EP0906397A2 - Utilisation de copolymeres pour augmenter la vitesse de dissolution de formulations detergentes particulaires dans l'eau - Google Patents

Utilisation de copolymeres pour augmenter la vitesse de dissolution de formulations detergentes particulaires dans l'eau

Info

Publication number
EP0906397A2
EP0906397A2 EP97924025A EP97924025A EP0906397A2 EP 0906397 A2 EP0906397 A2 EP 0906397A2 EP 97924025 A EP97924025 A EP 97924025A EP 97924025 A EP97924025 A EP 97924025A EP 0906397 A2 EP0906397 A2 EP 0906397A2
Authority
EP
European Patent Office
Prior art keywords
acid
esters
use according
weight
mixtures
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.)
Withdrawn
Application number
EP97924025A
Other languages
German (de)
English (en)
Inventor
Jürgen HUFF
Hans-Ulrich JÄGER
Martin Aus Dem Kahmen
Matthias Kroner
Jürgen Alfred LUX
Günter OETTER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0906397A2 publication Critical patent/EP0906397A2/fr
Withdrawn legal-status Critical Current

Links

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
    • C11D3/37—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • the invention relates to the use of copolymers which are obtainable by radical polymerization of
  • particulate detergent formulations as an additive to particulate detergent formulations to increase their dissolution rate in water in amounts of 0.1 to 10% by weight, based on the detergent formulations.
  • Particulate detergents should disintegrate into the individual components as quickly as possible in order to form the finished wash liquor.
  • the rate of dissolution of some particulate detergent formulations, in particular compact detergents, which have a bulk density of at least 550 g / l, for example, is still in need of improvement when combined with water.
  • the invention is based on the object of providing a detergent additive which leads to an increase in the rate of dissolution of particulate detergents in water.
  • particulate detergent formulations as an additive to particulate detergent formulations to increase their rate of dissolution in water in amounts of 0.1 to 10% by weight, based on the detergent formulations.
  • Copolymers to be used according to the invention are obtained, for example, if the copolymerization is used as (a) olefins with 2 to 30 C atoms, polymers containing at least one double bond of olefins with 3 to 10 C atoms, esters of C 3 - to C ⁇ -ethylenically unsaturated carboxylic acids and alcohols with 1 to 30 C atoms, vinyl esters of saturated Ci to C 30 carboxylic acids, half esters of ethylenically unsaturated C 4 to C ⁇ dicarboxylic acids and monohydric saturated alcohols with at least 5 C atoms, styrene and mixtures of the hydrophobic monomers mentioned and
  • Suitable olefins that are free of aromatic groups contain 2 to 30 carbon atoms.
  • Examples include ethylene, propylene, 1-butene, isobutylene, 1-pentene, cyclopentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, cyclohexene, 2, 3-dimethyl-1-butene , 3, 3-Dimethyl-1-butene, 2-ethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, diisobutene, cyclooctene , 1-Decen, 1-Dodecen, 1-Tetradecen, 1-Hexadecen, 1-Octadecen, 1-Eicosen, 1-Docosen, 1-Tetracosen, 1-Hexacosen, 1-Octacosen, 1-Triaconten, 1 -Tetracontene,
  • Polymers containing double bonds of olefins having 3 to 10 carbon atoms can be prepared by various processes. These are, for example, metallocene-catalyzed oligoolefins such as oligopropene, oligohexene and oligodecene or olefins obtainable by cationic polymerization with a high ⁇ -olefin content, such as polyisobutene or mixtures of different olefins. Such polymers contain at least one double bond in the molecule and have up to 150 carbon atoms / molecule.
  • esters of C 3 - to C ⁇ -ethylenically unsaturated carboxylic acids and alcohols with 1 to 30 C atoms examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert.
  • hydrophobic monomers are vinyl esters of saturated C 1 -C 30 -carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate and vinyl stearate.
  • the hydrophobic monomers can be used alone or as a mixture with one another in the copolymerization with the hydrophilic monomers.
  • Suitable hydrophilic monomers (b) are C 3 -C 6 -ethylenically unsaturated carboxylic acids, for example acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, ethacrylic acid and mesaconic acid.
  • the hydrophilic monomers also include the half-esters of monoethylenically unsaturated dicarboxylic acids and monohydric alcohols having 1 to 4 carbon atoms, such as monomethyl maleate, monoethyl maleate, monobutyl maleate, mono-n-butyl maleate, isopropyl maleate and maleic acid monoester .
  • esters of C 3 - to C ⁇ -monocarboxylic acids and polyalkylene glycols are suitable, for example esters of acrylic acid and polyethylene glycols with molar masses from 100 to 10,000.
  • hydrophilic monomers are addition products of ethylene oxide and, if appropriate, propylene oxide with monohydroxyalkyl vinyl ether, for example addition products of 1 to 100 Moles of ethylene oxide to 1 mole of 1,4-butanediol monovinyl ether.
  • Other hydrophilic monomers are vinyl sulfonic acid, methallylsulfonic acid, acrylamidopropanesulfonic acid and the alkali metal and ammonium salts of the sulfonic acid group-containing monomers and the alkali metal and ammonium salts of the carboxyl group-containing hydrophilic monomers.
  • maleic acid monomethyl ester maleic acid monoethyl ester, maleic acid monoisopropyl ester, esters of acrylic acid and polyethylene glycols with 2 to 50 ethylene glycol units, addition products of 1 to 50 mol of ethylene oxide with 1 mol of 1,4-butanediol diol monovinyl ether and mixtures of the hydrophilic monomers mentioned
  • the hydrophobic and hydrophilic monomers are copolymerized by known processes.
  • copolymers of ethylene and acrylic acid or copolymers of ethylene, acrylic acid and butyl acrylate are produced by the process of high-pressure polymerization of ethylene in the presence of free radical initiators, pressures above 1000 bar and temperatures from 150 to 250 ° C.
  • Copolymers of isobutene or Diisobutene and maleic acid are advantageously prepared by polymerizing diisobutene and maleic anhydride or by polymerizing isobutene and maleic anhydride and subsequent hydrolysis of the copolymers containing anhydride groups.
  • the polymerization can be carried out in bulk, as solution polymerization in a solvent or as precipitation polymerization in an aliphatic or aromatic hydrocarbon.
  • Copolymers containing maleic anhydride groups can be hydrophobically modified by reaction with, for example, long-chain alcohols, for example monohydric saturated C 1 -C 3 -alcohols. The corresponding half-ester groups result from the copolymerized anhydride groups.
  • Polymers that are suitable for the use according to the invention are, for example, copolymers
  • copolymers which can be obtained by copolymerizing the monomers in preferably nonionic surfactants, polyalkylene glycols or mixtures thereof.
  • Suitable surfactants are, for example, the alkoxylation products which are usually present in detergents and which, if appropriate, can also be esterified by reaction with sulfuric acid.
  • the nonionic surfactants are, for example, addition products of ethylene oxide and, if appropriate, propylene oxide onto monohydric alcohols with 10 to 30 carbon atoms, alkylphenols, fatty amines with 10 to 30 carbon atoms, fatty acids with 10 to 30 carbon atoms, Sorbitan esters, sucrose esters, glycerol esters, polyglycerol esters and alkyl (poly) saccharides.
  • the copolymerization can also advantageously be carried out in polyalkylene glycols.
  • Suitable polyalkylene glycols are, for example, the addition products of 1 to 100 moles of ethylene oxide and, if appropriate, up to 20 moles of propylene oxide with 1 mole of an at least dihydric alcohol.
  • at least dihydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, glycerol, erythritol, pentaerythritol, trimethylolpropane, mannitol, sorbitol or mixtures of the compounds mentioned.
  • Particularly preferred surfactants are the addition products of 2 to 25 moles of ethylene oxide and optionally up to 20 moles of propylene oxide with 1 mole of a monohydric alcohol having 12 to 22 carbon atoms.
  • the concentrations of monomers therein are, for example, 1 to 95, preferably 5 to 90,% by weight.
  • the surfactants or polyalkylene glycols used as diluents can be used in the copoly merization of the hydrophobic and the hydrophilic monomers are optionally grafted.
  • the usual amounts of compounds which form free radicals under the reaction conditions, such as peroxides, hydroperoxides, hydrogen peroxide, azo compounds, peroxydisulfates, etc., are used in the copolymerization.
  • the copolymerization can optionally be carried out in the presence of the customary polymerization regulators, for example carbon tetrachloride, chloroform, aldehydes, formic acid or formic acid esters, organic sulfides, disulfides, polysulfides and mercapto compounds.
  • the customary polymerization regulators for example carbon tetrachloride, chloroform, aldehydes, formic acid or formic acid esters, organic sulfides, disulfides, polysulfides and mercapto compounds.
  • Mercapto alcohols, mercaptocarboxylic acids and mercaptoalkanes with 2 to 30 carbon atoms in the molecule for example 2-mercaptoethanol, 1, 3-mercaptopropanol, 3-mercaptopropane-1, 2-diol, 1, 4-mercapto-butanol, cysteine, mercaptoacetic acid, are particularly preferred , 3-mercaptopropionic acid, mercaptosuccinic acid, n-butyl mercaptan, n-hexyl mercaptan, n-didecyl mercaptan or tert. -Dodecyl mercaptan.
  • polymerization regulators are used, they are used in the usual amounts, e.g. up to 10% by weight, preferably 0.1 to 5% by weight, based on the monomers in the reaction mixture.
  • the copolymers to be used according to the invention have, for example, molecular weights M w of from 500 to 500,000, preferably from 1000 to 100,000.
  • the weight-average molecular weights were determined by the light scattering method.
  • copolymers to be used according to the invention from hydroph ⁇ top and hydrophilic monomers are preferably by polymerizing
  • the copolymers are used in amounts of 0.1 to 10, preferably 0.5 to 2.5,% by weight as an additive to particulate detergent formulations to increase the rate of dissolution of the particulate detergents.
  • the copolymers of hydrophobic and hydrophilic monomers are mixed as homogeneously as possible with the other constituents of the detergent formulation.
  • the copolymers to be used according to the invention can also be applied to the surface of the finely divided detergent formulations in the amounts specified above.
  • the copolymers diffuse into the particulate detergents.
  • the detergents can be in powder form or in the form of granules, flakes, strands, spheres, platelets or tablets.
  • the average particle diameter of the particulate Wasch ⁇ is, for example 200 microns to 5 mm an d is preferably in the range of 1 mm to third
  • the detergent formulations can also be portioned in such a way that, for example, only one ball or tablet is required for a washing cycle in a washing machine.
  • Such spheres or tablets then have a much larger average particle diameter than stated above.
  • the advantage of such relatively large-volume particles lies in the simple metering.
  • the detergents can be full detergents or special detergents. Both anionic and nonionic or mixtures of anionic and nonionic surfactants are suitable as surfactants.
  • the surfactant content of the detergents is preferably 8 to 30% by weight.
  • Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18, carbon atoms, for example C 9 to Cn alcohol sulfates, C 2 to C 13 alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.
  • Suitable anionic surfactants are sulfated, ethoxylated C 8 to C 22 alcohols or their soluble salts.
  • Compounds of this type are prepared, for example, by first alkoxylating a C 8 to C 22 , preferably a C 0 to C 1 alcohol, and then sulfating the alkoxylation product.
  • the alkoxylation is preferably used
  • Ethylene oxide 2 to 50, preferably 3 to 20, moles of ethylene oxide being used per mole of fatty alcohol.
  • the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide.
  • Such alkoxylated C ⁇ 'to C 22 alcohols, the ethylene oxide and Propylen ⁇ are suitable also include oxide or ethylene oxide and butylene
  • the alkoxylated C 8 -. -C 22 -alcohols can contain the ethylene oxide, and butylene oxide units in the form Propylen ⁇ contained in blocks or in statistical distribution.
  • Suitable anionic surfactants are alkyl sulfonates such as C ⁇ - to C 24 -, preferably Cirj-Ci ⁇ -alkanesulfonates and soaps such as the salts of C 8 - to C 24 -carboxylic acids.
  • Suitable anionic surfactants are Cg to C 20 linear alkylbenzenesulfonates (LAS).
  • the polymers according to the invention are preferably used in low-LAS detergent formulations less than 4%, particularly preferably used in LAS-free formulations.
  • the anionic surfactants are preferably added to the detergent in the form of salts.
  • Suitable cations in these salts are alkali metal salts such as sodium, potassium, lithium and ammonium salts such as e.g. Hydroxyethylammonium, di (hydroxy ⁇ ethyl) ammonium and tri (hydroxyethyl) ammonium salts.
  • Suitable nonionic surfactants are, for example, alkoxylated C ⁇ to C 22 alcohols.
  • the alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant.
  • block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. 2 to 5, preferably 3 to 20, moles of at least one alkylene oxide are used per mole of alcohol.
  • Ethylene oxide is preferably used as the alkylene oxide.
  • the alcohols preferably have 10 to 18 carbon atoms.
  • alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. These compounds contain 1 to 20, preferably 1.1 to 5, glucoside units.
  • N-alkylglucamides of the general structure I or II
  • A is a C 6 to C 22 alkyl
  • B is an H or C 1 to C 4 alkyl
  • C is a polyhydroxyalkanyl radical having 5 to 12 C atoms and at least 3 hydroxyl groups.
  • A is preferably C 1 -C 18 -alkyl
  • B is CH 3
  • C is a C 5 or C 6 radical.
  • such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of
  • the detergent formulations preferably contain 3-12 mol ethylene oxide Cirj-Ci ⁇ -alcohols ethoxylated, particularly preferably ethoxylated fatty alcohols as nonionic surfactants.
  • Further preferred surfactants are the end group-capped fatty acid amide alkoxylates of the general formula known from WO-A-95/11225
  • R 1 is a C 5 - to C denotes 2 ⁇ alkyl or alkenyl
  • R 2 is a Ci to C 4 alkyl group
  • A is C 2 - to C 4 -alkylene
  • n is the number 2 or 3 and denotes x has a value from 1 to 6.
  • Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H 2 N- (CH 2 -CH 2 -0) 3 -C 4 H 9 with methyl dodecanoate or the reaction products of ethyltetraglycolamine of the formula H 2 N- ( CH 2 -CH 2 -0) 4 -C 2 H 5 with a commercially available mixture of saturated C 8 - to Ci ⁇ -fatty acid methyl esters.
  • the powder or granular detergents also one or more inorganic builders. All customary inorganic builders such as aluminosilicates, silicates, carbonates and phosphates are suitable as inorganic builder substances.
  • Suitable inorganic builders are e.g. Aluminum silicates with ion-exchanging properties such as Zeolites.
  • zeolites are suitable, in particular zeolite A, X, B, P, MAP and HS in their Na form or in forms in which Na is partly replaced by other cations such as Li, K, Ca, Mg or ammonium.
  • Suitable zeolites are described, for example, in EP-A-0 038 591, EP-A-0 021 491, EP-A-0 087 035, US-A-4 604 224, GB-A-2 013 259, EP-A- 0 522 726, EP-A-0 384 070A and WO-A-94/24251.
  • Suitable inorganic builders are e.g. amorphous or crystalline silicates such as e.g. amorphous disilicates, crystalline disilicates such as the layered silicate SKS-6 (manufacturer Hoechst AG).
  • the silicates can be used in the form of their alkali, alkaline earth or ammonium salts. Na, Li and Mg silicates are preferably used.
  • Suitable inorganic builder substances are carbonates and hydrogen carbonates. These can be used in the form of their alkali, alkaline earth or ammonium salts. Preferably be Na, Li and Mg carbonates or hydrogen carbonates, in particular sodium carbonate and / or sodium hydrogen carbonate.
  • the inorganic builders can be present in the detergents in quantities of 5 from 0 to 60% by weight together with organic cobuilders which may be used.
  • the inorganic builders can be incorporated into the detergent either alone or in any combination with one another. In powdery or granular detergents, they are added in amounts of 10 to 10 60% by weight, preferably in amounts of 20 to 50% by weight.
  • Organic cobuilders in amounts of 0.1 to 20% by weight, preferably in amounts of 1 to 15% by weight, are combined in powdered or granular or other solid detergent formulations
  • the powdery or granular heavy-duty detergents can also contain, as other conventional constituents, a bleaching system consisting of at least one bleaching agent, optionally in combination with a bleach activator and / or a bleaching catalyst.
  • Suitable bleaches are perborates and percarbonate in the form of their alkali metal salts, in particular their Na salts. They are contained in the formulations in amounts of 5 to 30% by weight, preferably 10 to 25% by weight.
  • Other suitable bleaching agents are 5 inorganic and organic peracids in the form of their alkali or magnesium salts or in some cases also in the form of the free acids.
  • suitable organic percarboxylic acids or salts are e.g. Mg monoterephthalate, phthalimidopercaproic acid and dodecane-1, 10-diper acid.
  • An example of an inorganic peracid salt is potassium peroxomonosulfate (oxone).
  • Suitable bleach activators are e.g.
  • Acylamines such as tetraacetylethylene diamine, tetraacetyl glycol 5 ril, N, N '-diacetyl-N, N' -dimethylurea and 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • acylated lactams such as acetylcaprolactam, octanoylcaprolactam and benzoylcaprolactam 0 substituted phenol esters of carboxylic acids such as e.g. Na acetoxybenzenesulfonate, Na octanoyloxybenzenesulfonate and Na nonanoyloxybenzenesulfonate
  • 5-acylated sugars such as pentaacetyl glucose Anthranil derivatives such as 2-methylanthranil or 2-phenylanthranil
  • Enol esters such as Isopropenyl acetate
  • Oxime esters such as O-acetylacetone oxime
  • Carboxylic anhydrides e.g. Phthalic anhydride or acetic anhydride.
  • Tetraacetylethylenediamine and Na nonanoyloxybenzenesulfonates are preferably used as bleach activators.
  • the bleach activators are heavy-duty detergents in amounts of 0.1 to 15% by weight, preferably in amounts of 1.0 to 8.0% by weight, particularly preferably in amounts of 1.5 to 6.0% by weight. % added.
  • Suitable bleaching catalysts are quaternized imines and sulfonimines as described in US-A-5 360 568, US-A-5 360 569 and EP-A-0 453 003 and Mn complexes, cf. e.g. WO-A-94/21777. If bleach catalysts are used in the detergent formulations, they are in amounts of up to 1.5% by weight, preferably up to 0.5% by weight, in the case of the very active manganese complexes in amounts of up to 0.1% by weight .% contain.
  • the detergents preferably contain an enzyme system. These are proteases, lipases, amylases and cellulases commonly used in detergents.
  • the enzyme system may be limited to a single one of the enzymes or may include a combination of different enzymes. As a rule, amounts of 0.1 to 1.5% by weight, preferably 0.2 to 1.0% by weight, of the finished enzyme are added to the detergents of the enzymes customary in the trade.
  • Suitable proteases are, in part, Savinase and Esperase (manufacturer Novo Nordisk).
  • a Lipase is, for example, Lipolase (manufacturer Novo Nordisk).
  • a suitable cellulase is, for example, Celluzym (manufacturer Novo Nordisk).
  • the detergents preferably contain soil release polymers and / or graying inhibitors as other common constituents. This is e.g. around
  • Polyesters from polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids are known, cf. for example US-A-3 557 039, GB-A-1 154 730, EP-A-0 185 427, EP-A-0 241 984, EP-A-0 241 985, EP-A-0 272 033 and US-A-5 142 020.
  • soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides, cf. US-A-4 746 456, US-A-4 846 995, DE-A-3 711 299, US-A-4 904 408, US-A-4 846 994 and US-A-4 849 126 or modi ⁇ fected celluloses such as Methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.
  • Graying inhibitors and soil release polymers are present in the detergent formulations in an amount of 0 to 2.5% by weight, preferably 0.2 to 1.5% by weight, particularly preferably 0.3 to 1.2% by weight.
  • Soil release polymers used with preference are the graft polymers of vinyl acetate on polyethylene oxide of molecular weight 2500-8000 in a weight ratio of 1.2: 1 to 3.0: 1, known from US Pat. No.
  • polyethylene terephthalate / polyoxyethylene terephthalates the molecular weight 3000 to 25000 from polyethylene oxides of the molecular weight 750 to 5000 with terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and the block polycondensates known from DE-A-4 403 866, the blocks from (a) contain ester units from polyalkylene glycols with a molecular weight of 500 to 7500 and aliphatic dicarboxylic acids and / or monohydroxymonocarboxylic acids and (b) ester units from aromatic dicarboxylic acids and polyhydric alcohols.
  • These amphiphilic block copolymers have molecular weights from 1500 to 25000.
  • a typical powder or granular heavy-duty detergent can have the following composition, for example:
  • a color transfer inhibitor based on water-soluble homopolymers of N-vinylpyrrolidone or N-vinylimidazole, water-soluble copolymers of N-vinylimidazole and N-vinylpyrrolidone Copolymers of N-vinyl imidazole and N-vinyl pyrrolidone with a particle size of 0.1 to 500, preferably up to 250 ⁇ m, these copolymers being 0.01 to 5, preferably 0.1 to 2% by weight of N, N ' -Divinylethyleneurea contain as crosslinker.
  • Further color transfer inhibitors are water-soluble and also crosslinked polymers of 4-vinylpyridine-N-oxide, which can be obtained by polymerizing 4-vinylpyridine and subsequent oxidation of the polymers,
  • a bleaching system is often completely or partially dispensed with in color-gentle special detergents (for example in so-called color detergents).
  • color detergents for example in so-called color detergents.
  • a typical powder or granular color detergent can have the following composition, for example:
  • a soil release polymer e.g. a graft polymer of vinyl acetate on polyethylene glycol.
  • the powdery or granular detergents can contain up to 60% by weight of inorganic stabilizers as other common constituents. Sodium sulfate is usually used for this. However, the detergents are preferably low in adjusting agents, i.e. they contain up to 20% by weight, particularly preferably up to 8% by weight, of adjusting agents.
  • the detergents can have different bulk densities in the range from 300 to 1000 g / l. Modern compact laundry detergents generally have high bulk densities, e.g. 550 to 1000 g / 1, and show a granulate structure. In most cases, the bulk density of the detergent formulations is at least 700 g / l.
  • the detergents can optionally contain other customary additives.
  • additives e.g. Complexing agents, phosphonates, optical brighteners, dyes, perfume oils, foam dampers and corrosion inhibitors can be included. They can also contain up to 20% by weight of water. The data in% mean percent by weight.
  • the monomer concentration in the polyethylene glycol was 40%.
  • a copolymer of styrene and acrylic acid with a molar mass M w of 30,000 was obtained.
  • the copolymer was used in the form of the sodium salt, which was prepared by neutralizing the acid form with aqueous sodium hydroxide solution.
  • a monomer mixture of vinyl acetate, acrylic acid and maleic anhydride was polymerized in a weight ratio of 50:35:35 in toluene at a temperature of 70 ° using 5% by weight of tert. -Butyl peroctoate as an initiator. Following the polymer The anhydride group-containing copolymer was reacted with n-butanol, so that a copolymer with units of vinyl acetate, acrylic acid and maleic acid mono-n-butyl ester was obtained. The toluene was removed using a steam distillation 5. An aqueous polymer solution with a
  • the copolymer was used in the form of the sodium salt.
  • Diisobutene and maleic anhydride were tert under pressure at a temperature of 160 ° C in the presence of 2% in an autoclave equipped with a stirrer.
  • An alternating copolymer with a molecular weight M w of 12,000 was obtained. It is used in the form of the sodium salt.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne l'utilisation de copolymères pouvant être obtenus par polymérisation par voie radicalaire, contenant (a) de 10 à 90 % en poids de monomères hydrophobes et (b) de 90 à 10 % en poids de monomères hydrophiles. Ces copolymères sont ajoutés à des formulations détergentes particulaires afin d'augmenter leur vitesse de dissolution dans l'eau, à raison de 0,1 à 10 % en poids par rapport aux formulations détergentes.
EP97924025A 1996-06-03 1997-05-28 Utilisation de copolymeres pour augmenter la vitesse de dissolution de formulations detergentes particulaires dans l'eau Withdrawn EP0906397A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19621983 1996-06-03
DE1996121983 DE19621983A1 (de) 1996-06-03 1996-06-03 Verwendung von Copolymeren aus hydrophilen und hydrophoben Monomeren zur Erhöhung der Lösegeschwindigkeit von teilchenförmigen Waschmittelformulierungen in Wasser
PCT/EP1997/002764 WO1997046657A2 (fr) 1996-06-03 1997-05-28 Utilisation de copolymeres pour augmenter la vitesse de dissolution de formulations detergentes particulaires dans l'eau

Publications (1)

Publication Number Publication Date
EP0906397A2 true EP0906397A2 (fr) 1999-04-07

Family

ID=7795860

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97924025A Withdrawn EP0906397A2 (fr) 1996-06-03 1997-05-28 Utilisation de copolymeres pour augmenter la vitesse de dissolution de formulations detergentes particulaires dans l'eau

Country Status (3)

Country Link
EP (1) EP0906397A2 (fr)
DE (1) DE19621983A1 (fr)
WO (1) WO1997046657A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19912031A1 (de) 1999-03-17 2000-09-21 Basf Ag Verwendung von quervernetztem Polyvinylpyrrolidon zur Erhöhung der Zerfallgeschwindigkeit von kompakten teilchenförmigen Wasch- und Reinigungsmitteln
DE102005047833A1 (de) * 2005-10-05 2007-04-19 Basf Ag Verfahren zur Herstellung von granulären oder pulverförmigen Waschmittelzusammensetzungen
WO2009007328A2 (fr) * 2007-07-06 2009-01-15 Basf Se Utilisation d'homo- et de copolymères pour la stabilisation de formulations de substances actives
EP4458923A3 (fr) 2015-12-10 2024-12-18 Specialty Operations France Copolymères séquencés formant des couches polyélectrolytes et compositions et leur utilisation
AR114185A1 (es) 2018-01-23 2020-07-29 Adama Makhteshim Ltd Síntesis de 5-cloro-2-[(3,4,4-trifluoro-3-buten-1-il)tio]-tiazol

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0080222B2 (fr) * 1981-11-16 1991-03-20 The Procter & Gamble Company Procédé de préparation de compositions détergentes granulaires contenant un agent tensio-actif anionique additionné et un polymer anionique
JPH0665720B2 (ja) * 1985-04-03 1994-08-24 花王株式会社 濃縮粉末洗剤組成物
FR2581323B1 (fr) * 1985-05-06 1987-05-29 Rhone Poulenc Spec Chim Nouvelle composition tensio-active, son procede d'obtention et ses applications
JPH02155928A (ja) * 1988-12-07 1990-06-15 Kao Corp ポリ（ｎ−アシルエチレンイミン）系ブロック共重合体及びその用途
JP2951851B2 (ja) * 1994-09-22 1999-09-20 花王株式会社 非イオン性粉末洗浄剤組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9746657A3 *

Also Published As

Publication number Publication date
WO1997046657A3 (fr) 1998-01-15
DE19621983A1 (de) 1997-12-04
WO1997046657A2 (fr) 1997-12-11

Similar Documents

Publication Publication Date Title
EP0471710B1 (fr) Copolymerisats formes par polymerisation de monomeres renfermant des blocs d'oxyde de polyalkylene, leur preparation et leur emploi
DE69019814T2 (de) Wasserlösliche Copolymere mit niedrigem Molekulargewicht, Verfahren zu deren Herstellung und diese enthaltende Wasch- und Reinigungsmittel.
DE112014006990T5 (de) Sulfonatgruppenhaltiges polymer und verfahren zur herstellung hiervon
EP1587848B1 (fr) Copolymeres partiellement esterifies d'anhydrides d'acide dicarboxylique monoethyleniquement insatures, de composes vinylaromatiques et d'autres monomeres monoethyleniquement insatures contenant des heteroatomes
EP0377448A2 (fr) Utilisation de copolymères de 1,2-di-alkoxyéthylènes et d'anhydrides d'acides dicarboxyliques insaturés monoéthyléniquement dans des détergents contenant ces copolymères
EP0637627B1 (fr) Formulations détergentes
EP0906396B1 (fr) Utilisation de copolymerisats contenant des unites nvi ou nvpo et solubles dans l'eau comme inhibiteurs de transfert de couleurs dans des compositions de lessive
EP0906397A2 (fr) Utilisation de copolymeres pour augmenter la vitesse de dissolution de formulations detergentes particulaires dans l'eau
EP1761622B1 (fr) Procede de production de compositions detergentes granulaires ou pulverulentes
EP1448642B1 (fr) Polymeres greffes presentant des chaines laterales qui contiennent des n-vinylamides cycliques
EP0706558A1 (fr) Detergents pour lave-vaisselle contenant des adjuvants biodegradables
DE19532718A1 (de) Pulverförmige, poröse, N-Vinylimidazol-Einheiten enthaltende Polymere, Verfahren zu ihrer Herstellung und ihre Verwendung
EP0901515B1 (fr) Utilisation d'alcools au moins trivalents et leurs produits d'alcoxylation pour augmenter la vitesse de dissolution de formulations de detergents particulaires dans l'eau
EP1941016B1 (fr) Procede pour produire des compositions detergentes en granules ou en poudre
EP0469018A1 (fr) Copolymeres a base d'anhydrides d'acide bicarbonique monoethyleniquement insatures, de dicetene et d'acides monocarboniques monoethyleniquement insatures; production et utilisation de ces copolymeres
DE3927811A1 (de) Copolymerisate aus carbonsaeureanhydriden und ketenderivaten
EP0938539B1 (fr) Usage des produits d'alcoxylation d' alcools au moins trivalents pour augmenter la vitesse de dissolution dans l' eau des detergents particulaires pour le linge
EP0541588B1 (fr) Utilisation de polymeres contenant des groupes n-(alkyloxy-polyalcoxymethyl)carbonamides comme additifs d'agents de lavage et de nettoyage
DE19648504A1 (de) Verwendung von hydrophobierten, alkoxylierten mindestens dreiwertigen Alkoholen zur Erhöhung der Lösegeschwindigkeit von teilchenförmigen Waschmittelformulierungen in Wasser
DE19608044A1 (de) Verwendung von hydrophob modifizierten Copolymerisaten aus monoethylenisch ungesättigten Dicarbonsäuren und Olefinen mit 2 bis 8 C-Atomen in Wasch- und Reinigungsmitteln
DE19647609A1 (de) Verwendung von mindestens dreiwertigen Alkoholen und deren Alkoxylierungsprodukten zur Erhöhung der Lösegeschwindigkeit von teilchenförmigen Waschmittelformulierungen in Wasser
DE19532715A1 (de) Waschmittel
EP0765352A1 (fr) Copolymeres contenant des unites vinylformiate, leur procede de preparation et leur utilisation dans des detergents et des nettoyants

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19981005

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE ES FR GB IT

17Q First examination report despatched

Effective date: 19991213

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 20000322