder unmöglich sein. Die Pulver oder Granulate dürfen bei der Herstellung, beim Mischen und beim Lagern der Mittel nicht zusammenbacken und die Streu- oder Rieselfahigkeit des Pulvers oder Granulats nicht beeinträchtigen.Solid or liquid formulations can be selected for the production of detergents, in particular textile detergents or cleaning agents, in particular dish detergents. Solid formulations can be present, for example, as powders or granules. The preparation of individual powder or granular detergent ingredients or ingredient mixtures can be difficult or impossible depending on the nature of the ingredients. The powders or granules must not cake together during the manufacture, mixing and storage of the agents and must not impair the spreadability or flowability of the powder or granules.
Der Einsatz von Chelatbildnem in Waschmitteln in fester Form ist bekannt. Die WO 95/29216 betrifft Detergenspul verZusammensetzungen, die einen Metallion- Chelat-Komplex und ein anionisches funktionalisiertes Polymer enthalten. Das Detergenspulver enthält einen Komplex aus einem Chelatbildner und einem Metallion, ausgewählt aus Magnesium, Calcium, Strontium, Zink und Aluminium sowie ein Polymer, das insbesondere Carboxylgruppen aufweist. Das Pulver wird durch Sprühtrocknen hergestellt. Die Chelatbildner können dabei aus einer Vielzahl von Verbindungen ausgewählt sein, Glycin-N,N-diessigsäure-Derivate sind jedoch nicht erwähnt. Unter den verwendbaren Polymeren sind Polycarboxylate aufgeführt, die wasserlösliche Salze von Homo- und Copolymeren von aliphatischen Carbonsäuren enthalten. Auch die EP-A-0 618 289 betrifft hochaktive granulatförmige Detergenszusammensetzungen, die Chelate und Polymere enthalten. Die Zusammensetzung weist ein anionisches Tensid, einen Chelatbildner und ein Polymer oder Copolymer auf. Die Chelatbildner können wiederum aus einer Vielzahl von Verbindungen ausgewählt sein. Glycin-N,N-diessigsäure-Derivate sind jedoch nicht aufgeführt. Unter den Polymeren sind insbesondere Polycarboxylate wie Polyacrylate aufgeführt.The use of chelating agents in detergents in solid form is known. WO 95/29216 relates to detergent powder compositions containing a metal ion chelate complex and an anionic functionalized polymer. The detergent powder contains a complex of a chelating agent and a metal ion selected from magnesium, calcium, strontium, zinc and aluminum as well as a polymer which in particular has carboxyl groups. The powder is made by spray drying. The chelating agents can be selected from a large number of compounds, but no mention is made of glycine-N, N-diacetic acid derivatives. The polymers that can be used include polycarboxylates which contain water-soluble salts of homopolymers and copolymers of aliphatic carboxylic acids. EP-A-0 618 289 also relates to highly active granular detergent compositions which contain chelates and polymers. The composition comprises an anionic surfactant, a chelating agent and a polymer or copolymer. The chelating agents can in turn be selected from a large number of compounds. However, glycine-N, N-diacetic acid derivatives are not listed. The polymers include, in particular, polycarboxylates such as polyacrylates.
Die Verwendung von Glycin-N,N-diessigsäure-Derivaten als Komplexbildner für Erdalkali- und Schwermetallionen in Wasch- und Reinigungsmitteln ist in der EP- A-0 845 456 beschrieben. Hier wird insbesondere die Herstellung von kristallinen Feststoffen aus Glycin-N.N-diessigsäure-Derivaten (MGDA-Derivaten) beschrieben. Hierbei wird ein spezielles Kristallisationsverfahren angewendet.The use of glycine-N, N-diacetic acid derivatives as complexing agents for alkaline earth and heavy metal ions in washing and cleaning agents is described in EP-A-0 845 456. Here, in particular, the production of crystalline solids from Glycine-N . N-diacetic acid derivatives (MGDA derivatives) described. A special crystallization process is used here.
Aufgabe der vorliegenden Erfindung ist die Bereitstellung von Glycin-N,N- diessigsäure-Derivate enthaltenden Mischpulvern oder Mischgranulaten für die Verwendung in festen Wasch- und Reinigungsmitteln. Dabei soll insbesondere die Schutt- und Rieselfähigkeit der Pulver oder Granulate erhalten bleiben.The object of the present invention is to provide mixed powders or mixed granules containing glycine-N, N-diacetic acid derivatives for use in solid washing and cleaning agents. In particular, the powders or granules should remain free from debris and flow.
Die Aufgabe wird erfindungsgemäß gelöst durch ein Mischpulver oder Mischgranulat, enthaltend mindestens 80 Gew.-% eines Gemisches ausThe object is achieved according to the invention by a mixed powder or mixed granules containing at least 80% by weight of a mixture
(a) 5 bis 70 Gew.-% mindestens eines Glycin-N.N-diessigsäure- Derivats der allgemeinen Formel (I)(a) 5 to 70% by weight of at least one glycine-N.N-diacetic acid derivative of the general formula (I)
MOOC-CHR-N(CH2COOM)2 (I)MOOC-CHR-N (CH 2 COOM) 2 (I)
mit der Bedeutungwith the meaning
R Ci.n-AlkylR Ci.n-alkyl
M Alkalimetall (b) 30 bis 95 Gew.-% mindestens eines Polycarboxylates, in dem bis zu 40 mol-% der Carboxylgruppen neutralisiert sind.M alkali metal (b) 30 to 95% by weight of at least one polycarboxylate in which up to 40 mol% of the carboxyl groups are neutralized.
Der verbleibende Mengenanteil kann auf weitere Hilfsstoffe entfallen, wie übliche Waschmittelzusatzstoffe oder Füllstoffe. Vorzugsweise besteht die Mischung im wesentlichen, besonders bevorzugt nur aus den Komponenten (a) und (b).The remaining proportion can be accounted for by other auxiliaries, such as conventional detergent additives or fillers. The mixture preferably consists essentially, particularly preferably only of components (a) and (b).
Es wurde erfindungsgemäß gefunden, daß eine Kombination von Alkalimetallsalzen von Glycin-N,N-diessigsäure-Derivaten mit Polycarboxylaten zu Pulvern oder Granulaten fuhrt, die eine geringe Hygroskopizität und ein gutes Lagerverhalten aufweisen und damit vorteilhaft in festen Wasch- und Reinigungsmitteln eingesetzt werden können. Die Mittel sind sehr lagerstabil und auch nach langen Zeiträumen noch schüft- und rieselfahig.It has been found according to the invention that a combination of alkali metal salts of glycine-N, N-diacetic acid derivatives with polycarboxylates leads to powders or granules which have low hygroscopicity and good storage behavior and can therefore be used advantageously in solid washing and cleaning agents. The agents are very stable in storage and can be stored and poured even after long periods of time.
Erfindungsgemäß einsetzbare Glycin-N,N-diessigsäure-Derivate sind beispielsweise in EP-A-0 845 456 beschrieben. In den Verbindungen der allgemeinen Formel (I) bedeutet M ein Alkalimetall, vorzugsweise Natrium oder Kalium, insbesondere Natrium.Glycine-N, N-diacetic acid derivatives which can be used according to the invention are described, for example, in EP-A-0 845 456. In the compounds of the general formula (I), M denotes an alkali metal, preferably sodium or potassium, in particular sodium.
R ist vorzugsweise ein Cι-6-Alkylrest, insbesondere ein Methyl- oder Ethylrest. Speziell bevorzugt wird Methylglycindiessigsäure (MGDA) eingesetzt, vorzugsweise als Trinatriumsalz.R is preferably a -6-alkyl radical, in particular a methyl or ethyl radical. Methylglycinediacetic acid (MGDA) is particularly preferably used, preferably as the trisodium salt.
Die Herstellung derartiger Glycin-N,N-diessigsäure-Derivate ist bekannt, vgl. EP- A-0 845 456 und darin zitierte Literatur.The preparation of such glycine-N, N-diacetic acid derivatives is known, cf. EP-A-0 845 456 and literature cited therein.
Als Komponente (b) wird ein Polycarboxylat eingesetzt, in dem bis zu 40 mol-% der Carboxylgruppen neutralisiert sind. Dabei handelt es sich vorzugsweise um ein Homo- oder Copolymer, das zu mindestens 50 Gew.-% aus den MonomerenA polycarboxylate is used as component (b) in which up to 40 mol% of the carboxyl groups are neutralized. It is preferably a homopolymer or copolymer which comprises at least 50% by weight of the monomers
Maleinsäure, (Meth)acrylsäure, Itaconsäure, Mesaconsäure, Fumarsäure, Aconitsäure, Citraconsäure und/oder Methylenmalonsäure oder deren Anhydriden aufgebaut ist. Bevorzugte Monomere sind dabei Maleinsäure, Fumarsäure, Acrylsäure und (Meth)acrylsäure, insbesondere Maleinsäure und Acrylsäure. Geeignete Polycarboxylate sind beispielsweise in US 3,308,067 beschrieben. Besonders bevorzugt wird ein Polycarboxylat eingesetzt, das zu mindestens 70 Gew.-% aus Acrylsäure und Maleinsäure oder deren Anhydriden aufgebaut ist. Besonders bevorzugt ist ein Copolymer aus Acrylsäure und Maleinsäure. Dabei beträgt der Anteil an Acrylsäure vorzugsweise 50 bis 80 Gew.-%. Das Molekulargewicht der Polycarboxylate beträgt vorzugsweise 1.500 bis 100.000, besonders bevorzugt 2.000 bis 80.000, insbesondere 3.000 bis 70.000.Maleic acid, (meth) acrylic acid, itaconic acid, mesaconic acid, fumaric acid, Aconitic acid, citraconic acid and / or methylene malonic acid or their anhydrides is built up. Preferred monomers are maleic acid, fumaric acid, acrylic acid and (meth) acrylic acid, in particular maleic acid and acrylic acid. Suitable polycarboxylates are described for example in US 3,308,067. A polycarboxylate is particularly preferably used which is composed of at least 70% by weight of acrylic acid and maleic acid or their anhydrides. A copolymer of acrylic acid and maleic acid is particularly preferred. The proportion of acrylic acid is preferably 50 to 80% by weight. The molecular weight of the polycarboxylates is preferably 1,500 to 100,000, particularly preferably 2,000 to 80,000, in particular 3,000 to 70,000.
Als Polycarboxylat kann zudem auch eine derivatisierte Cellulose wie eine carboxy-niedere Alkyl-Cellulose eingesetzt werden. Besonders bevorzugt wird in diesem Fall Carboxymethylcellulose eingesetzt.A derivatized cellulose such as a carboxy-lower alkyl cellulose can also be used as the polycarboxylate. In this case, carboxymethyl cellulose is particularly preferably used.
In den Polycarboxylaten sind bis zu 40 mol-% der Carboxylgruppen neutralisiert. Damit kann auch die reine Säure (0 % Neutralisierung) eingesetzt werden. Die Neutralisierung kann mit geeigneten Basen wie Alkalihydroxiden oder Aminen erfolgen. Sie können auch als Ammoniumsalze vorliegen.Up to 40 mol% of the carboxyl groups are neutralized in the polycarboxylates. This means that the pure acid (0% neutralization) can also be used. The neutralization can be carried out with suitable bases such as alkali hydroxides or amines. They can also be present as ammonium salts.
Der Anteil der Komponente (a) beträgt 5 bis 70 Gew.-%, vorzugsweise 10 bis 60 Gew.-%. Beispielhafte Anteile der Komponente (a) sind 30 oder 60 Gew.-%. Entsprechend liegt die Komponente (b) in einer Menge von 30 bis 95 Gew.-%, vorzugsweise 40 bis 90 Gew.-% vor. Beispielhaft sind Mengen von 40 oder 70 Gew.-%.The proportion of component (a) is 5 to 70% by weight, preferably 10 to 60% by weight. Exemplary proportions of component (a) are 30 or 60% by weight. Accordingly, component (b) is present in an amount of 30 to 95% by weight, preferably 40 to 90% by weight. Quantities of 40 or 70% by weight are exemplary.
Das erfindungsgemäße Mischpulver oder Mischgranulat reagiert in wässriger Lösung vorzugsweise sauer. Vorzugsweise weist eine wässrige Lösung des Mischpulvers oder Mischgranulats einen pH- Wert kleiner 7 auf. Hierdurch kann die Hygroskopizität des Mischpulvers oder Mischgranulats auf einen sehr kleinen Wert verringert werden. Die erfindungsgemäßen Mischpulver oder Mischgranulate können hergestellt werden durch Lösen der Komponenten (a) und (b) in einem Lösungsmittel und Sprühtrocknen des erhaltenen Gemisches, wobei sich ein Granulierungsschritt anschließen kann. Dabei können die Komponenten (a) und (b) getrennt gelöst werden, wobei die Lösungen nachfolgend vermischt werden, oder ein Pulvergemisch der Komponenten kann in Wasser gelöst werden.The mixed powder or mixed granulate according to the invention preferably reacts acidically in aqueous solution. An aqueous solution of the mixed powder or mixed granules preferably has a pH of less than 7. As a result, the hygroscopicity of the mixed powder or mixed granulate can be reduced to a very small value. The mixed powders or mixed granules according to the invention can be prepared by dissolving components (a) and (b) in a solvent and spray-drying the mixture obtained, which can be followed by a granulation step. Components (a) and (b) can be dissolved separately, the solutions subsequently being mixed, or a powder mixture of the components can be dissolved in water.
Die erfindungsgemäßen Mischpulver oder Mischgranulate werden vorzugsweise zur Herstellung von festen Wasch- und Reinigungsmitteln, bei der Wäsche von Textilien oder bei der Reinigung von Geschirr verwendet. Die Komponente (a) kann dabei als biologisch gut abbaubarer Komplexbildner wirken, während die Komponente (b) als Builder wirken kann. Damit entfalten beide Komponenten der Mischpulver oder Mischgranulate eine Wirkung in Wasch- und Reinigungsmitteln.The mixed powders or mixed granules according to the invention are preferably used for the production of solid washing and cleaning agents, for washing textiles or for cleaning dishes. Component (a) can act as a readily biodegradable complexing agent, while component (b) can act as a builder. Both components of the mixed powder or mixed granules thus have an effect in detergents and cleaning agents.
Die Mischpulver oder Mischgranulate können in pulverfbrmige Wasch- und Reinigungsmittel eingearbeitet werden, ohne daß diese verklumpen oder verbacken.The mixed powders or mixed granules can be incorporated into powder detergents and cleaning agents without them clumping or baking.
Die Erfindung betrifft auch ein festes Waschmittel, enthaltend ein wie vorstehend beschriebenes Mischpulver oder Mischgranulat und mindestens ein Tensid. Geeignete Waschmittelzusammensetzungen sind bekannt und beispielsweise in WO 95/29216 und EP-A-0 618 289 beschrieben.The invention also relates to a solid detergent comprising a mixed powder or mixed granulate as described above and at least one surfactant. Suitable detergent compositions are known and are described, for example, in WO 95/29216 and EP-A-0 618 289.
Die Erfindung betrifft ferner ein festes Geschirrreinigungsmittel, das ein Mischpulver oder Mischgranulat, wie es vorstehend beschrieben ist, enthält und zudem mindestens ein Tensid. Die Mittel liegen dabei vorzugsweise in Pulveroder Granulatform vor.The invention further relates to a solid dishwashing detergent which contains a mixed powder or mixed granules as described above and also at least one surfactant. The agents are preferably in powder or granule form.
Die Erfindung wird nachstehend anhand von Beispielen näher erläutert. BeispieleThe invention is explained in more detail below with the aid of examples. Examples
Als Komponente (a) wurde MGDA in Form des Trinatriumsalzes eingesetzt.MGDA in the form of the trisodium salt was used as component (a).
Als Komponente (b) wurde zum einen ein Acrylsäure/Maleinsäure-Copolymer aus 70 Gew.-% Acrylsäure und 30 Gew.-% Maleinsäure mit einem Molgewicht von 70.000 eingesetzt, das zu 40 % teilneutralisiert war (Natriumsalz) (Komponente bl). Zum anderen wurde ein Acrylsäure/Maleinsäure-Copolymer mit 50 Gew.-% Acrylsäureanteil und 50 Gew.-% Maleinsäureanteil in der reinen Säureform eingesetzt (Molekulargewicht 3.000) (Komponente b2).As component (b), an acrylic acid / maleic acid copolymer of 70% by weight acrylic acid and 30% by weight maleic acid with a molecular weight of 70,000 was used, which was 40% partially neutralized (sodium salt) (component bl). On the other hand, an acrylic acid / maleic acid copolymer with 50% by weight of acrylic acid and 50% by weight of maleic acid in the pure acid form was used (molecular weight 3,000) (component b2).
Die erfindungsgemäße Mischung 1 wurde durch Sprühtrocknen einer wässrigenMixture 1 according to the invention was prepared by spray drying an aqueous
Lösung eines Gemisches aus 70 Gew.-% der Komponente bl und 30 Gew.-% MGDA erhalten. Entsprechend wurde Mischung 2 durch Sprühtrocknen einer wässrigen Lösung eines Gemisches aus 40 Gew.-% Komponente b2 und 60Solution of a mixture of 70 wt .-% of component bl and 30 wt .-% MGDA obtained. Mixture 2 was correspondingly prepared by spray drying an aqueous solution of a mixture of 40% by weight of components b2 and 60
Gew.-% MGDA erhalten.Wt .-% MGDA obtained.
Zur Bestimmung der Hygroskopizität und des Lagerverhaltens wurde die Gewichtszunahme bei 22°C und 68% relativer Feuchte für einen längeren Zeitraum bestimmt. Dabei wurde untersucht, ob das Produkt rieselfahig (R), fest und nicht rieselfahig (F) oder klebrig und nicht rieselfahig (K) war. Die Ergebnisse für die einzelnen Komponenten und für die erfindungsgemäßen Mischungen sind in der nachstehenden Tabelle zusammengefaßt. To determine the hygroscopicity and storage behavior, the weight gain at 22 ° C and 68% relative humidity was determined for a longer period. It was examined whether the product was free-flowing (R), solid and not free-flowing (F) or sticky and not free-flowing (K). The results for the individual components and for the mixtures according to the invention are summarized in the table below.
Tabelletable
Aus den Ergebnissen der vorstehenden Tabelle geht hervor, daß insbesondere die in saurer Form vorliegenden erfindungsgemäßen Mischungen mit dem angegebenen Anteil an Polycarboxylaten eine sehr niedrige Hygroskopizität aufweisen und auch nach längerer Lagerungsdauer rieselfahig bleiben. The results of the above table show that in particular the mixtures according to the invention in acidic form with the stated proportion of polycarboxylates have a very low hygroscopicity and remain free-flowing even after prolonged storage.
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1999137345 DE19937345A1 (en) | 1999-08-11 | 1999-08-11 | Mixed powder or mixed granules based on glycine-N, N-diacetic acid |
| DE19937345.0 | 1999-08-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2001012768A1 true WO2001012768A1 (en) | 2001-02-22 |
Family
ID=7917578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2000/007628 Ceased WO2001012768A1 (en) | 1999-08-11 | 2000-08-04 | Mixed powder or mixed granulate based on glycine-n,n-diacetic acid |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE19937345A1 (en) |
| WO (1) | WO2001012768A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007532753A (en) * | 2004-04-15 | 2007-11-15 | イーコラブ インコーポレイティド | Binding agent for solidified matrix |
| JP2008505236A (en) * | 2004-07-02 | 2008-02-21 | ビーエーエスエフ アクチェンゲゼルシャフト | Mixed powder or mixed granule based on MGDA |
| WO2009103822A1 (en) * | 2008-04-01 | 2009-08-27 | Unilever Nv | Preparation of free flowing granules of methyglycine diacetic acid |
| CN102906062A (en) * | 2010-05-21 | 2013-01-30 | 陶氏环球技术有限责任公司 | Aminocarboxylate powders with improved purity and flow ability properties |
| KR101520121B1 (en) * | 2007-07-03 | 2015-05-18 | 바스프 에스이 | Process for producing a free-flowing and storage-stable solid comprising essentially alpha-alanine-n,n-diacetic acid and/or one or more derivatives of alpha-alanine-n,n-diacetic acid |
| US9096820B2 (en) | 2009-12-24 | 2015-08-04 | Akzo Nobel Chemicals International B.V. | Coated particles of a glumatic acid N,N-diacetate chelating agent |
| EP2520641B1 (en) * | 2005-06-30 | 2019-03-13 | The Procter & Gamble Company | Low phosphate automatic dishwashing detergent composition |
| CN111788293A (en) * | 2018-02-23 | 2020-10-16 | 荷兰联合利华有限公司 | Solid detergent composition comprising an aminopolycarboxylate and an organic acid |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2415695A (en) | 2004-07-02 | 2006-01-04 | Reckitt Benckiser Nv | Detergent composition comprising a chelating agent |
| US20120004147A1 (en) * | 2008-12-29 | 2012-01-05 | Akzo Nobel N.V. | Coated particles of a chelating agent |
| DE102009060814A1 (en) * | 2009-12-30 | 2011-07-07 | inprotec AG, 79423 | A process for producing a solid having a sufficiently low hygroscopicity containing glutamic acid N, N-diacetic acid (GLDA) or a derivative thereof |
| EP2380961B1 (en) * | 2010-04-23 | 2018-05-23 | The Procter and Gamble Company | Detergent composition |
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| US4698174A (en) * | 1985-02-13 | 1987-10-06 | Basf Aktiengesellschaft | Additives for detergents and cleaning agents |
| WO1995029216A1 (en) * | 1994-04-20 | 1995-11-02 | The Procter & Gamble Company | Detergent powder compositions comprising metal ion-chelant complex and anionic functional polymer |
| US5719111A (en) * | 1995-02-17 | 1998-02-17 | Lever Brothers Company, Division Of Conopco, Inc. | Process for preparing a solid detergent block |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007532753A (en) * | 2004-04-15 | 2007-11-15 | イーコラブ インコーポレイティド | Binding agent for solidified matrix |
| JP2008505236A (en) * | 2004-07-02 | 2008-02-21 | ビーエーエスエフ アクチェンゲゼルシャフト | Mixed powder or mixed granule based on MGDA |
| AU2005259456B2 (en) * | 2004-07-02 | 2010-10-28 | Basf Aktiengesellschaft | MGDA-based powder mixture or granulate mixture |
| EP2520641B1 (en) * | 2005-06-30 | 2019-03-13 | The Procter & Gamble Company | Low phosphate automatic dishwashing detergent composition |
| KR101520121B1 (en) * | 2007-07-03 | 2015-05-18 | 바스프 에스이 | Process for producing a free-flowing and storage-stable solid comprising essentially alpha-alanine-n,n-diacetic acid and/or one or more derivatives of alpha-alanine-n,n-diacetic acid |
| US8183410B2 (en) | 2008-04-01 | 2012-05-22 | Conopco, Inc. | Preparation of free flowing granules of methylglycine diacetic acid |
| EP3061744A1 (en) * | 2008-04-01 | 2016-08-31 | Unilever N.V. | Preparation of free flowing granules of methylglycine diacetic acid |
| EA031547B1 (en) * | 2008-04-01 | 2019-01-31 | Юнилевер Н.В. | Preparation of free flowing granules of methyglycine diacetic acid salts |
| WO2009103822A1 (en) * | 2008-04-01 | 2009-08-27 | Unilever Nv | Preparation of free flowing granules of methyglycine diacetic acid |
| US9096820B2 (en) | 2009-12-24 | 2015-08-04 | Akzo Nobel Chemicals International B.V. | Coated particles of a glumatic acid N,N-diacetate chelating agent |
| CN102906062A (en) * | 2010-05-21 | 2013-01-30 | 陶氏环球技术有限责任公司 | Aminocarboxylate powders with improved purity and flow ability properties |
| CN111788293A (en) * | 2018-02-23 | 2020-10-16 | 荷兰联合利华有限公司 | Solid detergent composition comprising an aminopolycarboxylate and an organic acid |
| EP3755779B1 (en) | 2018-02-23 | 2022-03-30 | Unilever Global IP Limited | Solid compositions comprising aminopolycarboxylate |
| US12134749B2 (en) | 2018-02-23 | 2024-11-05 | Conopco Inc. | Shaped detergent product composition comprising aminopolycarboxylate |
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