EP0541588B1 - Utilisation de polymeres contenant des groupes n-(alkyloxy-polyalcoxymethyl)carbonamides comme additifs d'agents de lavage et de nettoyage - Google Patents

Utilisation de polymeres contenant des groupes n-(alkyloxy-polyalcoxymethyl)carbonamides comme additifs d'agents de lavage et de nettoyage Download PDF

Info

Publication number
EP0541588B1
EP0541588B1 EP91912925A EP91912925A EP0541588B1 EP 0541588 B1 EP0541588 B1 EP 0541588B1 EP 91912925 A EP91912925 A EP 91912925A EP 91912925 A EP91912925 A EP 91912925A EP 0541588 B1 EP0541588 B1 EP 0541588B1
Authority
EP
European Patent Office
Prior art keywords
carboxylic acids
weight
polymer
monoethylenically unsaturated
acid
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.)
Expired - Lifetime
Application number
EP91912925A
Other languages
German (de)
English (en)
Other versions
EP0541588A1 (fr
Inventor
Matthias Kroner
Fritz Erdmann Kempter
Richard Baur
Paul Diessel
Volker Schwendemann
Walter Denzinger
Heinrich Hartmann
Manfred Niessner
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 EP0541588A1 publication Critical patent/EP0541588A1/fr
Application granted granted Critical
Publication of EP0541588B1 publication Critical patent/EP0541588B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines

Definitions

  • the invention relates to the use of polymers which, as an essential monomer, contain copolymerized N- (alkyloxy-polyalkoxymethyl) carboxamides of monoethylenically unsaturated C3- to C8-carboxylic acids, as an additive to detergents and cleaning agents and detergents and cleaning agents which contain such polymers.
  • EP-PS 0 116 930 describes water-soluble copolymers of 40 to 90% by weight of at least one ethylenically unsaturated monocarboxylic acid with 3 to 5 C atoms and 60 to 10% by weight of at least one ethylenically unsaturated dicarboxylic acid with 4 to 8 C Atoms and / or their corresponding dicarboxylic acid anhydrides are known, in which 2 to 60% by weight, based on the total weight of the carboxylic acids or carboxylic acid anhydrides, are esterified with alkoxylated C1 to C18 alcohols or C1 to C12 alkylphenols.
  • the partially esterified copolymers and their water-soluble salts are used, inter alia, in amounts of 0.5 to 10% by weight in liquid detergent formulations.
  • the compatibility of the partially esterified copolymers of at least one monoethylenically unsaturated monocarboxylic acid is and at least one monoethylenically unsaturated dicarboxylic acid is significantly cheaper than in the non-esterified products, so that there are fewer phase separations.
  • the partially esterified copolymers of the type described are not stable to hydrolysis, so that they hydrolyze in liquid detergent formulations. As a result, inhomogeneities occur, which can even go so far as to result in the phase separation of the liquid detergent.
  • EP-A-0 237 075 discloses liquid detergents which contain at least one nonionic surface-active agent in an amount of 5 to 25% by weight, 2 to 25% by weight of a builder, about 1 to 10% by weight of C4 - To C30 ⁇ -olefin-maleic anhydride copolymers and, to make up to 100 wt .-%, water. Although these liquid detergents initially represent clear solutions, they separate relatively quickly during storage.
  • liquid alkaline detergent formulations which, in addition to water and detergents as stabilizers, contain 0.1 to 5%, based on the entire formulation, of a hydrolyzed copolymer of an ⁇ , ⁇ -unsaturated carboxylic anhydride with a vinyl ester, vinyl ether or contain an ⁇ -olefin in partially esterified form.
  • the alcohol components used for esterification include addition products of alkylene oxides, in particular ethylene oxide onto alkylphenols, also come into consideration. Only 0.01 to 5% of the carboxyl groups of the copolymer are present as ester groups.
  • these liquid detergents contain components which are compatible with one another, the primary washing action of this liquid detergent formulation is still in need of improvement.
  • EP-A-0 215 251 describes the use of homopolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and methacrylic acid and of copolymers of ethylenically unsaturated dicarboxylic acids with 4 to 6 carbon atoms and acrylic acid or methacrylic acid in each case partially neutralized and / or with long-chain amines and / or partially amidated form as a graying-inhibiting additive to detergents and cleaning agents which promotes the primary washing action in quantities of 0.05 to 10% by weight.
  • the partially amidated homopolymers and copolymers are prepared by reacting the polymers with long-chain amines. In many cases they still contain free amines, which are undesirable in detergent formulations because of their smell and physiological concern.
  • copolymers of acrylic acid and methacrylic acid esters of ethoxylated alcohols as addition of detergents are known from US Pat. No. 4,797,223.
  • EP-A-0 368 214 is the use of copolymers of monoethylenically unsaturated C3- to C8-carboxylic acids, esters of these carboxylic acids with alkyl vinyl ethers or mixtures of these monomers and amides of monoethylenically unsaturated C3- to C8-carboxylic acids in which the amide groups are one C8- to C28 alkyl radical or contain a polyalkyleneoxy radical which is bonded to the nitrogen atom via an alkylene group, known as an additive to liquid detergents in amounts of up to 20% by weight.
  • Such copolymers allow the production of storage-stable liquid detergents, they hydrolyze relatively quickly at the high pH values of the detergent formulations.
  • the object of the present invention is to provide other polymers which are easy to prepare and hydrolysis-stable at high pH values for use in detergents and cleaning agents.
  • the polymers to be used in detergents and cleaning agents according to the invention contain as essential monomer at least 5% by weight of N- (alkyloxy-polyalkoxymethyl) carboxamides of monoethylenically unsaturated C3- to C8-carboxylic acids with amide groups of the structure I given above 11 of EP-B-0 063 018 obtainable by reacting N-isobutoxymethyl acrylamide in the presence of acids with alkoxylated alcohols.
  • the reaction products of alcohol and polytetrahydrofuran can be used as a possible reaction component.
  • Compounds of the formula III are obtained by reacting monovalent C1 to C28 alcohols, monovalent C3 to C28 alkenols, phenol and C1- to C18 alkylphenols with alkylene oxides with 2-4 carbon atoms.
  • the compounds containing OH groups mentioned can be reacted, for example, with ethylene oxide, propylene oxide or butylene oxide.
  • the alkylene oxides can be used either alone or as a mixture in the alkoxylation will. In the latter case, the alkoxylation produces products which contain the alkylene oxides copolymerized in a random distribution. However, the alkylene oxides can also be used in succession in the alkoxylation reaction, so that block copolymers are formed.
  • a compound of the general formula R1-OH in which R1 has the meaning given in formula III, is first reacted with ethylene oxide, then with propylene oxide and then with butylene oxide.
  • R1 has the meaning given in formula III
  • Further possible variations result from the fact that the alkoxylation is first started with propylene oxide, then ethylene oxide and then again propylene oxide.
  • Further possible variations are conceivable for the preparation of compounds of the formula III, namely addition of alkylene oxides onto compounds of the formula R 1 -OH in the order of ethylene oxide, butylene oxide, propylene oxide or butylene oxide-ethylene oxide-propylene oxide.
  • the alkoxylation products of monohydric C1 to C18 alcohols and of monohydric C3- to C18 alkenols, especially oleyl alcohol are preferably used as compounds of formula III for the preparation of the essential monomers.
  • Ethylene oxide and / or propylene oxide are preferably used as alkoxylating agents. They are preferably used in an amount of 3 to 100 mol / mol alcohol.
  • the compounds of formula III are preferably water-soluble.
  • Suitable monoethylenically unsaturated C3- to C8-carboxylic acids are, for example, acrylic acid, methacrylic acid, vinyl acetic acid, 2-ethyl acrylic acid, maleic acid, fumaric acid, crotonic acid and itaconic acid. Acrylic acid, methacrylic acid and maleic acid are preferred.
  • Suitable esters of the above-mentioned carboxylic acids with C1 to C28 alcohols are, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, tert-butyl acrylate Butyl ester of methacrylic acid, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, isobutyl acrylate, isobutyl methacrylate, palmitylacrylate, palmityl methacrylate, stearyl acrylate, stearyl methacrylate, maleate dimethyl ester, maleate diethy
  • polymers which contain copolymerized as comonomers of group b) esters of monoethylenically unsaturated C3- to C8-carboxylic acids and polyhydric alcohols, for example hydroxylethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl acid and acrylic methacrylate, and the ester of methacrylate and methacrylate 1,6-hexanediol.
  • esters of monoethylenically unsaturated C3- to C8-carboxylic acids and polyhydric alcohols for example hydroxylethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl acid and acrylic methacrylate, and the ester of methacrylate and methacrylate 1,
  • Suitable esters of monoethylenically unsaturated C3- to C8-carboxylic acids with reaction products from alcohols and alkylene oxides are, for example, the esters of acrylic acid and methacrylic acid with ethoxylated C1- to C2 ein--alcohols, the one or one by adding 1 to 100 moles of ethylene oxide to 1 mole polyhydric alcohol.
  • Mixtures of alkylene oxides can also be used in the ethoxylation of the alcohols, e.g. Mixtures of ethylene oxide, propylene oxide and / or butylene oxide. In this case, statistical additions of the alkylene oxides to the alcohols are obtained.
  • Suitable monomers of group b) are C1 to C28 alkyl vinyl ethers, for example methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, dodecyl vinyl ether and octadecyl vinyl ether.
  • Styrene can also be used as the monomer of group b).
  • amides and nitriles of monoethylenically unsaturated C3- to C8-carboxylic acids especially acrylamide, methacrylamide, acrylonitrile and methacrylonitrile come into consideration.
  • N-Alkyloxymethyl-carboxamides with C1 to C18 alkyl radicals serve as starting products for the preparation of the monomers a) by reaction with alkoxylated alcohols and as a monomer of group b).
  • starting products are: N-methoxymethylacrylamide, N-methoxymethyl methacrylamide, N-ethoxymethylacrylamide, N-ethoxymethyl methacrylamide, N-propoxymethylacrylamide, N-propoxymethyl-methacrylamide, N-iso-propoxymethylacrylamide, N-iso-propoxymethyl methacrylamide, N-iso-propoxymethyl methacrylamide Btuoxymethyl methacrylamide, N-iso-butoxymethylacrylamide, N-iso-butoxymethyl methacrylamide, N-tert-butoxymethylacrylamide, N-tert-butoxymethyl methacrylamide, as well as higher homologues such as N-decyloxymethylacrylamide, N-decyloxymethyl methacrylamide, N-o
  • N-alkoxymethyl carboxamides N-butoxymethylacrylamide, N-butoxymethyl methacrylamide, N-iso-butoxymethylacrylamide and N-iso-butoxymethyl methacrylamide are preferably used.
  • Suitable vinyl esters of saturated carboxylic acids having 1 to 20 carbon atoms are, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and vinyl stearate.
  • Suitable monomers of group b) are: N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinyl acetamide and monomers containing sulfo groups, such as acrylamidopropanesulfonic acid, allylsulfonic acid, vinyl sulfonic acid and their alkali metal and ammonium salts.
  • the monomers of group b) can be used either alone or in the form of mixtures in the preparation of the polymers.
  • the polymers can, for example, contain copolymerized acrylic acid and maleic acid or methacrylic acid and maleic acid as a monomer of group b).
  • monomer combinations that may be considered are, for example, acrylic acid and vinyl acetate, acrylic acid and vinyl propionate, acrylic acid and ethyl acrylate, acrylic acid and ethyl methacrylate, acrylic acid and methyl acrylate, acrylic acid and methyl methacrylate, and also acrylic acid and N-butoxymethylacrylamide, acrylic acid and N-butoxymethyacrylamide, acrylic acid and n-butoxymethyl acrylamide -Butoxymethylacrylamid, acrylic acid and N-iso-Butoxymethylmethacrylamid as well as acrylic acid and vinyl propionate.
  • the monomers of group b) are preferably 1 to 90% by weight involved in the construction of the copolymers.
  • the polymers can optionally contain, as group c), polymerized monomers having at least two ethylenically unsaturated double bonds.
  • suitable chain extenders are, for example, diacrylates or dimethacrylates of at least dihydric saturated alcohols, for example ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, butanediol-1,4-diacrylate, butanediol-1,4-dimethacrylate , Hexanediol diacrylate, hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methylpentanediol diacrylate and 3-methylpentanediol methacrylate.
  • Acrylic acid and methacrylic acid esters of alcohols with more than two hydroxyl groups are also suitable chain extenders, for example Trimethylolpropane triacrylate or trimethylolpropane trimethacrylate.
  • Another class of chain extenders are the acrylates and the methacrylates of polyethylene glycols or polypropylene glycols with molecular weights which are preferably in the range from 400 to 2000 each.
  • block copolymers of ethylene oxide and propylene oxide or static copolymers of ethylene oxide and propylene oxide are also suitable, each of which is esterified in the ⁇ , ⁇ position with acrylic acid, methacrylic acid, maleic acid or itaconic acid.
  • Chain extenders of this type are, for example, esters of glycols with maleic acid in a molar ratio of 1: 2, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate and / or tetraethylene glycol dimethacrylate as well as the diacrylates or dimethacrylate of a polyethylene glycol group of polyglycols which are also suitable for use as polyethylene glycols ethylenically unsaturated C3- to C6-carboxylic acids, for example vinyl acrylate, vinyl methacrylate or vinyl itaconate.
  • vinyl esters of saturated carboxylic acids containing at least 2 carboxyl groups and the di- and polyvinyl ethers of at least dihydric alcohols for example divinyl adipate, butanediol divinyl ether and trimethylolpropane trivinyl ether.
  • Further monomers of group c) are, for example, allyl esters of ethylenically unsaturated carboxylic acids, for example allyl acrylate and allyl ether, triallylsucrose and pentaallylsucrose.
  • Methylenebisacrylamide, methylenebismethacrylamide and N-divinylethyleneurea, divinylbenzene, divinyldioxane, tetraallylsilane and tetravinylsilane are also suitable as monomers of group c). If the monomers of group c) are used in the preparation of the polymers, they are present in the polymers in amounts of from 0.01 to 20, preferably 0.05 to 10,% by weight in polymerized form. The monomers of group c) can be used either alone or as a mixture with one another.
  • the polymers to be used according to the invention can be obtained by polymerizing the monomers a) alone or in a mixture with at least one monomer from group b) and / or from group c). They can be prepared by all customary polymerization processes, for example by bulk, solution, precipitation or suspension polymerization.
  • the copolymers are preferably obtained by solution polymerization. In all polymerization processes, the initiators which break down into free radicals under polymerization conditions are used.
  • the polymerization temperatures are in the range from 20 to 200, preferably 30 to 150 ° C.
  • the mono- and dicarboxylic acids of the monomers of group b) can be used both as free carboxylic acids, in partially or completely neutralized form in the copolymerization.
  • the degree of neutralization - especially when using dicarboxylic acids as the monomer of group b) - can have a considerable influence on the course of the polymerization, e.g. Turnover, speed, molecular weight and residual monomer content in the copolymer.
  • inorganic or organic bases can be used, for example sodium hydroxide solution, potassium hydroxide solution, ammonia, amines, such as dimethylamine, triethanolamine, triethylamine, trimethylamine, tributylamine, ethanolamine or diethanolamine.
  • Mixtures of different bases can also be used for neutralization, e.g. Mixtures of sodium hydroxide solution and triethanolamine. If the copolymerization is carried out in aqueous solutions, the monomers from group b) containing acid groups are preferably used in neutralized form.
  • the pH of the aqueous monomer solution is preferably above 6.5, e.g. in the range of 7 to 11 or even above.
  • the non-neutralized carboxylic acid can also be used in anhydrous media.
  • initiators can be soluble or insoluble in water.
  • Water-soluble initiators are, for example, inorganic peroxides, such as potassium, sodium and ammonium peroxodisulfate and hydrogen peroxide.
  • organic peroxides hydroperoxides, peracids, ketone peroxides, perketals and peresters
  • organic peroxides for example methyl ethyl ketone hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1- (di-tert-butyl peroxy) cyclohexane, di- (tert-butyl) peroxide, tert-butyl oxyperpivalate, ethylhexyl peroctoate, tert-butyl monoperoxy maleate, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide, diacetyl peroxide, didecanoyl peroxide and mixtures of peroxides.
  • Redox systems are also suitable which contain a reducing component in addition to a peroxy compound.
  • Suitable reducing components are, for example, cerium III and iron II salts, sodium sulfite, sodium hydrogen sulfite, Sodium dithionite, ascorbic acid and sodium formaldehyde sulfoxylate.
  • Suitable initiators are preferably selected by using compounds which form free radicals and which have a half-life of less than 3 hours at the polymerization temperature chosen in each case.
  • the polymerization is initially started at a lower temperature and ends at a higher temperature, it is advisable to work with at least two initiators which disintegrate at different temperatures, namely firstly an initiator which already disintegrates at a lower temperature for the start of the polymerization and then the Complete the main polymerization with an initiator that decomposes at a higher temperature.
  • the decomposition temperature of the peroxidic catalysts can be reduced.
  • Suitable initiators are also azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2,4 -dimethylvaleronitrile) and dimethyl-2,2'-azobisisobutyrate.
  • Hydrogen peroxide, potassium, sodium and ammonium peroxodisulfate, tert-butyl perpivalate, 2,2'-azobis (2,4-dimethylvaleronitrile) and di-tert-butyl peroxide are particularly preferably used as initiators in the polymerization.
  • the polymerization is preferably carried out in the presence of a diluent.
  • a diluent can be solvents for the monomers and the polymers or only solvents for the monomers.
  • Suitable solvents for solvent polymerization are, for example, aromatic hydrocarbons, such as toluene, xylene, cumene and tetralin, aliphatic hydrocarbons, such as hexane, heptane, octane, cyclohexane and isooctane, and preferably ethers, such as diethyl ether, dibutyl ether, diisobutyl ether, methyl tert-butyl ether , Cyclic ethers, such as tetrahydrofuran and dioxane, mono- or dialkyl ethers of mono- or polyethylene glycols, for example ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethyl
  • the alkylene oxide units in the reaction products can be randomly distributed or can be in the form of blocks.
  • Such reaction products are components of liquid detergents. Since the polymers are used in detergents, they are advantageously prepared as solvents in the addition products described and the resulting polymer solution can be used directly to prepare the detergent formulation.
  • Preferred solvents for the polymerization are e.g. Reaction products of monohydric C1 to C28 aliphatic alcohols or C1 to C18 alkylphenols with ethylene oxide, propylene oxide and / or butylene oxide, e.g. the addition products of 3 to 11 moles of ethylene oxide to one mole of a C13 / C15 alcohol, addition products of 5 to 15 moles of ethylene oxide to 1 mole of nonylphenol, addition products of 7 to 11 moles of ethylene oxide and 3 to 5 moles of propylene oxide to 1 mole of oleyl alcohol and addition products of 5 to 15 moles of ethylene oxide with 1 mole of stearyl alcohol or tallow fatty alcohol.
  • Reaction products of monohydric C1 to C28 aliphatic alcohols or C1 to C18 alkylphenols with ethylene oxide, propylene oxide and / or butylene oxide e.g. the addition products of 3 to 11 moles of ethylene oxide to one mole of a
  • ethylene oxide, propylene oxide and butylene oxide with polyhydric alcohols, e.g. Glycol, diethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, block copolymers of ethylene oxide and propylene oxide, glycerol and oligoglycerols. From this group of compounds, diethylene glycol is particularly preferred.
  • Suitable solvents are C1 to C6 alcohols, such as methanol, ethanol, isopropanol, n-propanol, butanols, n-hexanol and cyclohexanol, ketones, e.g. Acetone, ethyl methyl ketone and cyclohexanone, esters, e.g. Ethyl acetate, and water and mixtures of water with water-soluble organic solvents. If an inert solvent is used in the polymerization, the concentrations of the monomers therein are 10 to 90, preferably 15 to 70% by weight.
  • the polymerization of the monomers of groups a) to c) can optionally also be carried out in the presence of regulators.
  • Suitable regulators are, for example, mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, butyl mercaptan and dodecyl mercaptan.
  • allyl compounds such as allyl alcohol, aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, propionic acid, hydroxylammonium sulfate and butenols.
  • Regulators are used in particular when larger amounts of monomers from group c) are used in the polymerization. In such cases, the use of the regulators gives water-soluble polymers or Polymers that are easily dispersible in water. If the polymerization is carried out in the presence of regulators, 0.05 to 20% by weight, based on the monomers to be polymerized, are used.
  • the polymerization is carried out in conventional devices which are provided with mixing elements. For example, flasks, kettles, autoclaves and cylindrical reactors equipped with stirrers are suitable.
  • the polymerization can also be carried out in vessels, cascades or in interconnected polymerization devices.
  • the polymerization can be carried out batchwise or continuously. Kneaders are also suitable as the polymerization device.
  • the polymerization can also be carried out by the reverse suspension polymerization method or by the water-in-oil emulsion polymerization method.
  • the polymerization is preferably carried out as solution polymerization.
  • the production of polymers by the precipitation polymerization method can be of interest for special applications.
  • the polymerization can also be initiated by the action of high-energy radiation, e.g. by UV radiation or by exposure to ⁇ , ⁇ or ⁇ rays.
  • high-energy radiation e.g. by UV radiation or by exposure to ⁇ , ⁇ or ⁇ rays.
  • the polymerization is usually carried out in apparatus designed to be pressure-tight.
  • the polymerization is preferably carried out in the absence of oxygen in an inert gas atmosphere, e.g. under nitrogen, argon, helium or carbon dioxide at normal pressure.
  • the monomers In the case of smaller polymerization batches in which the heat of polymerization can be dissipated sufficiently quickly, it is possible to charge the monomers to be polymerized together with at least one polymerization initiator and to polymerize by heating to the polymerization temperature required in each case. However, it is more advantageous if initially only some of the monomers and the initiator are initially introduced into the polymerization device and the remaining monomers and the initiator are added continuously or batchwise in accordance with the progress of the polymerization.
  • the monomers of components a) and b) can be introduced into the polymerization reactor either in the form of a solution or without a diluent.
  • the monomers of groups a) and b) to be polymerized are mixed and metered in the form of a solution in an inert solvent continuously or batchwise into a polymerization reactor.
  • the monomers can also be introduced into the polymerization reactor in bulk or in the form of a solution.
  • homopolymers or copolymers are obtained which have K values from 8 to 200, preferably 10 to 100.
  • polymerization is carried out in organic solvents, it is expedient to first neutralize the copolymers and only then to convert them into aqueous solutions or dispersions, which are then used as additives in detergents and cleaning agents. If it is necessary to separate off the organic solvents, it can be done, for example, by distillation.
  • the polymers described above which contain the essential monomer N (alkyloxy-polyalkoxymethyl) carboxamides, monoethylenically unsaturated C3- to C8-carboxylic acids with amide groups of structure I, are used as additives to detergents and cleaners in order to reduce the primary and secondary washing power of the Increase detergent and cleaning agent formulations.
  • the detergents and cleaning agents contain at least one anionic surfactant, a nonionic surfactant or mixtures thereof as essential components.
  • the detergents and cleaning agents can be in the form of a powder or a liquid formulation.
  • the copolymers to be used according to the invention are particularly suitable for the preparation of liquid detergent formulations.
  • Suitable anionic surfactants are, for example, sodium alkylbenzenesulfonates, fatty alcohol sulfates and fatty alcohol polyglycol ether sulfates.
  • Individual compounds of this type are, for example, C8 to C12 alkyl benzene sulfonates, C12 to C16 alkane sulfonates, C12 to C16 alkyl sulfates, C12 to C16 alkyl sulfosuccinates and sulfated ethoxylated C12 to C16 alkanols.
  • anionic surfactants are sulfated fatty acid alkanolamides, fatty acid monoglycerides or reaction products of 1 to 4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols.
  • anionic surfactants are fatty acid esters or fatty acid amides of hydroxy or amino carboxylic acids or sulfonic acids, such as, for example, the fatty acid sarcosides, glycolates, lactates, taurides or isethionates.
  • the anionic surfactants can be organic in the form of the sodium, potassium and ammonium salts and also as soluble salts Bases such as mono-, di- or triethanolamine or other substituted amines are present.
  • the anionic surfactants also include the usual soaps, ie the alkali salts of the natural fatty acids.
  • Nonionic surfactants e.g. Addition products of 3 to 40, preferably 4 to 20, moles of ethylene oxide and 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used.
  • the addition products of 5 to 16 moles of ethylene oxide with coconut oil or tallow fatty alcohols, with oleyl alcohol or with synthetic alcohols with 8 to 18, preferably 12 to 18 carbon atoms, and with mono- or dialkylphenols with 6 to 14 carbon atoms in are particularly important the alkyl residues.
  • non-fully or not fully water-soluble polyglycol ethers with 1 to 4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
  • non-ionic surfactants which can be used are the water-soluble adducts of ethylene oxide with 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol ether, alkylene diaminopolypropylene glycol and alkyl polypropylene glycols with 1 to 10 C atoms in the alkyl chain, in which the polypropylene glycol ether chain acts as a hydrophobic residue.
  • Nonionic surfactants of the amine oxide or sulfoxide type can also be used.
  • the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants. A reduction can also be achieved by adding non-surfactant-like organic substances.
  • the liquid, aqueous detergents contain 10 to 50% by weight of surfactants. You can contain an anionic or nonionic surfactant in the amount specified. However, it is also possible to use mixtures of anionic and nonionic surfactants. In such a case, the content of anionic surfactants in the liquid detergent is chosen from 10 to 30% by weight and the content of nonionic surfactants in the liquid detergent from 5 to 20% by weight, based on the total detergent formulation.
  • Liquid detergents contain, as an essential component, the copolymers to be used according to the invention in amounts of 0.1 to 20, preferably 1 to 10 wt .-% and optionally water in amounts of 10 to 60, preferably 20 to 50 wt .-%.
  • Liquid detergents may also contain other substances for modification. These include, for example, alcohols, such as ethanol, n-propanol and isopropanol. If used, these substances are used in amounts of 3 to 8% by weight, based on the total detergent formulation.
  • the liquid detergents may also contain hydrotropes. This includes compounds such as 1,2-propanediol, cumene sulfonate and toluene sulfonate. If such compounds are used to modify the liquid detergent, their amount, based on the total weight of the liquid detergent, is 2 to 5% by weight. In many cases, addition of complexing agents has also proven to be advantageous for modification.
  • Complexing agents are, for example, ethylenediaminetetraacetic acid, nitrilotriacetate and isoserinediacetic acid, and phosphonates, such as aminotrismethylenephosphonic acid, hydroxyethane diphosphonic acid, ethylenediaminetetramethylenephosphonic acid and their salts.
  • the complexing agents are used in amounts of 0 to 10% by weight, based on the liquid detergent.
  • the liquid detergents can also contain citrates, di- or triethanolamine, opacifiers, optical brighteners, enzymes, perfume oils and dyes. If they are used to modify the liquid detergents, these substances are present together in amounts of up to 5% by weight.
  • the liquid detergents are preferably phosphate-free.
  • phosphates e.g. Pentasodium triphosphate and / or tetrapotassium pyrophosphate. If phosphates are used, the proportion of the phosphates in the total formulation of the liquid detergent is 10 to 25% by weight, calculated as pentasodium triphosphate.
  • liquid detergents described above have the advantage over the powder detergents that they are easy to dose and have a very good fat and oil dissolving power at greasy soiled laundry at lower washing temperatures.
  • Liquid detergents contain high levels of detergent substances, which remove dirt from the textile fabric at washing temperatures of 40 to 60 ° C.
  • the dispersing properties of polymers have hitherto not been able to be used in aqueous liquid detergents because, as a result of high electrolyte concentrations in the detergents, it was not possible to obtain stable solutions with the polymers. With the homopolymers and copolymers to be used according to the invention, it is now possible to produce stable aqueous solutions of liquid detergents and the washing properties of liquid detergents to improve significantly.
  • the effectiveness of the homopolymers and copolymers to be used according to the invention in liquid detergents is demonstrated in the examples with the aid of the primary and secondary washing action of these detergents.
  • the primary washing effect is the actual removal of dirt from the textile material.
  • the difference in the degree of whiteness between the unwashed and the washed textile material after washing is determined as the degree for dirt removal.
  • Cotton, cotton / polyester and polyester fabrics with standard soiling are used as the textile test material. After each wash, the degree of whiteness of the fabric in% remission is determined in an Elrephophotometer from Zeiss.
  • Secondary washing is understood to mean the effects which arise from the re-accumulation of the dirt detached from the fabric on the fabric in the wash liquor.
  • the secondary washing effect can only take place after several washes, e.g. 3, 5, 10 or even 20 washes become visible, which becomes increasingly gray (noticeable), i.e. Accumulation of dirt from the wash liquor on the fabric.
  • standard soiling fabric is washed several times together with white test fabric and the soiled fabric is renewed after each wash.
  • the dirt detached from the dirt fabric, which is drawn onto the white test fabric during washing causes a drop in the degree of whiteness that is measured.
  • the homopolymers and copolymers to be used according to the invention in detergents or their water-soluble salts can also be used for the formulation of powder detergents.
  • composition of powder detergent formulations can vary widely. The same applies to the composition of detergent formulations.
  • Detergent and cleaning agent formulations usually contain surfactants and optionally builders. This information applies to both liquid and powder detergent formulations. Examples of the composition of detergent formulations which are common in Europe, the USA and Japan can be found, for example, in Chemical and Engn. News, Vol. 67, 35 (1989) in tabular form and in Ullmann's Encyclopedia of Industrial Chemistry, Verlag Chemie, Weinheim 1983, 4th edition, pages 63-160.
  • the percentages in the examples are% by weight.
  • the K values were determined according to H. Fikentscher, Zellulosechemie, Vol. 13, 58-64 and 71-74 (1932).
  • the K values of the water-soluble polymers were measured in aqueous solution at 25 ° C., a pH of 7.5 and a polymer concentration of 1% by weight.
  • the K values of the water-dispersible polymers were measured as 1% solutions in the unneutralized form in tetrahydrofuran (THF) at 25 ° C.
  • the K values determined in this way are in all cases between 8 and 200, preferably between 10 and 100.
  • tetrahydrofuran 125 g of tetrahydrofuran are placed under a nitrogen atmosphere in a 500 ml round-bottomed flask equipped with a stirrer, reflux condenser, nitrogen inlet and feed devices and heated to boiling under reflux.
  • a solution of 37.5 g of acrylic acid in 35 g of tetrahydrofuran, a solution of 37.5 g of acrylamide derivative 1 in 35 g of tetrahydrofuran and a solution of 1 within 2 hours are then simultaneously added to this template from 3 feed vessels within 1 hour. 5 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 20 g of tetrahydrofuran.
  • reaction mixture is heated to boiling under reflux for a further 2 hours, cooled to 20 ° C. and neutralized by adding a mixture of 124 g of triethanolamine and 50 g of tetrahydrofuran.
  • the wax-like flask contents are mixed with 300 g of water and the solution obtained is freed from tetrahydrofuran by distillation.
  • a slightly yellowish, clear, aqueous, viscous solution with a solids content of 27% and a K value of 32 (measured in aqueous solution) is obtained.
  • aqueous solution of 135 g of acrylic acid in 150 g of water is neutralized with 227 g of 50% strength aqueous potassium hydroxide solution and a solution of 67 g of the acrylamide derivative 1 in 200 g of isopropanol is added.
  • the resulting clear solution is continuously added over a period of 1 hour and simultaneously a solution of 2 g of mercaptopropionic acid in 20 g of water and 20 g of isopropanol in the polymerizer described in the preparation of polymer 3 and polymerized at a bath temperature of 90.degree 6.7 9 30% aqueous hydrogen peroxide dissolved in 30 g of water and 30 g of isopropanol are added as the polymerization initiator within 2 hours.
  • reaction mixture After the hydrogen peroxide has been added, the reaction mixture is refluxed for a further 2 hours and the excess isopropanol is distilled off. A cloudy solution with a solids content of 38% is obtained.
  • the K value of the polymer is 26 (measured in aqueous solution). The 38% aqueous solution becomes clear and colorless when diluted to a solids content of about 15% by weight.
  • 100 g of tetrahydrofuran are placed in the apparatus described for the preparation of polymer 3 and heated to boiling under reflux. After the start of boiling, a solution of 140 g of acrylamide derivative 1 and 60 g of acrylic acid in 100 g of tetrahydrofuran is metered into the initial charge within 2 hours and a solution of 8 g of 75% tert-butyl perpivalate in 50 g of tetrahydrofuran within 2.5 hours. After the initiator addition has ended, the reaction mixture is heated to boiling for a further hour, cooled and then neutralized by adding 67 g of 50% strength aqueous sodium hydroxide solution and 400 g of water.
  • the tetrahydrofuran is then distilled off and the solids content of the aqueous solution is then adjusted to 15% by adding water.
  • the 15% aqueous solution has a viscosity of 1062 mPas at a temperature of 20 ° C.
  • the K value is 25.6 (measured in aqueous solution).
  • Polymers 6 to 12 are prepared in accordance with the process specification given above using the starting materials shown in Table 1.
  • the procedure is as described for the preparation of polymer 14, except that 50 g of acrylamide derivative 3, 40 g of vinyl acetate and 10 g of acrylic acid in 100 g of tetrahydrofuran are polymerized with 4 g of 75% tert-butyl perpivalate in 50 g of tetrahydrofuran. After the polymerization, 11 g of 50% strength are added aqueous sodium hydroxide solution in 200 g of water. After distillation and dilution of the mixture with water, a 30% strongly cloudy polymer solution with a viscosity of 12833 mPas is obtained. The K value of the polymer in the unneutralized form is 20.3 (determined on solutions of the polymer in THF).
  • acrylamide derivative 3 40 g of N- (isobutoxymethyl) acrylamide and 10 g of acrylic acid in 100 g of tetrahydrofuran are polymerized with 4 g of 75% tert-butyl perpivalate in 50 g of tetrahydrofuran and then polymerized with 11 neutralized g 50% sodium hydroxide solution and diluted by adding 200 g water. After the tetrahydrofuran has been distilled off, a slightly cloudy solution with a solids content of 38% and a viscosity of 3420 mPas is obtained.
  • the K value is 19.1 (determined on solutions of the polymer in THF).
  • acrylamide derivative 3 40 g of N- (isobutoxymethyl) acrylamide and 10 g of acrylic acid in 100 g of tetrahydrofuran are polymerized with 4 g of 75% tert-butyl perpivalate in 50 g of tetrahydrofuran and added by adding 11 g of 50% sodium hydroxide solution neutralized. 200 g of water are then added and, after distillation, a very cloudy solution in the warm state and only a slightly cloudy solution in the cold state with a solids content of 40% and a viscosity of 2432 mPas.
  • the K value is 18.2 (determined on aqueous polymer solutions).
  • the polymers 22-27 were produced using the starting materials listed in Table 2.
  • 60 g of tetrahydrofuran are placed in a mechanically stirred 250 ml round-bottomed flask with a reflux condenser and metering devices and heated to boiling.
  • a solution of 20 g of acrylamide derivative 1 and 60 g of acrylic acid in 50 g of tetrahydrofuran and 20 g of N-vinylpyrrolidone, dissolved in 20 g of tetrahydrofuran, are metered into this template within 30 minutes.
  • an initiator solution consisting of 2 g of 75% tert-butyl perpivalate and 30 g of tetrahydrofuran is added dropwise within 40 minutes.
  • the mixture is refluxed for a further hour, allowed to cool and neutralized with 140 g of 25% strength aqueous sodium hydroxide solution.
  • the tetrahydrofuran is distilled off and the resulting solution of the copolymer is adjusted to 30% by weight solids content by adding water.
  • the K value is 48.3 (measured in a 1% strength aqueous solution).
  • tetrahydrofuran 125 g of tetrahydrofuran are placed in a 500 ml 4-necked flask with stirrer, reflux condenser and 4 metering devices and heated to boiling. 53 g of acrylic acid and simultaneously 23 g of acrylamide derivative 4 dissolved in 35 g of tetrahydrofuran are metered in over the course of 2 hours, and a solution of 1.5 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 20 g of tetrahydrofuran is added within 2.5 hours . The mixture is refluxed for a further hour and cooled. 109 g of triethanolamine are added to the solution of the copolymer within 30 minutes and the mixture is diluted with 100 g of water. After the tetrahydrofuran has been distilled off, a solids content of 40% is established. The K value (measured in a 1% aqueous solution) is 27.8.
  • a polymer-free detergent formulation was tested for comparison.
  • the polymers to be used according to the invention significantly improve the primary washing action of the detergent formulations. At the same time, an improvement in the graying inhibition is observed.
  • the polymers to be used according to the invention can be incorporated into the detergent formulations A and B without problems and result in stable, homogeneous solutions.

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (7)

  1. Utilisation de polymères qui contiennent en liaison polymère, comme monomère essentiel, au moins 5% en poids de N-(alkyloxy-polyalcoxyméthyl)carboxamides d'acides carboxyliques en C₃-C₈ à insaturation monoéthylénique renfermant des groupements amide de structure



            -CO-NH-CH₂-R   (I)



    dans laquelle
    Figure imgb0014

            R¹-O-(CH₂-CH₂-CH₂-CH₂-O)m



    où
    R¹ =   alkyle en C₁-C₂₈, alcényle en C₃-C₂₈, phényle ou (alkyl en C₁-C₁₈)phényle,
    R², R³ =   H, CH₃, C₂H₅,
    n =   1 à 200 et
    m =   1 à 100,
    comme additifs à des produits de lavage et de nettoyage pauvres en phosphates et sans phosphates, dans des proportions de 0,1 à 20% en poids par rapport au produit de lavage et de nettoyage.
  2. Utilisation selon la revendication 1, caractérisée en ce que les polymères contiennent en liaison polymère
    a) 10 à 99% en poids de N-(alkyloxy-polyalcoxyméthyl)carboxamides d'acides carboxyliques en C₃-C₈ à insaturation monoéthylénique renfermant des groupements amide de structure I et
    b) 90 à 1% en poids d'autres monomeres à insaturation monoéthylénique.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que les polymères contiennent en liaison polymère, en tant que comonomères
    b) des acides carboxyliques en C₃-C₈ à insaturation monoéthylénique, leurs esters avec des alcools en C₁-C₂₈, des esters d'acides carboxyliques en C₃-C₈ à insaturation monoéthylénique avec des produits de réaction d'alcools en C₁-C₂₈ et d'oxyde d'éthylène, d'oxyde de propylène et/ou d'oxyde de butylène dans un rapport molaire de 1:1 à 1:100, des amides, N-(alkyl en C₁-C₁₈)oxyméthylamides et nitriles d'acides carboxyliques en C₃-C₈ à insaturation monoéthylénique, des esters vinyliques d'acides carboxyliques saturés à 1-20 atomes de carbone, des oxydes de vinyle et d'alkyle en C₁-C₂₈, du styrène ou des mélanges de ceux-ci.
  4. Utilisation selon la revendication 1 ou 2, caractérisée en ce que les polymères contiennent en plus en liaison polymère, en tant que monomère (c), 0,01 à 20% en poids de composés comportant au moins deux doubles liaisons non conjuguées à insaturation ethylénique.
  5. Utilisation selon la revendication 1, caractérisée en ce qu'on utilise des homopolymères de N-(alkyloxy-polyalcoxyméthyl)carboxamides d'acides carboxyliques en C₃-C₈ à insaturation monoéthylénique renfermant des groupements amide de structure I ou des copolymères de ces monomères entre eux.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce qu'on utilise des solutions de polymères qui sont obtenues par polymérisation des monomères dans des produits d'addition d'oxydes d'alkylène à 2-4 atomes de carbone à des alcools en C₁-C₂₈ ou à des (alkyl en C₁-C₁₈)phénols.
  7. Produits de lavage et de nettoyage qui contiennent, comme composants essentiels,
    1) au moins un tenside anionique, un tenside non ionique ou des mélanges de ceux-ci et
    2) 0,1 à 20% en poids de polymères,
    caractérisés en ce qu'ils contiennent, en tant que composant (2), des polymères qui contiennent en liaison polymère, comme monomère essentiel, au moins 5% en poids de N-(alkyloxy-polyalcoxyméthyl)carboxamides d'acides carboxyliques en C₃-C₈ à insaturation monoéthylénique renfermant des groupements amide de structure



            -CO-NH-CH₂-R   (I)



    dans laquelle
    Figure imgb0015

            R¹-O-(CH₂-CH₂-CH₂-CH₂-O)m



    où
    R¹ =   alkyle en C₁-C₂₈, alcényle en C₃-C₂₈, phényle ou (alkyl en C₁-C₁₈)phényle,
    R², R³ =   H, CH₃, C₂H₅,
    n =   1 à 200 et
    m =   1 à 100.
EP91912925A 1990-07-27 1991-07-19 Utilisation de polymeres contenant des groupes n-(alkyloxy-polyalcoxymethyl)carbonamides comme additifs d'agents de lavage et de nettoyage Expired - Lifetime EP0541588B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4023820A DE4023820A1 (de) 1990-07-27 1990-07-27 Verwendung von n-(alkyloxy-polyalkoxymethyl)carbonamid-gruppen aufweisenden polymerisaten als zusatz zu wasch- und reinigungsmitteln
DE4023820 1990-07-27
PCT/EP1991/001360 WO1992002606A1 (fr) 1990-07-27 1991-07-19 Utilisation de polymeres contenant des groupes n-(alkyloxy-polyalcoxymethyl)carbonamides comme additifs d'agents de lavage et de nettoyage

Publications (2)

Publication Number Publication Date
EP0541588A1 EP0541588A1 (fr) 1993-05-19
EP0541588B1 true EP0541588B1 (fr) 1994-10-19

Family

ID=6411084

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91912925A Expired - Lifetime EP0541588B1 (fr) 1990-07-27 1991-07-19 Utilisation de polymeres contenant des groupes n-(alkyloxy-polyalcoxymethyl)carbonamides comme additifs d'agents de lavage et de nettoyage

Country Status (6)

Country Link
EP (1) EP0541588B1 (fr)
JP (1) JPH05509118A (fr)
AT (1) ATE113069T1 (fr)
CA (1) CA2081199A1 (fr)
DE (2) DE4023820A1 (fr)
WO (1) WO1992002606A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE9602226D0 (sv) * 1996-06-05 1996-06-05 Astra Ab Biocompatible glue

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395524A (en) * 1981-04-10 1983-07-26 Rohm And Haas Company Acrylamide copolymer thickener for aqueous systems
DE3305637A1 (de) * 1983-02-18 1984-08-23 Basf Ag, 6700 Ludwigshafen Copolymerisate, ihre herstellung und ihre verwendung als hilfsmittel in wasch- und reinigungsmitteln
DE3716543A1 (de) * 1987-05-16 1988-11-24 Basf Ag Verwendung von wasserloeslichen copolymerisaten, die monomere mit mindestens zwei ethylenisch ungesaettigten doppelbindungen einpolymerisiert enthalten, in wasch- und reinigungsmitteln
DE3838093A1 (de) * 1988-11-10 1990-05-17 Basf Ag Verwendung von copolymerisaten als zusatz zu fluessigwaschmitteln
US4946627A (en) * 1989-07-19 1990-08-07 National Starch And Chemical Investment Holding Corporation Hydrophobically modified polycarboxylate polymers utilized as detergent builders

Also Published As

Publication number Publication date
ATE113069T1 (de) 1994-11-15
DE59103296D1 (de) 1994-11-24
JPH05509118A (ja) 1993-12-16
EP0541588A1 (fr) 1993-05-19
WO1992002606A1 (fr) 1992-02-20
CA2081199A1 (fr) 1992-01-28
DE4023820A1 (de) 1992-01-30

Similar Documents

Publication Publication Date Title
EP0451508B1 (fr) Procédé de préparation de homo- et copolymères d'acides dicarboxyliques insaturés monoéthyléniquement et leur usage
EP0471710B1 (fr) Copolymerisats formes par polymerisation de monomeres renfermant des blocs d'oxyde de polyalkylene, leur preparation et leur emploi
EP0367049B1 (fr) Utilisation de copolymères estérifiés partiellement pour compositions détergentes liquides
EP0824553B1 (fr) Copolymeres solubles dans l'eau, leur procede de production et leur utilisation
EP0368214B1 (fr) Utilisation de copolymères estérifiés partiellement pour compositions détergentes liquides
EP0457205B1 (fr) Utilisation de protéines greffées solubles ou dispersables dans l'eau comme additifs pour détergents et solutions nettoyantes
EP0116930B2 (fr) Copolymères, leur préparation et leur usage dans les produits de lavage et de nettoyage
EP0573463B1 (fr) Utilisation de polyacetals dans des produits de lavage et des detergents
EP0603236B1 (fr) Copolymeres d'hydroxyalkylvinylethers et utilisation d'homopolymeres et de copolymeres d'hydroxyalkylvinylethers dans des produits de lavage et de nettoyage
WO1995030731A1 (fr) Utilisation de polymeres greffes comme additifs dans des detergents et des nettoyants
DE112014006990T5 (de) Sulfonatgruppenhaltiges polymer und verfahren zur herstellung hiervon
EP1761622B1 (fr) Procede de production de compositions detergentes granulaires ou pulverulentes
EP0377448A2 (fr) Utilisation de copolymères de 1,2-di-alkoxyéthylènes et d'anhydrides d'acides dicarboxyliques insaturés monoéthyléniquement dans des détergents contenant ces copolymères
EP1587848B1 (fr) Copolymeres partiellement esterifies d'anhydrides d'acide dicarboxylique monoethyleniquement insatures, de composes vinylaromatiques et d'autres monomeres monoethyleniquement insatures contenant des heteroatomes
WO1991019778A1 (fr) Utilisation de copolymeres greffes dans des produits de lavage et de nettoyage
EP0541588B1 (fr) Utilisation de polymeres contenant des groupes n-(alkyloxy-polyalcoxymethyl)carbonamides comme additifs d'agents de lavage et de nettoyage
DE102005047833A1 (de) Verfahren zur Herstellung von granulären oder pulverförmigen Waschmittelzusammensetzungen
DE3744592C2 (de) Wasserlösliche Polymerisate enthaltende Geschirrspülmittel
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

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: 19921006

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LI SE

17Q First examination report despatched

Effective date: 19931109

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19941019

Ref country code: DK

Effective date: 19941019

Ref country code: BE

Effective date: 19941019

REF Corresponds to:

Ref document number: 113069

Country of ref document: AT

Date of ref document: 19941115

Kind code of ref document: T

REF Corresponds to:

Ref document number: 59103296

Country of ref document: DE

Date of ref document: 19941124

ITF It: translation for a ep patent filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19941103

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19950119

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19950623

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19950717

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19950719

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19950727

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19950731

Ref country code: CH

Effective date: 19950731

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19960719

Ref country code: DE

Effective date: 19960719

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19960719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19970328

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050719