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EP1971675B1 - Mixed powder or mixed granule based on glutamic acid-n,n-diacetic acid and salts thereof - Google Patents

Mixed powder or mixed granule based on glutamic acid-n,n-diacetic acid and salts thereof Download PDF

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Publication number
EP1971675B1
EP1971675B1 EP06841537A EP06841537A EP1971675B1 EP 1971675 B1 EP1971675 B1 EP 1971675B1 EP 06841537 A EP06841537 A EP 06841537A EP 06841537 A EP06841537 A EP 06841537A EP 1971675 B1 EP1971675 B1 EP 1971675B1
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EP
European Patent Office
Prior art keywords
mixed
powder
weight
component
mixture
Prior art date
Legal status (The legal status 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 status listed.)
Not-in-force
Application number
EP06841537A
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German (de)
French (fr)
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EP1971675A1 (en
Inventor
Tanja Seebeck
Lars Kissau
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BASF SE
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BASF SE
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Publication of EP1971675A1 publication Critical patent/EP1971675A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the invention relates to a mixed powder or mixed granules based on glutamic acid-N, N-diacetic acid or their salts.
  • solid or liquid formulations can be selected.
  • Solid formulations may be present, for example, as powders or granules.
  • the preparation of individual powder or granular detergent ingredients or ingredient mixtures may be difficult or impossible depending on the nature of the ingredients.
  • the powder or granules must not cake together during preparation, mixing and storage of the means and should not affect the spreading or flowability of the powder or granules.
  • the 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 having in particular carboxyl groups.
  • the powder is prepared by spray drying.
  • the chelating agents may be selected from a variety of compounds, glutamic acid-N, N-diacetic acid and their salts are not mentioned.
  • polycarboxylates containing water-soluble salts of homo- and copolymers of aliphatic carboxylic acids.
  • the EP-A-0 618 289 relates to highly active granular detergent compositions containing chelates and polymers.
  • the composition comprises an anionic surfactant, a chelating agent and a polymer or copolymer.
  • the chelating agents may be selected from a variety of compounds. However, glutamic acid-N, N-diacetic acid and its salts are not listed.
  • polymers in particular polycarboxylates such as polyacrylates are listed.
  • the object of the present invention is to provide mixed powders or mixed granules containing glutamic acid N, N-diacetic acid or their salts for use in solid detergents and cleaners.
  • the bulk and flowability of the powder or granules should be preserved.
  • the remaining amount can be accounted for by other auxiliaries, such as conventional detergent additives or fillers.
  • the mixture preferably consists essentially, more preferably only of components (a) and (b).
  • the mixture contains as component (b) 5 to 95 wt .-% of at least one polyethylene glycol or at least one nonionic surfactant or a mixture thereof.
  • PVP polyvinylpyrrolidones
  • the funds are very stable on storage and even after long periods still pourable and pourable.
  • Suitable glutamic acid N, N-diacetic acid and its salts are accordingly compounds of the general formula (I) in the M is hydrogen, ammonium or alkali metal.
  • M is hydrogen (H), ammonium (NH 4 ) or an alkali metal (eg Li, Na.K,), preferably sodium or potassium, more preferably sodium.
  • Component (b) used is at least one polyethylene glycol or at least one nonionic surfactant or a mixture thereof or a polymer selected from the group consisting of polyvinyl alcohols, polyvinylpyrrolidones (PVP), polyalkylene glycols and derivatives thereof.
  • PVP polyvinylpyrrolidones
  • As component (b) is preferably used a polyethylene glycol, more preferably having an average molecular weight (weight average molecular weight) of 500 to 30,000 g / mol.
  • the polyethylene glycol used as component (b) has OH end groups and / or C 1-6 -alkyl end groups.
  • a polyethylene glycol which has OH and / or methyl end groups is particularly preferred.
  • the polyethylene glycol used in the mixture according to the invention has a molecular weight (weight average molecular weight) of 1000 to 5000 g / mol, most preferably from 1200 to 2000 g / mol.
  • nonionic surfactants can be used as component (b). These are preferably selected from the group consisting of alkoxylated, primary alcohols, alkoxylated fatty alcohols, alkyl glycosides, alkoxylated fatty acid alkyl esters, amine oxides and polyhydroxy fatty acid amides.
  • nonionic surfactants are preferably alkoxylated, preferably ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in which the alcohol radical may linear or preferably methyl-branched in the 2-position or may contain linear and branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols containing 3 EO, 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-14 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means that may be a whole or fractional number for a particular product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution ("narrow range ethoxylates", NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohols with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.
  • block copolymers with EO-PO block units, or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) can be used, in which R is a primary straight-chain or methyl-branched especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G the symbol is that which represents a glycose unit having 5 or 6 C atoms, preferably glycose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
  • Nonionic surfactants of the amine oxide type for example N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (III) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 C atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 C atoms
  • R 3 is H, a linear, branched or a cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 C atoms, where C 1-4 -alkyl or phenyl radicals are preferred
  • (Z) is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups , or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this group.
  • (Z) is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants are preferably used which have a melting point above room temperature. Accordingly, preferred blends are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably from 25 to 100 ° C, and most preferably from 30 to 50 ° C , contain.
  • Suitable nonionic surfactants which have melting and softening points in the temperature range mentioned are, for example, low-foam nonionic surfactants which may be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have a waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such nonionic (PO / EO / PO) surfactants are also characterized by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant resulting from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 mol, ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred nonionic surfactant which is solid at room temperature is selected from a straight-chain fatty alcohol having 16 to 20 C atoms (C 16-20 -alcohol), preferably a C 18 -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 moles of ethylene oxide per mole of alcohol.
  • C 16-20 -alcohol a straight-chain fatty alcohol having 16 to 20 C atoms
  • C 18 -alcohol preferably a C 18 -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 moles of ethylene oxide per mole of alcohol.
  • the so-called “narrow range ethoxylates" are particularly preferred.
  • mixtures according to the invention contain ethoxylated (s); nonionic surfactant (s) consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles Ethylene oxide per mole of alcohol was won (n).
  • ethoxylated s
  • nonionic surfactant s
  • the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes more than 30 wt .-%, more preferably more than 50 wt .-% and in particular more than 70 wt .-% of the total molecular weight of such nonionic surfactants.
  • Preferred rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of nonionic surfactant.
  • Nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • the mixture according to the invention contains as another preferred nonionic surfactant a compound of the formula (IV) R 4 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 5 (IV) in which R 4 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 C atoms or mixtures thereof, R 5 denotes a linear or branched hydrocarbon radical having 2 to 26 C atoms or mixtures thereof, and x for values of 0.5 to 1.5 and y stands for a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula (V) R 6 O [CH 2 CH (R 8 ) O] z [CH 2 ] k CH (OH) [CH 2 ] j OR 7 (V) in which R 6 and R 7 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 C atoms, R 8 is hydrogen or a methyl, ethyl, n-propyl, iso-propyl, n is -butyl, 2-butyl or 2-methyl-2-butyl, z is from 1 to 30, k and j are from 1 to 12, preferably from 1 to 5.
  • each R 8 in formula (V) may be different.
  • R 6 and R 7 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 8 hydrogen, methyl or ethyl are particularly preferred.
  • Particularly preferred values for z are in the range from 1 to 20, in particular from 6 to 15.
  • each R 8 in formula (V) may be different if z ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for z has been chosen here by way of example and may well be greater, with the variation range increasing with increasing z value and including, for example, a large number of EO groups combined with a small number of PO groups or vice versa.
  • R 6 , R 7 and R 8 are as defined in formula (V) and z is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 6 and R 7 have 9 to 14 C atoms, R 8 is hydrogen and z assumes values of 6 to 15.
  • mixtures according to the invention which contain poly (oxyalkylated) compounds of the formula (V) which end-capped as nonionic surfactants, in which R 6 and R 7 are linear or branched, saturated or unsaturated, aliphatic hydrocarbon radicals having 1 to 30 C atoms, R 8 is hydrogen or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, z is values between 1 and 30, k and j are values from 1 to 12, preferably from 1 to 5, wherein surfactants of the formula (VI) in which z is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • R 6 and R 7 are linear or branched, saturated or unsaturated, aliphatic hydrocarbon radicals having 1 to 30 C atoms
  • R 8 is hydrogen or a methyl, ethyl, n-propyl, iso-propyl,
  • component (b) to nonionic surfactants which are obtainable under the trade name Pluronic® from BASF AG.
  • the proportion of component (a) is 5 to 95 wt .-%, preferably 40 to 60 wt .-%.
  • An exemplary proportion of component (a) is 50% by weight.
  • component (b) is present in an amount of 5 to 95% by weight, preferably 40 to 60% by weight.
  • An example is an amount of 50 wt .-%.
  • the mixed powders or mixed granules according to the invention can be prepared by mixing both components as a powder and then heating the mixture, in particular to a temperature above the melting or softening point of component (b). In this case, component (b) melts and intimately mixes with component (a). In the subsequent cooling and shaping process, the powder properties such as particle size and bulk density are adjusted.
  • the present invention also relates to a process for producing the mixed powders or mixed granules according to the invention by mixing the components (a) and (b) as a powder, heating the mixture and adjusting the powder properties in the subsequent cooling and shaping process.
  • component (a) can also be stirred into the melt of component (b).
  • the subsequent solidification and shaping takes place in accordance with the known processes of melt fabrication, for example by prilling or on cooling belts with, if necessary, downstream steps for adjusting the powder properties, such as grinding and sieving.
  • the mixed powders or mixed granules according to the invention can also be prepared by dissolving components (a) and (b) in a solvent and spray-drying the resulting mixture, wherein a granulation step can follow.
  • the components (a) and (b) can be dissolved separately, wherein the solutions are subsequently mixed, or a powder mixture of the components can be dissolved in water.
  • the solvent all of them can be used; which are able to dissolve components (a) and (b), preference is given to using, for example, alcohols and / or water, more preferably water.
  • the present invention thus also relates to a process for the preparation of the mixed powders or mixed granules according to the invention by dissolving components (a) and (b) in a solvent and spray-drying the resulting mixture, wherein a granulation step and / or a melt granulation step (see above) can follow.
  • the present invention also relates to the use of the mixed powders or mixed granules according to the invention for the production of solid detergents and cleaners, in the washing of textiles or in the cleaning of dishes. Both components unfold as mixed powder or mixed granules an effect in detergents and cleaning agents, for example as a dishwashing detergent for dishwashers.
  • the mixed powders or mixed granules can be incorporated into pulverulent detergents and cleaners without these clumping or caking.
  • the invention also relates to a solid detergent containing a mixed powder or mixed granules as described above and optionally at least one further surfactant.
  • Suitable detergent compositions are known and example, in WO 95/29216 and EP-A-0 618 289 described.
  • the invention further relates to a solid dishwashing detergent containing a mixed powder or mixed granules, as described above, and also optionally at least one (further) surfactant.
  • the agents are preferably present in powder or granular form.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

What is described is a mixed powder or mixed granule comprising at least 80% by weight of a mixture of (a) from 5 to 95% by weight of at least one glutamic acid-N,N-diacetic acid derivative of the general formula (I) MOOC-(CH2)2C(COOM)-N(CH2COOM)2 (I) where M is hydrogen, ammonium, alkali metal, (b) from 5 to 95% by weight of at least one polyethylene glycol or of at least one nonionic surfactant or of a mixture thereof or of a polymer selected from the group consisting of polyvinyl alcohols, polyvinylpyrrolidones (PVPs), polyalkylene glycols and derivatives thereof, processes for producing these mixed powders or mixed granules, the use of these mixed powders or mixed granules, and also a solid washing composition and a solid dishwasher detergent comprising the inventive mixed powder or mixed granule.

Description

Die Erfindung betrifft ein Mischpulver oder Mischgranulat auf Basis von Glutaminsäure-N,N-diessigsäure oder ihren Salzen.The invention relates to a mixed powder or mixed granules based on glutamic acid-N, N-diacetic acid or their salts.

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 Rieselfähigkeit des Pulvers oder Granulats nicht beeinträchtigen.For the preparation of detergents, in particular laundry detergents, or cleaning agents, in particular dishwashing detergents, solid or liquid formulations can be selected. Solid formulations may be present, for example, as powders or granules. The preparation of individual powder or granular detergent ingredients or ingredient mixtures may be difficult or impossible depending on the nature of the ingredients. The powder or granules must not cake together during preparation, mixing and storage of the means and should not affect the spreading or flowability of the powder or granules.

Der Einsatz von Chelatbildnern in Waschmitteln in fester Form ist bekannt. Die WO 95/29216 betrifft Detergenspulverzusammensetzungen, 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, Glutaminsäure-N,N-diessigsäure und ihre Salze sind jedoch nicht erwähnt. Unter den verwendbaren Polymeren sind Polycarboxylate aufgeführt, die wasserlösliche Salze von Homo- und Copolymeren von aliphatischen Carbonsäuren enthalten.The use of chelating agents in detergents in solid form is known. The 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 having in particular carboxyl groups. The powder is prepared by spray drying. The chelating agents may be selected from a variety of compounds, glutamic acid-N, N-diacetic acid and their salts are not mentioned. Among the useful polymers are listed polycarboxylates containing water-soluble salts of homo- and copolymers of aliphatic carboxylic acids.

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. Glutaminsäure-N,N-diessigsäure und ihre Salze sind jedoch nicht aufgeführt. Unter den Polymeren sind insbesondere Polycarboxylate wie Polyacrylate aufgeführt.Also the EP-A-0 618 289 relates to highly active granular detergent compositions containing chelates and polymers. The composition comprises an anionic surfactant, a chelating agent and a polymer or copolymer. Again, the chelating agents may be selected from a variety of compounds. However, glutamic acid-N, N-diacetic acid and its salts are not listed. Among the polymers, in particular polycarboxylates such as polyacrylates are listed.

Aufgabe der vorliegenden Erfindung ist die Bereitstellung von Glutaminsäure-N,N-di-essigsäure oder ihre Salze enthaltenden Mischpulvern oder Mischgranulaten für die Verwendung in festen Wasch- und Reinigungsmitteln. Dabei soll insbesondere die Schütt- und Rieselfähigkeit der Pulver oder Granulate erhalten bleiben.The object of the present invention is to provide mixed powders or mixed granules containing glutamic acid N, N-diacetic acid or their salts for use in solid detergents and cleaners. In particular, the bulk and flowability of the powder or granules should be preserved.

Die Aufgabe wird erfindungsgemäß gelöst durch ein Mischpulver oder Mischgranulat, enthaltend mindestens 80 Gew.-% eines Gemisches aus

  1. (a) 5 bis 95 Gew.-% Glutaminsäure-N,N-diessigsäure und/oder ein oder mehrere ihrer Salze der allgemeinen Formel (I)

            MOOC-(CH2)2-CH(COOM)-N(CH2COOM)2     (I)

    mit der Bedeutung
    M H, NH4, Alkalimetall
  2. (b) 5 bis 95 Gew.-% mindestens eines Polyethylenglykols oder mindestens eines nichtionischen Tensids oder einer Mischung davon oder eines Polymers ausgewählt aus der Gruppe bestehend aus Polyvinylalkoholen, Polyvinylpyrrolidonen (PVP), Polyalkylenglykolen und Derivaten davon.
The object is achieved by a mixed powder or mixed granules containing at least 80 wt .-% of a mixture of
  1. (a) 5 to 95% by weight of glutamic acid N, N-diacetic acid and / or one or more of its salts of general formula (I)

    MOOC- (CH 2 ) 2 -CH (COOM) -N (CH 2 COOM) 2 (I)

    with the meaning
    MH, NH 4 , alkali metal
  2. (B) 5 to 95 wt .-% of at least one polyethylene glycol or at least one nonionic surfactant or a mixture thereof or a polymer selected from the group consisting of polyvinyl alcohols, polyvinylpyrrolidones (PVP), polyalkylene glycols and derivatives thereof.

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 amount can be accounted for by other auxiliaries, such as conventional detergent additives or fillers. The mixture preferably consists essentially, more preferably only of components (a) and (b).

In einer Ausführungsform enthält das Gemisch als Komponente (b) 5 bis 95 Gew.-% mindestens eines Polyethylenglykols oder mindestens eines nichtionischen Tensids oder einer Mischung davon.In one embodiment, the mixture contains as component (b) 5 to 95 wt .-% of at least one polyethylene glycol or at least one nonionic surfactant or a mixture thereof.

Es wurde erfindungsgemäß gefunden, dass eine Kombination von Alkalimetallsalzen von Glutaminsäure-N,N-diessigsäure mit mindestens einem Polyethylenglykol oder mindestens einem nichtionischen Tensid oder einer Mischung davon oder einem Polymer ausgewählt aus der Gruppe bestehend aus Polyvinylalkoholen, Polyvinylpyrrolidonen (PVP), Polyalkylenglykolen und Derivaten davon zu Pulvern oder Granulaten führt, 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 schütt- und rieselfähig.It has been found according to the invention that a combination of alkali metal salts of glutamic acid-N, N-diacetic acid with at least one polyethylene glycol or at least one nonionic surfactant or a mixture thereof or a polymer selected from the group consisting of polyvinyl alcohols, polyvinylpyrrolidones (PVP), polyalkylene glycols and derivatives resulting in powders or granules, which have a low hygroscopicity and a good storage behavior and thus can be used advantageously in solid detergents and cleaners. The funds are very stable on storage and even after long periods still pourable and pourable.

Geeignete Glutaminsäure-N,N-diessigsäure und ihre Salze sind demnach Verbindungen der allgemeinen Formel (I)

Figure imgb0001
in der
M Wasserstoff, Ammonium oder Alkalimetall bedeuten.Suitable glutamic acid N, N-diacetic acid and its salts are accordingly compounds of the general formula (I)
Figure imgb0001
 in the
M is hydrogen, ammonium or alkali metal.

In den Verbindungen der allgemeinen Formel (I) bedeutet M Wasserstoff (H), Ammonium (NH4) oder ein Alkalimetall (z. B. Li, Na. K,), bevorzugt Natrium oder Kalium, besonders bevorzugt Natrium.In the compounds of the general formula (I), M is hydrogen (H), ammonium (NH 4 ) or an alkali metal (eg Li, Na.K,), preferably sodium or potassium, more preferably sodium.

Als Komponente (b) wird mindestens ein Polyethylenglykol oder mindestens ein nichtionisches Tensid oder eine Mischung davon oder ein Polymer ausgewählt aus der Gruppe bestehend aus Polyvinylalkoholen, Polyvinylpyrrolidonen (PVP), Polyalkylenglykolen und Derivaten davon eingesetzt.Component (b) used is at least one polyethylene glycol or at least one nonionic surfactant or a mixture thereof or a polymer selected from the group consisting of polyvinyl alcohols, polyvinylpyrrolidones (PVP), polyalkylene glycols and derivatives thereof.

Als Komponente (b) wird bevorzugt ein Polyethylenglykol, besonders bevorzugt mit einem mittleren Molekulargewicht (Gewichtsmittel des Molekulargewichts) von 500 bis 30000 g/mol eingesetzt.As component (b) is preferably used a polyethylene glycol, more preferably having an average molecular weight (weight average molecular weight) of 500 to 30,000 g / mol.

In einer bevorzugten Ausführungsform weist das als Komponente (b) eingesetzte Polyethylenglykol OH-Endgruppen und/oder C1-6-Alkyl-Endgruppen auf. Besonders bevorzugt wird in die erfindungsgemäße Mischung als Komponente (b) ein Polyethylenglykol eingesetzt, welches OH- und/oder Methylendgruppen aufweist.In a preferred embodiment, the polyethylene glycol used as component (b) has OH end groups and / or C 1-6 -alkyl end groups. In the mixture according to the invention it is particularly preferred to use as component (b) a polyethylene glycol which has OH and / or methyl end groups.

Bevorzugt weist das in der erfindungsgemäßen Mischung eingesetzte Polyethylenglykol ein Molekulargewicht (Gewichtsmittel des Molekulargewichts) von 1000 bis 5000 g/mol, ganz besonders bevorzugt von 1200 bis 2000 g/mol auf.Preferably, the polyethylene glycol used in the mixture according to the invention has a molecular weight (weight average molecular weight) of 1000 to 5000 g / mol, most preferably from 1200 to 2000 g / mol.

Als geeignete Verbindungen können als Komponente (b) nichtionische Tenside eingesetzt werden. Diese sind bevorzugt ausgewählt aus der Gruppe bestehend aus alkoxylierten, primären Alkoholen, alkoxylierten Fettalkoholen, Alkylglykosiden, alkoxylierten Fettsäurealkylestern, Aminoxiden und Polyhydroxyfettsäureamiden.As suitable compounds, nonionic surfactants can be used as component (b). These are preferably selected from the group consisting of alkoxylated, primary alcohols, alkoxylated fatty alcohols, alkyl glycosides, alkoxylated fatty acid alkyl esters, amine oxides and polyhydroxy fatty acid amides.

Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann bzw. lineare und verzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxilate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z. B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 3 EO, 4 EO oder 7 EO, C9-11-Alkohole mit 7 EO, C13-15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-14-Alkohol mit 3 EO und C12-14-Alkohol mit 7 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf ("narrow range ethoxylates", NRE).As nonionic surfactants are preferably alkoxylated, preferably ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in which the alcohol radical may linear or preferably methyl-branched in the 2-position or may contain linear and branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, are alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C 12-14 alcohols containing 3 EO, 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-14 -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means that may be a whole or fractional number for a particular product. Preferred alcohol ethoxylates have a narrow homolog distribution ("narrow range ethoxylates", NRE).

Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohole mit 14 EO, 25 EO, 30 EO oder 40 EO. Auch nichtionische Tenside, die EO- und PO-Gruppen zusammen im Molekül enthalten, sind erfindungsgemäß einsetzbar. Hierbei können Blockcopolymere mit EO-PO-Blockeinheiten, bzw. PO-EO-Blockeinheiten eingesetzt werden, aber auch EO-PO-EO-Copolymere bzw. PO-EO-PO-Copolymere. Selbstverständlich sind auch gemischt alkoxylierte nichtionische Tenside einsetzbar, in denen EO- und PO-Einheiten nicht blockweise, sondern statistisch verteilt sind. Solche Produkte sind durch gleichzeitige Einwirkung von Ethylen- und Propylenoxid auf Fettalkohole erhältlich.In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohols with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units, or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, it is also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are not distributed in blocks, but randomly. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel RO(G), eingesetzt werden, in der R einen primären geradkettigen oder methylverzweigten insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glykose steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4.In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) can be used, in which R is a primary straight-chain or methyl-branched especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G the symbol is that which represents a glycose unit having 5 or 6 C atoms, preferably glycose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester.Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.Nonionic surfactants of the amine oxide type, for example N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Weitere nichtionische Tenside sind Polyhydroxyfettsäureamide der Formel (II)

Figure imgb0002
in der RC=O für einen aliphatischen Acylrest mit 6 bis 22 C-Atomen, R1 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 C-Atomen und (Z) für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 C-Atomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further nonionic surfactants are polyhydroxy fatty acid amides of the formula (II)
Figure imgb0002
 in the RC = O for an aliphatic acyl radical having 6 to 22 C atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 C atoms and (Z) for a linear or branched polyhydroxyalkyl radical having 3 to 10 C Atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (III)

Figure imgb0003
in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 C-Atomen, R2 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 C-Atomen und R3 für H, einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 C-Atomen steht, wobei C1-4-Alkyl- oder Phenylreste bevorzugt sind und (Z) für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte, Derivate dieses Restes. (Z) wird vorzugsweise durch reduktive Aminierung eines Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.The group of polyhydroxy fatty acid amides also includes compounds of the formula (III)
Figure imgb0003
 in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 C atoms, R 2 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 C atoms and R 3 is H, a linear, branched or a cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 C atoms, where C 1-4 -alkyl or phenyl radicals are preferred and (Z) is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups , or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this group. (Z) is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Es werden bevorzugt schwachschäumende, nichtionische Tenside eingesetzt, die einen Schmelzpunkt oberhalb Raumtemperatur aufweisen. Demzufolge sind bevorzugte Mischungen dadurch gekennzeichnet, dass sie nichtionische(s) Tensid(e) mit einem Schmelzpunkt oberhalb von 20 °C, vorzugsweise oberhalb 25 °C, besonders bevorzugt von 25 bis 100 °C, und insbesondere bevorzugt von 30 bis 50 °C, enthalten.Low-foaming, nonionic surfactants are preferably used which have a melting point above room temperature. Accordingly, preferred blends are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably from 25 to 100 ° C, and most preferably from 30 to 50 ° C , contain.

Geeignete nichtionische Tenside, die Schmelz- und Erweichungspunkte im genannten Temperaturbereich aufweisen, sind beispielsweise schaumärmere nichtionische Tenside, die bei Raumtemperatur fest oder hochviskos sein können. Werden bei Raumtemperatur hochviskose nichtionische Tenside eingesetzt, so ist bevorzugt, dass diese eine Viskosität oberhalb von 20 Pas, vorzugsweise oberhalb 35 Pas und insbesondere oberhalb 40 Pas aufweisen. Auch nichtionische Tenside, die bei Raumtemperatur eine wachsartige Konsistenz besitzen, sind bevorzugt.Suitable nonionic surfactants which have melting and softening points in the temperature range mentioned are, for example, low-foam nonionic surfactants which may be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have a waxy consistency at room temperature are also preferred.

Bevorzugt als bei Raumtemperatur feste einzusetzende nichtionische Tenside stammen aus den Gruppen der alkoxylierten nichtionischen Tenside, insbesondere der ethoxylierten primären Alkohole und Mischungen dieser Tenside mit strukturell komplizierter aufgebauten Tensiden wie Polyoxypropylen/Polyoxyethylen/Polyoxypropylen(PO/EO/PO)-Tenside. Solche nichtionischen (PO/EO/PO)-Tenside zeichnen sich darüber hinaus durch gute Schaumkontrolle aus.Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such nonionic (PO / EO / PO) surfactants are also characterized by good foam control.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung ist das nichtionische Tensid mit einem Schmelzpunkt oberhalb Raumtemperatur ein ethoxyliertes nichtionisches Tensid, das aus der Reaktion von einem Monohydroxyalkanol oder Alkylphenol mit 6 bis 20 C-Atomen mit vorzugsweise mindestens 12 Mol, besonders bevorzugt mindestens 15 Mol, insbesondere mindestens 20 Mol, Ethylenoxid pro Mol Alkohol bzw. Alkylphenol hervorgegangen ist.In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant resulting from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 mol, ethylene oxide per mole of alcohol or alkylphenol emerged.

Ein besonders bevorzugtes, bei Raumtemperatur festes, einzusetzendes nichtionisches Tensid wird aus einem geradkettigen Fettalkohol mit 16 bis 20 C-Atomen (C16-20-Alkohol), vorzugsweise einem C18-Alkohol und mindestens 12 Mol, vorzugsweise mindestens 15 Mol und insbesondere mindestens 20 Mol, Ethylenoxid pro Mol Alkohol gewonnen. Hierunter sind die so genannten "narrow range ethoxylates" (siehe oben) besonders bevorzugt.A particularly preferred nonionic surfactant which is solid at room temperature is selected from a straight-chain fatty alcohol having 16 to 20 C atoms (C 16-20 -alcohol), preferably a C 18 -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 moles of ethylene oxide per mole of alcohol. Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Demnach enthalten besonders bevorzugte erfindungsgemäße Mischungen ethoxylierte(s); nichtionische(s) Tensid(e), das/die aus C6-20-Monohydroxyalkanolen oder C6-20-Alkylphenolen oder C16-20-Fettalkoholen und mehr als 12 Mol, vorzugsweise mehr als 15 Mol und insbesondere mehr als 20 Mol Ethylenoxid pro Mol Alkohol gewonnen wurde(n).Accordingly, particularly preferred mixtures according to the invention contain ethoxylated (s); nonionic surfactant (s) consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles Ethylene oxide per mole of alcohol was won (n).

Das nichtionische Tensid besitzt vorzugsweise zusätzlich Propylenoxideinheiten im Molekül. Vorzugsweise machen solche PO-Einheiten bis zu 25 Gew.-%, besonders bevorzugt bis zu 20 Gew.-% und insbesondere bis zu 15 Gew.-% der gesamten Molmasse des nichtionischen Tensids aus. Besonders bevorzugte nichtionische Tenside sind ethoxylierte Monohydroxyalkanole oder Alkylphenole, die zusätzlich Polyoxyethylen-Polyoxypropylen Blockcopolymereinheiten aufweisen. Der Alkohol- bzw. Alkylphenolteil solcher nichtionischer Tensidmoleküle macht dabei vorzugsweise mehr als 30 Gew.-%, besonders bevorzugt mehr als 50 Gew.-% und insbesondere mehr als 70 Gew.-% der gesamten Molmasse solcher nichtionischer Tenside aus. Bevorzugte Klarspülmittel sind dadurch gekennzeichnet, dass sie ethoxylierte und propoxylierte nichtionische Tenside enthalten, in denen die Propylenoxideinheiten im Molekül bis zu 25 Gew.-%, bevorzugt bis zu 20 Gew.-% und insbesondere bis zu 15 Gew.-% der gesamten Molmasse des nichtionischen Tensids ausmachen, enthalten.The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes more than 30 wt .-%, more preferably more than 50 wt .-% and in particular more than 70 wt .-% of the total molecular weight of such nonionic surfactants. Preferred rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of nonionic surfactant.

Weitere besonders bevorzugt einzusetzende nichtionische Tenside mit Schmelzpunkter oberhalb Raumtemperatur enthalten 40 bis 70% eines Polyoxypropylen/Polyoxyethylen/Polyoxypropylen-Blockpolymerblends, der 75 Gew.-% eines umgekehrten Block-Copolymers von Polyoxyethylen und Polyoxypropylen mit 17 Mol Ethylenoxid und 44 Mol Propylenoxid und 25 Gew.-% eines Block-Copolymers von Polyoxyethylen und Polyoxypropylen, initiiert mit Trimethylolpropan und enthaltend 24 Mol Ethylenoxid und 99 Mol Propylenoxid pro Mol Trimethylolpropan.Other particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Die erfindungsgemäße Mischung enthält als weiteres bevorzugtes nichtionisches Tensid eine Verbindung der Formel (IV)

        R4O[CH2CH(CH3)O]x[CH2CH2O]yCH2CH(OH)R5     (IV),

in der R4 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 18 C-Atomen oder Mischungen hieraus besteht, R5 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 C-Atomen oder Mischungen hieraus bezeichnet, und x für Werte von 0,5 bis 1,5 und y für einen Wert von mindestens 15 steht.The mixture according to the invention contains as another preferred nonionic surfactant a compound of the formula (IV)

R 4 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 5 (IV)

in which R 4 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 C atoms or mixtures thereof, R 5 denotes a linear or branched hydrocarbon radical having 2 to 26 C atoms or mixtures thereof, and x for values of 0.5 to 1.5 and y stands for a value of at least 15.

Weitere bevorzugt einsetzbare nichtionische Tenside sind die endgruppenverschlossenen poly(oxyalkylierten) nichtionischen Tenside der Formel (V)

        R6O[CH2CH(R8)O]z[CH2]kCH(OH)[CH2]jOR7     (V),

in der R6 und R7 für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 30 C-Atomen stehen, R8 für Wasserstoff oder einen Methyl-, Ethyl, n-Propyl-, iso-Propyl-, n-Butyl-, 2-Butyl- oder 2-Methyl-2-butylrest steht, z für Werte von 1 bis 30, k und j für Werte von 1 bis 12, vorzugsweise von 1 bis 5 stehen. Wenn der Wert z ≥ 2 ist, kann jedes R8 in Formel (V) unterschiedlich sein. R6 und R7 sind vorzugsweise lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 6 bis 22 C-Atomen, wobei Reste mit 8 bis 18 C-Atomen besonders bevorzugt sind. Für den Rest R8 sind Wasserstoff, Methyl- oder Ethyl- besonders bevorzugt. Besonders bevorzugte Werte für z liegen im Bereich von 1 bis 20, insbesondere von 6 bis 15.Further preferably usable nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula (V)

R 6 O [CH 2 CH (R 8 ) O] z [CH 2 ] k CH (OH) [CH 2 ] j OR 7 (V)

in which R 6 and R 7 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 C atoms, R 8 is hydrogen or a methyl, ethyl, n-propyl, iso-propyl, n is -butyl, 2-butyl or 2-methyl-2-butyl, z is from 1 to 30, k and j are from 1 to 12, preferably from 1 to 5. When the value z ≥ 2, each R 8 in formula (V) may be different. R 6 and R 7 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R 8 , hydrogen, methyl or ethyl are particularly preferred. Particularly preferred values for z are in the range from 1 to 20, in particular from 6 to 15.

Wie vorstehend beschrieben, kann jedes R8 in Formel (V) unterschiedlich sein, falls z ≥ 2 ist. Hierdurch kann die Alkylenoxideinheit in der eckigen Klammer variiert werden. Steht z beispielsweise für 3, kann der Rest R8 ausgewählt werden, um Ethylenoxid-(R8 = H) oder Propylenoxid-(R8 = CH3) Einheiten zu bilden, die in jedweder Reihenfolge aneinandergefügt sein können, beispielsweise (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) und (PO)(PO)(PO). Der Wert 3 für z ist hierbei beispielhaft gewählt worden und kann durchaus größer sein, wobei die Variationsbreite mit steigendem z-Wert zunimmt und beispielsweise eine große Anzahl EO-Gruppen, kombiniert mit einer geringen Anzahl PO-Gruppen einschließt oder umgekehrt.As described above, each R 8 in formula (V) may be different if z ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when z is 3, the radical R 8 can be selected to form ethylene oxide (R 8 = H) or propylene oxide (R 8 = CH 3 ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for z has been chosen here by way of example and may well be greater, with the variation range increasing with increasing z value and including, for example, a large number of EO groups combined with a small number of PO groups or vice versa.

Insbesondere bevorzugte endgruppenverschlossene poly(oxyalkylierte) Alkohole der Formel (V) weisen Werte von k = 1 und j = 1 auf, so dass sich die Formel (V) zu Formel (VI) vereinfacht:

        R6O[CH2CH(R8)]zCH2CH(OH)CH2OR7     (VI).

Particularly preferred end-capped poly (oxyalkylated) alcohols of the formula (V) have values of k = 1 and j = 1, so that the formula (V) simplifies to formula (VI):

R 6 O [CH 2 CH (R 8 )] z CH 2 CH (OH) CH 2 OR 7 (VI).

In Formel (VI) sind R6, R7 und R8 wie in Formel (V) definiert und z steht für Zahlen von 1 bis 30, vorzugsweise von 1 bis 20 und insbesondere von 6 bis 18. Besonders bevorzugt sind Tenside, bei denen die Reste R6 und R7 9 bis 14 C-Atome aufweisen, R8 für Wasserstoff steht und z Werte von 6 bis 15 annimmt.In formula (VI) R 6 , R 7 and R 8 are as defined in formula (V) and z is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 6 and R 7 have 9 to 14 C atoms, R 8 is hydrogen and z assumes values of 6 to 15.

Fasst man die letztgenannten Aussagen zusammen, sind erfindungsgemäße Mischungen bevorzugt, die als nichtionische Tenside endgruppenverschlossene poly(oxyalkylierte) Verbindungen der Formel (V) enthalten, in der R6 und R7 für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische Kohlenwasserstoffreste mit 1 bis 30 C-Atomen stehen, R8 für Wasserstoff oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, 2-Butyl- oder 2-Methyl-2-butylrest steht, z für Werte zwischen 1 und 30, k und j für Werte von 1 bis 12, vorzugsweise von 1 bis 5 stehen, wobei Tenside der Formel (VI), in der z für Zahlen von 1 bis 30, vorzugsweise von 1 bis 20 und insbesondere von 6 bis 18 steht, besonders bevorzugt sind.Summarizing the last-mentioned statements, mixtures according to the invention are preferred which contain poly (oxyalkylated) compounds of the formula (V) which end-capped as nonionic surfactants, in which R 6 and R 7 are linear or branched, saturated or unsaturated, aliphatic hydrocarbon radicals having 1 to 30 C atoms, R 8 is hydrogen or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, z is values between 1 and 30, k and j are values from 1 to 12, preferably from 1 to 5, wherein surfactants of the formula (VI) in which z is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

Ganz besonders bevorzugt liegen in der erfindungsgemäßen Mischung als Komponente (b) nichtionische Tenside vor, die unter dem Handelsnamen Pluronic® von der BASF AG erhältlich sind.Very particular preference is given in the mixture according to the invention as component (b) to nonionic surfactants which are obtainable under the trade name Pluronic® from BASF AG.

Der Anteil der Komponente (a) beträgt 5 bis 95 Gew.-%, vorzugsweise 40 bis 60 Gew.-%. Ein beispielhafter Anteil der Komponente (a) ist 50 Gew.-%. Entsprechend liegt die Komponente (b) in einer Menge von 5 bis 95 Gew.-%, vorzugsweise 40 bis 60 Gew.-% vor. Beispielhaft ist eine Menge von 50 Gew.-%.The proportion of component (a) is 5 to 95 wt .-%, preferably 40 to 60 wt .-%. An exemplary proportion of component (a) is 50% by weight. Accordingly, component (b) is present in an amount of 5 to 95% by weight, preferably 40 to 60% by weight. An example is an amount of 50 wt .-%.

Die erfindungsgemäßen Mischpulver oder Mischgranulate können hergestellt werden durch Mischen beider Komponenten als Pulver und anschließendes Erwärmen der Mischung, insbesondere auf eine Temperatur oberhalb des Schmelz- oder Erweichungspunktes der Komponente (b). Dabei schmilzt Komponente (b) und vermischt sich innig mit Komponente (a). Im anschließenden Kühl- und Formgebungsprozess werden die Pulvereigenschaften wie Partikelgröße und Schüttgewicht eingestellt.The mixed powders or mixed granules according to the invention can be prepared by mixing both components as a powder and then heating the mixture, in particular to a temperature above the melting or softening point of component (b). In this case, component (b) melts and intimately mixes with component (a). In the subsequent cooling and shaping process, the powder properties such as particle size and bulk density are adjusted.

Die vorliegende Erfindung betrifft auch ein Verfahren zur Herstellung der erfindungsgemäßen Mischpulver oder Mischgranulate durch Mischen der Komponenten (a) und (b) als Pulver, Erwärmen der Mischung und Einstellen der Pulvereigenschaften im anschließenden Kühl- und Formgebungsprozess.The present invention also relates to a process for producing the mixed powders or mixed granules according to the invention by mixing the components (a) and (b) as a powder, heating the mixture and adjusting the powder properties in the subsequent cooling and shaping process.

Weiterhin ist es möglich, die Komponente (a) mit der bereits aufgeschmolzenen Komponente (b) zu granulieren und anschließend abzukühlen.Furthermore, it is possible to granulate the component (a) with the already melted component (b) and then to cool it.

Bei geeigneten Mischungsverhältnissen (a) / (b) kann auch die Komponente (a) in die Schmelze der Komponente (b) eingerührt werden. Die anschließende Erstarrung und Formgebung erfolgt entsprechend der bekannten Verfahren der Schmelzkonfektionierung, beispielsweise durch Prillen oder auf Kühlbändern mit bei Bedarf nachgeschalteten Schritten zur Einstellung der Pulvereigenschaften, wie Mahlung und Siebung.With suitable mixing ratios (a) / (b), component (a) can also be stirred into the melt of component (b). The subsequent solidification and shaping takes place in accordance with the known processes of melt fabrication, for example by prilling or on cooling belts with, if necessary, downstream steps for adjusting the powder properties, such as grinding and sieving.

Die erfindungsgemäßen Mischpulver oder Mischgranulate können auch 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. Als Lösungsmittel können alle die eingesetzt werden; die die Komponenten (a) und (b) lösen können, bevorzugt werden beispielsweise Alkohole und/oder Wasser, besonders bevorzugt Wasser eingesetzt.The mixed powders or mixed granules according to the invention can also be prepared by dissolving components (a) and (b) in a solvent and spray-drying the resulting mixture, wherein a granulation step can follow. In this case, the components (a) and (b) can be dissolved separately, wherein the solutions are subsequently mixed, or a powder mixture of the components can be dissolved in water. As the solvent, all of them can be used; which are able to dissolve components (a) and (b), preference is given to using, for example, alcohols and / or water, more preferably water.

Die vorliegende Erfindung betrifft somit auch ein Verfahren zur Herstellung der erfindungsgemäßen Mischpulver oder Mischgranulate durch Lösen der Komponenten (a) und (b) in einem Lösungsmittel und Sprühtrocknen des erhaltenen Gemisches, wobei sich ein Granulierungsschritt und/oder ein Schmelzgranulierungsschritt (s.o.) anschließen kann.The present invention thus also relates to a process for the preparation of the mixed powders or mixed granules according to the invention by dissolving components (a) and (b) in a solvent and spray-drying the resulting mixture, wherein a granulation step and / or a melt granulation step (see above) can follow.

Die vorliegende Erfindung betrifft auch die Verwendung der erfindungsgemäßen Mischpulver oder Mischgranulate zur Herstellung von festen Wasch- und Reinigungsmitteln, bei der Wäsche von Textilien oder bei der Reinigung von Geschirr. Beide Komponenten entfalten als Mischpulver oder Mischgranulate eine Wirkung in Wasch- und Reinigungsmitteln, beispielsweise als Geschirr-Reinigungsmittel für GeschirrSpülmaschinen.The present invention also relates to the use of the mixed powders or mixed granules according to the invention for the production of solid detergents and cleaners, in the washing of textiles or in the cleaning of dishes. Both components unfold as mixed powder or mixed granules an effect in detergents and cleaning agents, for example as a dishwashing detergent for dishwashers.

Die Mischpulver oder Mischgranulate können in pulverförmige Wasch- und Reinigungsmittel eingearbeitet werden, ohne dass diese verklumpen oder verbacken.The mixed powders or mixed granules can be incorporated into pulverulent detergents and cleaners without these clumping or caking.

Die Erfindung betrifft auch ein festes Waschmittel, enthaltend ein wie vorstehend beschriebenes Mischpulver oder Mischgranulat und gegebenenfalls mindestens ein weiteres Tensid. Geeignete Waschmittelzusammensetzungen sind bekannt und beispiels weise in WO 95/29216 und EP-A-0 618 289 beschrieben.The invention also relates to a solid detergent containing a mixed powder or mixed granules as described above and optionally at least one further surfactant. Suitable detergent compositions are known and example, in WO 95/29216 and EP-A-0 618 289 described.

Die Erfindung betrifft ferner ein festes Geschirrreinigungsmittel, das ein Mischpulver oder Mischgranulat, wie es vorstehend beschrieben ist, enthält und zudem gegebenenfalls mindestens ein (weiteres) Tensid. Die Mittel liegen dabei vorzugsweise in Pulver- oder Granulatform vor.The invention further relates to a solid dishwashing detergent containing a mixed powder or mixed granules, as described above, and also optionally at least one (further) surfactant. The agents are preferably present in powder or granular form.

Claims (12)

  1. A mixed powder or mixed granule comprising at least 80% by weight of a mixture of
    (a) from 5 to 95% by weight of glutamic acid-N,N-diacetic acid and/or one or more salts thereof of the general formula (I)

            MOOC- (CH2)2-HC (COOM) -N (CH2COOM)2     (I)

    where
    M is H, NH4, alkali metal,
    (b) from 5 to 95% by weight of at least one polyethylene glycol or of at least one nonionic surfactant or of a mixture thereof or of a polymer selected from the group consisting of polyvinyl alcohols, polyvinylpyrrolidones (PVP), polyalkylene glycols and derivatives thereof.
  2. The mixed powder or mixed granule according to claim 1, wherein component (a) is an alkali metal salt of glutamic acid-diacetic acid.
  3. The mixed powder or mixed granule according to claim 1 or 2, wherein the polyethylene glycol in component (b) has an average molecular weight (weight-average molecular weight) of from 500 to 30 000 g/mol.
  4. The mixed powder or mixed granule according to any of claims 1 to 3, wherein the polyethylene glycol in component (b) has OH and/or C1-6-alkyl end groups.
  5. The mixed powder as claimed in any of claims 1 to 4, wherein the nonionic surfactant in component (b) is selected from the group consisting of alkoxylated primary alcohols, alkoxylated fatty alcohols, alkylglycosides, alkoxylated fatty acid alkyl esters, amine oxides and polyhydroxy fatty acid amides.
  6. The mixed powder according to any of claims 1 to 5, wherein the nonionic surfactant in component (b) has a melting point of above 20°C.
  7. A process for producing mixed powders or mixed granules according to any of claims 1 to 6 by dissolving components (a) and (b) in a solvent and spray-drying the resulting mixture, which may be followed by a granulation step.
  8. A process for producing mixed powders or mixed granules according to any of claims 1 to 6 by mixing components (a) and (b) as a powder, heating the mixture and adjusting the powder properties in the subsequent cooling and shaping process.
  9. The use of mixed powders or mixed granules according to any of claims 1 to 6 for producing solid laundry detergents and cleaning compositions, for the laundering of textiles or for the cleaning of tableware and kitchenware.
  10. A solid laundry detergent comprising a mixed powder or mixed granule according to any of claims 1 to 6 and optionally at least one (further) surfactant.
  11. A solid dishwasher detergent comprising a mixed powder or mixed granule according to any of claims 1 to 6 and optionally at least one further surfactant.
  12. The composition as claimed in claim 10 or 11 in powder or granule form.
EP06841537A 2006-01-03 2006-12-21 Mixed powder or mixed granule based on glutamic acid-n,n-diacetic acid and salts thereof Not-in-force EP1971675B1 (en)

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EP06100033A EP1803801A1 (en) 2006-01-03 2006-01-03 Powder or granulate based on glutamic-N,N,diacetic acid and its salts
EP06841537A EP1971675B1 (en) 2006-01-03 2006-12-21 Mixed powder or mixed granule based on glutamic acid-n,n-diacetic acid and salts thereof
PCT/EP2006/070063 WO2007077143A1 (en) 2006-01-03 2006-12-21 Mixed powder or mixed granule based on glutamic acid-n,n-diacetic acid and salts thereof

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CA2633735A1 (en) 2007-07-12
US20080300159A1 (en) 2008-12-04
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US7867966B2 (en) 2011-01-11
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