EP1761622A1 - Procede de production de compositions detergentes granulaires ou pulverulentes - Google Patents

Procede de production de compositions detergentes granulaires ou pulverulentes

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Publication number
EP1761622A1
EP1761622A1 EP05758640A EP05758640A EP1761622A1 EP 1761622 A1 EP1761622 A1 EP 1761622A1 EP 05758640 A EP05758640 A EP 05758640A EP 05758640 A EP05758640 A EP 05758640A EP 1761622 A1 EP1761622 A1 EP 1761622A1
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EP
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Prior art keywords
sub
mol
sup
hydrogen
monoethylenically unsaturated
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EP05758640A
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German (de)
English (en)
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EP1761622B1 (fr
Inventor
Kathrin Michl
Tanja Seebeck
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the present invention relates to a process for the preparation of granular or powdered detergent compositions, comprising the preparation of a detergent base powder by drying an aqueous detergent slurries, and detergent compositions containing a by radical copolymerization of
  • R 1 is hydrogen or methyl;
  • R 3 are identical or different C 2 -C 4 -alkylene radicals which may be arranged in blocks or randomly, the proportion of ethylene radicals being at least 50 mol%;
  • R 4 is hydrogen, C 1 -C 4 -alkyl- 1 -SO 3 M or -PO 3 M 2 ;
  • R 6 is -O- [R 3 -O] n -R 4 , where the radicals - [R 3 -O] n - may be different from the other radicals contained in formula I - [R 3 -O] n -;
  • R 7 is hydrogen or ethyl; M alkali metal or hydrogen; n 4
  • EP-A-778 340 describes the use of these copolymers and of copolymers of acrylic acid and both propoxylated and ethoxylated allyl ethers as coating inhibitors in automatic dishwashing detergents.
  • copolymers based on unsaturated mono- and / or dicarboxylic acids having a hydrophilic backbone and hydrophobic side chains can also be used for this purpose.
  • the side chains are bonded to the skeleton via ester, ether or amide functions and can consist of polyalkylene oxides which either have a high proportion of C 3 -C 4 -alkylene oxides or are end-group-capped by long-chain alkyl radicals.
  • the object of the invention was to make possible the production of solid detergent compositions by employing viscosity-reducing polymers in an advantageous manner.
  • the polymers used should have advantageous an ⁇ technical effect in the resulting detergents.
  • R 1 is hydrogen or methyl;
  • R 3 are the same or different C 2 -C 4 -alkylene radicals which may be arranged blockwise or statically, the proportion of ethylene radicals being at least 50 mol%;
  • R 4 is hydrogen, C 1 -C 4 -alkyl, -SO 3 M or -PO 3 M 2 ;
  • R 6 is -O- [R 3 -O) n -R 4 , where the radicals - [R 3 -O] n - may be different from the other radicals contained in formula I - [R 3 O] n -;
  • R 7 is hydrogen or ethyl; M alkali metal or hydrogen; n 4 to 250
  • copolymers used according to the invention contain as copolymerized monomer (A) a monoethylenically unsaturated monocarboxylic acid, preferably a CrCe monocarboxylic acid, and / or a water-soluble salt, in particular an alkali metal salt, such as potassium and, above all, sodium salt, or ammonium salt, of this acid ,
  • A a monoethylenically unsaturated monocarboxylic acid, preferably a CrCe monocarboxylic acid, and / or a water-soluble salt, in particular an alkali metal salt, such as potassium and, above all, sodium salt, or ammonium salt, of this acid ,
  • Suitable monomers (A) are: acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. Of course, mixtures of these acids can also be used.
  • Particularly preferred monomer (A) is acrylic acid.
  • the copolymers used according to the invention contain from 50 to 99.5 mol% of the monomer (A). If the copolymers are composed only of the monomers (A) and (B), the content of the monomer (A) is generally from 80 to 99.5 mol%, preferably from 90 to 98 mol%. Terpolymers of the monomers (A), (B) and (C) generally contain from 60 to 98 mol%, preferably from 70 to 95 mol%, of the monomer (A).
  • the copolymers used according to the invention comprise an alkoxylated monoethylenically unsaturated monomer of the formula I.
  • H 2 C C-R 2 -
  • R 1 is hydrogen or methyl, preferably hydrogen;
  • R 3 are the same or different C 2 -C 4 -alkylene radicals which may be arranged in blocks or randomly, the proportion of ethylene radicals being at least 50 mol%, preferably at least 75 mol% and particularly preferably 100 mol%;
  • R 4 is hydrogen, C 1 -C 4 -alkyl, -SO 3 M or -PO 3 M 2 ;
  • R 5 is hydrogen or
  • particularly suitable monomers (B) are the alkoxylation products of the following unsaturated monomers: (meth) allyl alcohol, (meth) allylamines, diallylamines, glycerol monoallyl ethers, trimethylolpropane monoallyl ethers, vinyl ethers, vinylamides and vinylamines.
  • monomers (B) based on allyl alcohol, glycerol monoallyl ether, trimethylolpropane monoallyl ether and diallylamine are particularly preferred.
  • Very particularly preferred monomer (B) are ethoxylated allyl alcohols, which contain in particular 5 to 20, especially 10 to 100 moles EO / mol.
  • the monomers (B) can be prepared by well-known standard methods of organic chemistry, for. Example by amidation and transamidation of ge suitable (meth) acrylic acids, by alkoxylation of allyl alcohol, glycerol monoallyl ether or Trimethylolpropanmonoallylether, by etherification of allyl halides with poly-C 2 -C 4 alkylene oxides and by vinylation of polyalkylene oxides with OH or NH End group with acetylene.
  • copolymers used according to the invention have -SO 3 M or -PO 3 M 2 end groups, these can be introduced by sulfation or phosphation of the monomers (B) or else the copolymers themselves, for example with chlorosulfonic acid or polyphosphoric acid ,
  • the copolymers used according to the invention contain from 0.5 to 20 mol% of the monomer (B). If the copolymers are composed only of the monomers (A) and (B), the content of the monomer (B) is usually from 0.5 to 20 mol%, preferably at 1 to 10 mol%. Terpolymers of the monomers (A), (B) and (C) generally contain from 1 to 15 mol%, preferably from 1 to 10 mol%, of the monomer (B).
  • the copolymers used according to the invention may contain as copolymerized monomer (C) a monoethylenically unsaturated dicarboxylic acid, preferably a C 4 -C 8 -dicarboxylic acid.
  • C copolymerized monomer
  • a monoethylenically unsaturated dicarboxylic acid preferably a C 4 -C 8 -dicarboxylic acid.
  • an alkali metal salt such as potassium and, above all, sodium salt, or ammonium salt
  • Suitable monomers (C) are: maleic acid, fumaric acid, methylenemalonic acid, citraconic acid and itaconic acid. Of course, mixtures of these acids can also be used.
  • Particularly preferred monomer (C) is maleic acid.
  • the monomer (C) When the monomer (C) is contained in the copolymers used in the invention, its content is usually 1 to 30 mol%, preferably 5 to 30 mol%.
  • copolymers used according to the invention are preferably composed only of the monomers (A) and (B) or of the monomers (A), (B) and (C).
  • they may also contain another monoethylenically unsaturated monomer (D) other than the monomers (A) to (C) but copolymerizable with these monomers.
  • D monoethylenically unsaturated monomer
  • Examples of suitable monomers (D) are:
  • esters of monoethylenically unsaturated C 3 -C 8 -carboxylic acids in particular (meth) acrylic esters, such as methyl, ethyl, propyl, hydroxypropyl, n-butyl, isobutyl, 2-ethylhexyl, decyl, lauryl iso-bomyl, cetyl, palmityl and stearyl (meth) acrylate;
  • (Meth) acrylamides such as (meth) acrylamide, N- (C r C 12 alkyl) - and N, N-di (CrC 4 alkyl) - (meth) acrylamides such as N-methyl, N, N- Dimethyl, N-ethyl, N-propyl, N-tert-butyl, N-tert-octyl and N-undecyl (meth) acrylamide;
  • Vinyl aromatics such as styrene and substituted styrenes, e.g. Alkylstyrenes, such as methylstyrene and Ethylstyroi.
  • monomers (D) are present in the copolymers used according to the invention, their content is generally from 1 to 20 mol%, preferably from 1 to 10 mol%. If hydrophobic monomers are used as monomer (D), their content should be selected so that the copolymer retains its hydrophilic character as a whole.
  • the copolymers used according to the invention have an average molecular weight M w of from 30,000 to 500,000 g / mol, preferably from 50,000 to 300,000 g / mol (determined by gel permeation chromatography at room temperature with aqueous eluent).
  • K values are accordingly from 40 to 150, preferably from 50 to 125 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C., according to H. Finkentscher, Cellulose-Chemie, Vol. 13, pp. 58-64 and 71-74 (1932)).
  • copolymers used according to the invention can be obtained by the known radical polymerization processes.
  • solution and emulsion polymerization should be mentioned, with the solution polymerization being preferred.
  • the polymerization is preferably carried out in water as a solvent.
  • it can also be carried out in alcoholic solvents, in particular in C 1 -C 4 -alcohols, such as methanol, ethanol and isopropanol, or in mixtures of these solvents with water.
  • Suitable polymerization initiators are both thermally and photochemically (photoinitiators) decomposing and thereby radical-forming compounds.
  • thermally activatable polymerization initiators are initiators having a decomposition temperature in the range of 20 to 180 0 C, in particular from 50 to 12O 0 C, be ⁇ preferred.
  • suitable thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (ammonium and preferably sodium peroxodisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxo compounds, such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, Didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toloyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert-butyl permalate, tert-butyl perisobutyrate, tert-butyl perpivalate
  • initiators can be used in combination with reducing compounds as starter / regulator systems.
  • reducing compounds include phosphorus-containing compounds, such as phosphorous acid, hypophosphites and phosphinates, and sulfur-containing compounds, such as sodium hydrogen sulfite, sodium sulfite and sodium formaldehyde sulfoxilate.
  • transition metal catalysts for example salts of iron, cobalt, nickel, copper, vanadium and manganese.
  • Suitable salts are, for example, iron (II) sulfate, cobalt (II) chloride, nickel (II) sulfate, copper (I) chloride.
  • the reducing transition metal salt is usually used in an amount of from 0.1 to 1000 ppm, based on the sum of the monomers.
  • combinations of hydrogen peroxide and iron (II) salts are particularly advantageous, such as a combination of 0.5 to 30% by weight hydrogen peroxide and 0.1 to 500 ppm FeSO 4 .7H 2 O, in each case based on the sum of the monomers.
  • photoinitiators examples include benzophenone, acetophenone, benzoin ethers, Benzyldialkylketone and derivatives thereof.
  • thermal initiators are used, with inorganic peroxo compounds, in particular hydrogen peroxide and especially sodium peroxodisulfate (sodium persulfate) being preferred.
  • inorganic peroxo compounds in particular hydrogen peroxide and especially sodium peroxodisulfate (sodium persulfate) being preferred.
  • the peroxo compounds are used in combination with sulfur-containing reducing agents, sodium hydrogen sulfite, as a redox initiator system.
  • sulfur-containing reducing agents sodium hydrogen sulfite
  • this starter / regulator system is used, copolymers are obtained which, as end groups, contain -SO 3 " Na + and / or -SO 4 ' Na + .
  • phosphorus-containing starter / regulator systems may also be used, e.g. Hypophosphites / phosphinates.
  • photoinitiator or starter / regulator system are to be matched to the particular monomers used. If, for example, the preferred system peroxydisulphate / hydrogen sulphite is used, it is customary to use from 2 to 6% by weight, preferably from 3 to 5% by weight, of peroxodisulphate and generally from 5 to 30% by weight, preferably from 5 to 10 wt .-%, hydrogen sulfite, in each case based on the sum of the monomers Liste ⁇ sets.
  • polymerization regulators can also be used. Suitable compounds known to those skilled in the art, e.g. Sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecylmercaptan.
  • polymerization regulators are used, their amount used is generally from 0.1 to 15% by weight, preferably from 0.1 to 5% by weight and more preferably from 0.1 to 2.5% by weight, based on the sum of the monomers.
  • the polymerization temperature is generally from 30 to 200 ° C., preferably from 50 to 150 ° C., and more preferably from 80 to 130 ° C.
  • the polymerization is preferably carried out under protective gas, such as nitrogen or argon, and can be carried out under atmospheric pressure, but it is preferably carried out in a closed system under the developing autogenous pressure.
  • protective gas such as nitrogen or argon
  • copolymers used according to the invention are usually obtained in the form of a polymer solution which has a solids content of from 10 to 70% by weight, preferably from 25 to 60% by weight.
  • the viscosity of aqueous detergent slurries in particular of the slurries which are dried to produce granular or pulverulent detergent compositions, can be lowered effectively, so that even highly concentrated slurries can be handled without problems.
  • the slurry concentrations may always be ⁇ 50% by weight, preferably> 60% by weight and more preferably> 65% by weight, based on the anhydrous detergent components.
  • copolymers according to the invention additionally bring about stabilization and homogenization of the slurries and prevent separations.
  • copolymers used according to the invention are not only outstandingly suitable as process auxiliaries for detergent production because of their viscosity-lowering and stabilizing action, but are also notable for their advantageous performance properties during the washing process themselves. Thus, they act in solid and liquid detergent compositions both incrustation-inhibiting and graying-inhibiting.
  • Solid detergent formulations according to the invention which comprise the copolymers used according to the invention advantageously have e.g. following composition:
  • Liquid detergent formulations according to the invention may e.g. be composed as follows:
  • Suitable nonionic surfactants (b) are, in particular:
  • the alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide. There may be block copolymers or random copolymers. They usually contain from 2 to 50 mol, preferably from 3 to 20 mol, of at least one alkylene oxide per mole of alcohol. Preferred alkylene oxide is ethylene oxide.
  • the alcohols preferably have 10 to 18 carbon atoms.
  • Alkylphenolalkoxylate especially alkylphenol ethoxylates containing C 6 -C 14 alkyl chains and 5 to 30 moles of alkylene oxide / mol.
  • N-alkylglucamides fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.
  • Suitable anionic surfactants are, for example:
  • Sulfated alkoxylated C 8 -C 22 -alcohols (alkyl ether sulfates): Compounds of this type are prepared, for example characterized in that firstly a C 8 -C 22 -, preferably a pre-Ci 0 -C 8 alcohol, for example a fatty alcohol alkoxylated and the alkoxylation product is subsequently sulfated.
  • alkoxylation is preferably used ethylene oxide.
  • Linear C 8 -C 20 -alkylbenzenesulfonates LAS
  • LAS linear C 9 -C 13 -alkylbenzenesulfonates and -alkyltoluenesulfonates.
  • Alkanesulfonates in particular C 8 -C 24 -, preferably C 10 -C 18 -alkanesulfonates.
  • Soaps such as the Na and K salts of C 8 -C 24 carboxylic acids.
  • the anionic surfactants are preferably added to the detergent in the form of salts.
  • Suitable salts are e.g. Alkali metal salts such as sodium, potassium and lithium salts, and ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
  • Particularly suitable cationic surfactants are:
  • Esterquats in particular quaternary esterified mono-, di- and trialkanolamines esterified with C 8 -C 22 -carboxylic acids;
  • R 8 is C 1 -C 5 -alkyl or C 2 -C 25 -alkynyl I; R 9 is C 1 -C 4 -alkyl or hydroxy-C 1 -C 4 -alkyl; R 10 is C 1 -C 4 -alkyl, 1 is hydroxy-dC 4 -alkyl or a radical R 8 is - (CO) -X- (CH 2 ) P - (X: -O- or -NH-; p: 2 or 3 ), wherein at least one radical R 8 is C 7 -C 22 -alkyl.
  • Suitable inorganic builders are, in particular:
  • Crystalline and amorphous aluminosilicates with ion-exchanging properties especially zeolites:
  • zeolites Various types are suitable, in particular the zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially soluble other cations such as Li, K, Ca, Mg or ammonium are exchanged.
  • Crystalline silicates in particular disilicates and sheet silicates, for example ⁇ - and ⁇ -Na 2 Si 2 O 5 .
  • the silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preference being given to the Na, Li and Mg silicates.
  • Amorphous silicates such as sodium metasilicate and amorphous disilicate.
  • Carbonates and bicarbonates can be used in the form of their alkali metal, Erd ⁇ alkali metal or ammonium salts. Preference is given to Na.Li and Mg carbonates and hydrogen carbonates, in particular sodium carbonate and / or sodium bicarbonate.
  • Polyphosphates such as pentasodium triphosphate.
  • organic cobuilders are particularly suitable:
  • Low molecular weight carboxylic acids such as citric acid, hydrophobically modified citric acid, eg. , Agaricic acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, oxydisuccinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, alkyl and alkenylsuccinic acids and aminopolycarboxylic acids, e.g.
  • Nitrilotriacetic acid Nitrilotriacetic acid, .beta.-alanine diacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, ethylenediaminedisuccinic acid and methyl- and ethylglycinediacetic acid.
  • Oligomeric and polymeric carboxylic acids such as homopolymers of acrylic acid and aspartic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid, methacrylic acid or C 1 -C 4 -olefins, for example isobutene or long-chain ⁇ -olefins, vinyl C 1 -C 8 -alkyl ethers, vinyl acetate, vinyl propionate, ( Meth) acrylic esters of C 1 - C ⁇ alcohols and styrene.
  • the oligomeric and polymeric carboxylic acids are used in acid form or as the sodium salt.
  • Suitable bleaching agents are, for example, adducts of hydrogen peroxide with inorganic salts, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate perhydrate, and percarboxylic acids, such as phthalimidopercaproic acid.
  • Suitable bleach activators are e.g. N, N, N ', N'-tetraacetylethylenediamine (TAED), sodium p-nonanoyloxybenzenesulfonate and N-methylmorpholinium acetonitrile methylsulfate.
  • TAED tetraacetylethylenediamine
  • Enzymes preferably used in detergents are proteases, lipases, amylases, cellulases, oxidases and peroxidases.
  • Suitable color transfer inhibitors are, for example, homopolymers, copolymers and graft polymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-vinylpyridine N-oxide. Homo- and copolymers of 4-vinylpyridine reacted with chloroacetic acid are also suitable as color transfer inhibitors.
  • Example 2 A polymer solution having a solids content of 46.2% by weight and a K value of 66.5 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C.) was obtained.
  • Example 2 A polymer solution having a solids content of 46.2% by weight and a K value of 66.5 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C.) was obtained.
  • Example 2 A polymer solution having a solids content of 46.2% by weight and a K value of 66.5 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C.) was obtained.
  • a polymer solution having a solids content of 39.6% by weight and a K value of 52.9 (measured at pH 7 in 1% strength by weight aqueous solution at 25.degree. C.) was obtained.
  • a polymer solution having a solids content of 43.7% by weight and a K value of 65.9 (measured at pH 7 in 1% strength by weight aqueous solution at 25.degree. C.) was obtained.
  • Example 14 A polymer solution having a solids content of 28.3% by weight and a K value of 101.8 (measured at pH 7 in 1% strength by weight aqueous solution at 25.degree. C.) was obtained.
  • Example 14 A polymer solution having a solids content of 28.3% by weight and a K value of 101.8 (measured at pH 7 in 1% strength by weight aqueous solution at 25.degree. C.) was obtained.
  • a polymer solution having a solids content of 40.8% by weight and a K value of 69.6 (measured at pH 7 in 1% strength by weight aqueous solution at 25.degree. C.) was obtained.
  • Three different detergent slurries were prepared with stirring in a 500 ml heatable double-walled stainless steel vessel.
  • the liquid components were first heated to 50 ° C. with stirring for 10 minutes.
  • the stirrer used added over a torque pickup.
  • the previously mixed solid components were then uniformly metered in over 4 minutes, the slurry being stirred further at 150 rpm.
  • the slurry was stirred with constant Umdre ⁇ tion number while determining the torque.
  • the torque reflects the force needed to stir the slurry at a constant speed of rotation.
  • Table 1 lists the compositions of the detergent slurries.
  • the ge called quantities refer to feedstocks in anhydrous form, i. without water or water of crystallization contained in the total water content.
  • the inorganic tissue deposits were determined in the form of the ash content.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
EP05758640A 2004-06-25 2005-06-18 Procede de production de compositions detergentes granulaires ou pulverulentes Not-in-force EP1761622B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004031040A DE102004031040A1 (de) 2004-06-25 2004-06-25 Verfahren zur Herstellung von granulären oder pulverförmigen Waschmittelzusammensetzungen
PCT/EP2005/006597 WO2006000357A1 (fr) 2004-06-25 2005-06-18 Procede de production de compositions detergentes granulaires ou pulverulentes

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Publication Number Publication Date
EP1761622A1 true EP1761622A1 (fr) 2007-03-14
EP1761622B1 EP1761622B1 (fr) 2009-02-25

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US (1) US20070238637A1 (fr)
EP (1) EP1761622B1 (fr)
JP (1) JP2008503623A (fr)
CN (1) CN1973025B (fr)
AT (1) ATE423836T1 (fr)
BR (1) BRPI0512512A (fr)
CA (1) CA2571706C (fr)
DE (2) DE102004031040A1 (fr)
ES (1) ES2320787T3 (fr)
MX (1) MXPA06014512A (fr)
WO (1) WO2006000357A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005041349A1 (de) * 2005-08-31 2007-03-01 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate
US8034752B2 (en) 2008-03-11 2011-10-11 Afton Chemical Corporation Lubricating composition
JP5570144B2 (ja) * 2009-06-12 2014-08-13 花王株式会社 衣料洗剤用高分子ビルダー
ES2426730T3 (es) * 2011-05-10 2013-10-24 Sika Technology Ag Polímero de ácido maleico, éteres alílicos y compuestos de ácido (met)acrílico, su preparación y su utilización
US9127236B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid terpolymer for hard water scale control
US9127235B2 (en) * 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8928023D0 (en) * 1989-12-12 1990-02-14 Unilever Plc Detergent compositions
DE4328817A1 (de) * 1993-08-27 1995-03-02 Basf Ag Wasserlösliche, Carboxylgruppen enthaltende Copolymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung als Scaleinhibitor
US5723427A (en) * 1994-12-05 1998-03-03 Colgate-Palmolive Company Granular detergent compositions containing deflocculating polymers and processes for their preparation
DE19516957C2 (de) * 1995-05-12 2000-07-13 Stockhausen Chem Fab Gmbh Wasserlösliche Copolymere und Verfahren zu ihrer Herstellung und ihre Verwendung
US5733861A (en) * 1995-05-23 1998-03-31 Basf Corporation Hydrophilic copolymers for reducing the viscosity of detergent slurries
US5595968A (en) * 1995-05-23 1997-01-21 Basf Corporation Polymeric dispersants for soda ash based detergent slurries
WO1996037597A1 (fr) * 1995-05-23 1996-11-28 Basf Corporation Formulations de detergents
US5618782A (en) * 1995-05-23 1997-04-08 Basf Corporation Hydrophilic copolymers for reducing the viscosity of detergent slurries

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006000357A1 *

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CN1973025A (zh) 2007-05-30
DE502005006702D1 (de) 2009-04-09
CA2571706A1 (fr) 2006-01-05
JP2008503623A (ja) 2008-02-07
ES2320787T3 (es) 2009-05-28
CA2571706C (fr) 2013-06-11
ATE423836T1 (de) 2009-03-15
DE102004031040A1 (de) 2006-01-12
EP1761622B1 (fr) 2009-02-25
US20070238637A1 (en) 2007-10-11
CN1973025B (zh) 2010-05-05
WO2006000357A1 (fr) 2006-01-05
BRPI0512512A (pt) 2008-03-11
MXPA06014512A (es) 2007-03-23

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