EP1765967B1 - Mischpulver oder mischgranulat auf basis von mgda - Google Patents

Mischpulver oder mischgranulat auf basis von mgda Download PDF

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Publication number
EP1765967B1
EP1765967B1 EP05756996.4A EP05756996A EP1765967B1 EP 1765967 B1 EP1765967 B1 EP 1765967B1 EP 05756996 A EP05756996 A EP 05756996A EP 1765967 B1 EP1765967 B1 EP 1765967B1
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EP
European Patent Office
Prior art keywords
mixed
powder
component
weight
mixture
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EP05756996.4A
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German (de)
English (en)
French (fr)
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EP1765967A1 (de
Inventor
Helmut Witteler
Michael Schoenherr
Markus Hartmann
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BASF SE
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BASF SE
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Priority to PL05756996T priority Critical patent/PL1765967T3/pl
Publication of EP1765967A1 publication Critical patent/EP1765967A1/de
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/825Mixtures of compounds all of which are non-ionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707Polyethers, e.g. polyalkyleneoxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753Polyvinylalcohol; Ethers or esters thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776Heterocyclic compounds, e.g. lactam

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.
  • 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, but glycine-N, N-diacetic acid derivatives 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, glycine-N, N-diacetic acid derivatives are not listed.
  • polymers in particular polycarboxylates such as polyacrylates are listed.
  • glycine-N, N-diacetic acid derivatives as complexing agents for alkaline earth and heavy metal ions in detergents and cleaners is in the EP-A-0 845 456 described.
  • MGDA derivatives glycine-N, N-diacetic acid derivatives
  • a special crystallization process is used.
  • the bulk and flowability of the powder or granules should be preserved.
  • N-diacetic acid derivatives with polycarboxylates has the advantage that o.g. Distinguish mixtures by improved flowability.
  • M is an alkali metal, preferably sodium or potassium, more preferably sodium.
  • R is a C 1-12 -alkyl radical, preferably a C 1-6 -alkyl radical, more preferably a methyl or ethyl radical.
  • Particularly preferred component (a) used is an alkali metal salt of methylglycinediacetic acid (MGDA). Most preferably, the trisodium salt of methylglycinediacetic acid is used.
  • At least one polyethylene glycol or at least one nonionic surfactant with at least one polyethylene glycol is used.
  • 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, advantageously 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 residue 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
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • 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.
  • nonionic surfactants are polyhydroxy fatty acid amides of the formula (II)
  • 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)
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 3 is a linear, branched or cyclic Alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1-4 alkyl or phenyl radicals are preferred and (Z) is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this radical.
  • (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 moles, preferably at least 15 moles and especially at least 20 moles, of ethylene oxide.
  • 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 moles, preferably at least 15 moles and especially at least 20 moles, of ethylene oxide.
  • the so-called “narrow range ethoxylates" are particularly preferred.
  • particularly preferred mixtures according to the invention comprise ethoxylated (s), nonionic surfactant (s) which are prepared from C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (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 moiety of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, 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 selected 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). This melts component (b) and mixed intimately 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. Furthermore, it is possible to granulate the component (a) with the already melted component (b) and then to cool it.
  • 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.
  • solvents it is possible to use all those which can dissolve components (a) and (b); preference is given, for example, to using 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, as mixed powders or mixed granules have an effect in washing and detergents, for example as dishwashing detergents for dishwashing machines.
  • 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.
  • Suitable detergent compositions are known and, for example, in WO 95/29216 and EP-A-0 618 289 described.
  • the invention further relates to a solid dishwashing detergent comprising a mixed powder or mixed granules as described above.
  • the agents are preferably present in powder or granular form.
  • MGDA methylglycinediacetic acid
  • PEG 1500 polyethylene glycol having a molecular weight of about 1500 g / mol
  • the mixture according to the invention was prepared after melt blending a mixture of MGDA and the polyethylene glycol.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
EP05756996.4A 2004-07-02 2005-07-01 Mischpulver oder mischgranulat auf basis von mgda Active EP1765967B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL05756996T PL1765967T3 (pl) 2004-07-02 2005-07-01 Mieszany proszek lub mieszany granulat na bazie mgda

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004032320A DE102004032320A1 (de) 2004-07-02 2004-07-02 Mischpulver oder Mischgranulat auf Basis von MGDA
PCT/EP2005/007132 WO2006002954A1 (de) 2004-07-02 2005-07-01 Mischpulver oder mischgranulat auf basis von mgda

Publications (2)

Publication Number Publication Date
EP1765967A1 EP1765967A1 (de) 2007-03-28
EP1765967B1 true EP1765967B1 (de) 2018-04-25

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EP05756996.4A Active EP1765967B1 (de) 2004-07-02 2005-07-01 Mischpulver oder mischgranulat auf basis von mgda

Country Status (15)

Country Link
US (1) US8048838B2 (es)
EP (1) EP1765967B1 (es)
JP (1) JP2008505236A (es)
KR (1) KR101117367B1 (es)
CN (1) CN1977036B (es)
AU (1) AU2005259456B2 (es)
BR (1) BRPI0512778B8 (es)
CA (1) CA2572311C (es)
DE (1) DE102004032320A1 (es)
ES (1) ES2676526T3 (es)
MX (1) MXPA06014753A (es)
NO (1) NO20070375L (es)
PL (1) PL1765967T3 (es)
TR (1) TR201810622T4 (es)
WO (1) WO2006002954A1 (es)

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AU2005259456B2 (en) 2010-10-28
BRPI0512778A (pt) 2008-04-08
CA2572311A1 (en) 2006-01-12
JP2008505236A (ja) 2008-02-21
BRPI0512778B1 (pt) 2019-04-02
KR101117367B1 (ko) 2012-03-07
AU2005259456A1 (en) 2006-01-12
NO20070375L (no) 2007-01-30
CN1977036B (zh) 2010-06-16
WO2006002954A1 (de) 2006-01-12
US20080045430A1 (en) 2008-02-21
MXPA06014753A (es) 2007-03-23
TR201810622T4 (tr) 2018-08-27
DE102004032320A1 (de) 2006-01-19
CA2572311C (en) 2013-02-26
PL1765967T3 (pl) 2018-09-28
KR20070036164A (ko) 2007-04-02
ES2676526T3 (es) 2018-07-20
US8048838B2 (en) 2011-11-01
BRPI0512778B8 (pt) 2019-11-19
CN1977036A (zh) 2007-06-06
EP1765967A1 (de) 2007-03-28

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