EP0291808B1 - Utilisation de copolymerisates solubles dans l'eau contenant des monomères ayant au moins deux liaisons insaturées éthyléniques dans les agents de lavage et de nettoyage - Google Patents

Utilisation de copolymerisates solubles dans l'eau contenant des monomères ayant au moins deux liaisons insaturées éthyléniques dans les agents de lavage et de nettoyage Download PDF

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EP0291808B1
EP0291808B1 EP88107406A EP88107406A EP0291808B1 EP 0291808 B1 EP0291808 B1 EP 0291808B1 EP 88107406 A EP88107406 A EP 88107406A EP 88107406 A EP88107406 A EP 88107406A EP 0291808 B1 EP0291808 B1 EP 0291808B1
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mol
monoethylenically unsaturated
water
soluble
weight
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EP0291808A1 (fr
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Wolfgang Dr. Trieselt
Richard Dr. Baur
Ekhard Dr. Winkler
Paul Diessel
Hans-Peter Dr. Seelmann-Eggebert
Dieter Dr. Boeckh
Heinrich Dr. Hartmann
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • builders In laundry detergents and cleaning agents, as is well-known, builders (builder) are required as ingredients in addition to surface-active substances.
  • the builders have a variety of tasks in detergent and cleaning agent formulations, e.g. should they support the surfactants in the detachment of dirt, render the hardness formers of the water harmless, be it by sequestering the alkaline earth metal ions or by dispersing the hardness formers precipitated out of the water, promote the dispersion and stabilization of the dirt that is colloidally distributed in the wash liquor and to keep the optimal pH Value as a buffer during washing.
  • the builders should make a positive contribution to a good powder structure or flowability.
  • Phosphate-based builders largely perform the tasks described above that are placed on a builder. For a long time, pentasodium triphosphate was indisputably the most important builder in detergents and cleaning agents. However, the phosphates contained in detergents reach the wastewater practically unchanged. As the phosphates are a good nutrient for aquatic plants and algae, they are responsible for the eutrophication of lakes and slow-flowing waters. In sewage treatment plants that do not have a so-called third purification stage, in which the phosphates are specially precipitated, they are not sufficiently removed. It was therefore early on to look for substances that could replace phosphates in detergents as builders.
  • water-soluble ion exchangers based on zeolites have found their way into phosphate-free or low-phosphate detergents.
  • the zeolites cannot replace the phosphates as builders alone.
  • the action of the zeolites is supported by other detergent additives which are compounds containing carboxyl groups, such as citric acid, tartaric acid, nitrilotriacetic acid and, above all, polymeric compounds containing carboxyl groups or their salts.
  • the homopolymers of acrylic acid and the copolymers of acrylic acid and maleic acid are particularly important as detergent additives, cf. U.S. Patent 3,308,067 and EP Patent 25,551.
  • the polymers mentioned are ecologically harmless because they are adsorbed on the activated sludge in the sewage treatment plants and are thus removed from the water cycle. However, these polymers are not sufficiently biodegradable in the sense of today's requirements for the wastewater constituents.
  • the object of the present invention is to provide additives for detergents and cleaning agents based on polymers which have a far better biodegradability than the polymers previously used for them.
  • copolymers described above act as builders in detergents and cleaning agents and thus contribute to a washing activation of surfactants in the detergents and cleaning agents, a reduction in the incrustation on the washed textile and to a dirt dispersion in the washing liquor.
  • these copolymers are surprisingly biodegradable and, in some cases, even more effective than the polymers previously used in detergents.
  • component a) of the water-soluble copolymers monoethylenically unsaturated C 3 to C e monocarboxylic acids come into consideration.
  • Suitable carboxylic acids of this type are, for example, acrylic acid, methacrylic acid, ethacrylic acid, vinyl acetic acid, allylacetic acid and crotonic acid.
  • Acrylic acid and / or methacrylic acid is preferably used as the monomer of component a).
  • the monomers of component a) make up 99.5 to 15 mol% of the copolymers.
  • the monomers of component b) are an essential component of the copolymers. These are comonomers which have at least two ethylenically unsaturated, non-conjugated double bonds and at least one -CO-OH group and / or their salt with an alkali metal, ammonium or alkaline earth metal base. These comonomers generally bring about an increase in the molecular weight of the copolymers and make up 0.5 to 20, preferably 1 to 12, mol% of the copolymers.
  • the comonomers b) can be obtained by reacting
  • polyhydric alcohols containing 2 to 6 carbon atoms water-soluble or water-insoluble polyalkylene glycols of a molecular weight of up to 400, water-soluble polyalkylene glycols of a molecular weight of more than 400 to 10,000, polyglycerols, polyamines of a molecular weight Polyalkylene polyamines, polyethyleneimines, amino alcohols, hydroxyamino or diaminocarboxylic acids, such as in particular lysine and serine, copolymers of alkylene oxide and carbon dioxide, polyvinyl alcohol with a molecular weight of up to 10,000, allyl alcohol, allylamine, hydroxyalkyl esters with 2 to 6 carbon atoms in the hydroxyalkyl unsaturated group of mono C 3 - to C e -carboxylic acids or of saturated C 3 - to C 8 -hydroxy
  • Polyhydric alcohols containing 2 to 6 carbon atoms are, for example, glycol, glycerol, pentaerythritol and monosaccharides, such as glucose, mannose, galactose, uronic acids, such as galacturonic acid, and sugar acids, such as mucic acid or galactonic acid.
  • Water-soluble polyalkylene glycols are to be understood as meaning the addition products of ethylene oxide, propylene oxide, n-butylene oxide and isobutylene oxide or their mixtures with polyhydric alcohols having 2 to 6 carbon atoms, e.g. the adducts of ethylene oxide with glycol, adducts of ethylene oxide with glycerol, adducts of ethylene oxide with pentaerythritol, sorbitol, adducts of ethylene oxide with monosaccharides, and also adducts of mixtures of the alkylene oxides mentioned with polyhydric alcohols.
  • addition products can be block copolymers of ethylene oxide and propylene oxide, of ethylene oxide and butylene oxides or of ethylene oxide, propylene oxide and butylene oxides.
  • addition products are also suitable which contain the alkylene oxides mentioned in copolymerized form in a random distribution.
  • the molecular weight of the polyalkylene glycols is advantageously up to 5,000, preferably up to 2,000.
  • preference is given to using diethylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycol with a molecular weight of up to 1,500.
  • component b2) are polyglycerols with a molecular weight of up to 2,000. Of this class of substances, preference is given to using diglycerin, triglycerin and tetraglycerin.
  • Suitable polyamines are, for example, preferably diamines, such as ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and 1,6-hexamethylenediamine and melamine.
  • suitable polyalkylene polyamines are diethylene triamine, triethylene tetramine, pentaethylene hexamine, N- (3-aminopropyl) -1,3-propidiamine and 3- (2-aminoethyl) aminopropylamine.
  • Particularly suitable polyethyleneimines have a molecular weight of up to 5,000.
  • Amino alcohols such as ethanolamine, 2-aminopropanol-1, neopentanolamine and 1-methylamino-2-propanol, are also suitable as component b2).
  • component b2) are copolymers of ethylene oxide and carbon dioxide, which can be obtained by copolymerizing ethylene oxide and carbon dioxide.
  • polyvinyl alcohols with a molecular weight of up to 10,000, preferably polyvinyl alcohols with a molecular weight of up to 2,000.
  • the polyvinyl alcohols which are produced by hydrolysis from polyvinyl acetate can be wholly or partly hydrolyzed.
  • Other suitable compounds of component b2) are lysine, serine, allyl alcohol, allylamine and hydroxyalkyl esters with 2 to 6 carbon atoms in the hydroxyalkyl group from monoethylenically unsaturated C 3 to Ce mono- and dicarboxylic acids.
  • the hydroxyalkyl ester groups of the last-mentioned monomers are derived from polyhydric alcohols, for example glycol, glycerol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, mixtures of the Butanediols or propanediols, 1,6-hexanediol and neopentyl glycol.
  • the polyhydric alcohols are esterified with monoethylenically unsaturated C 3 to C 6 carboxylic acids. These are the carboxylic acids mentioned above under a) and c).
  • Suitable components b2) are thus, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxy-n-propyl methacrylate, hydroxy-n-propylacrylate, hydroxyisopropyl acrylate, hydroxyisopropyl methacrylate, hydroxy-n-butyl acrylate, hydroxyisobutylacrylate, hydroxy-n-butyl methobutylethyl acrylate, hydroxyl nyl butyl methacrylate, hydroxyl Hydroxypropyldimaleinate, hydroxy-n-butylmonomaleinate, hydroxy-n-butyldimaleinate and hydroxyethylmonoitaconate.
  • hydroxyalkyl esters of the monoethylenically unsaturated dicarboxylic acids both the mono- and the diesters of the dicarboxylic acids with the polyhydric alcohols mentioned above come into consideration.
  • hydroxyalkyl esters of saturated C 3 to C e hydroxycarboxylic acids such as hydroxyacetic acid glycol monoesters, lactic acid glycol monoesters and hydroxypivalic acid neopentylglycol esters.
  • Monoethylenically unsaturated C 4 - to C e -dicarboxylic acids are used as the monomer of component c). These are, for example, maleic acid, itaconic acid, citraconic acid, mesaconic acid, fumaric acid and methylene malonic acid. Maleic acid or itaconic acid are preferably used as Monomerc).
  • the monomers c) make up 0 to 84.5, preferably 5 to 60 mol% of the copolymers.
  • the copolymers may optionally contain copolymerized hydroxyalkyl esters with 2 to 6 carbon atoms in the hydroxyalkyl group of monoethylenically unsaturated C 3 to C e carboxylic acids as component d).
  • the hydroxyalkyl ester groups of this group of monomers are derived from polyhydric alcohols, for example glycol, glycerin, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, mixtures of the Butanediols or propanediols, 1,6-hexanediol and neopentyl glycol.
  • the polyhydric alcohols are reacted with monoethylenically unsaturated C 3 - to C e -carboxylic acids esterified. These are the carboxylic acids mentioned above under a) and c).
  • Suitable as component d) are thus, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxy-n-propyl methacrylate, hydroxy-n-propyl acrylate, hydroxyisopropyl acrylate, hydroxyisopropyl methacrylate, hydroxy-n-butyl acrylate, hydroxyisobutylacrylate, hydroxy-n-butyl methylacylate, hydroxymethyl acrylate, hydroxymethyl Hydroxypropyldimaleinate, hydroxy-n-butylmonomaleinate, hydroxy-n-butyldimaleinate and hydroxyethylmonoitaconate.
  • Preferably used as component d) is hydroxyethyl acrylate, hydroxyethyl methacrylate, butane-1,4-diol monoacrylate and the technical-grade mixtures of hydroxypropyl acrylates.
  • hydroxyethyl acrylate hydroxyethyl methacrylate
  • butane-1,4-diol monoacrylate and the technical-grade mixtures of hydroxypropyl acrylates.
  • the isomer mixtures of 2-hydroxy-1-propyl acrylate and 1-hydroxy-2-propyl acrylate are of particular technical importance.
  • These hydroxyalkyl acrylates are produced by reacting acrylic acid with propylene oxide.
  • the monomers of group d) are present in the copolymer in 0 to 20, preferably 0 to 15 mol% in polymerized form.
  • the copolymers may optionally contain, as component e), other water-soluble monoethylenically unsaturated monomers copolymerizable with a), b), c) and d).
  • Suitable monomers of this type are, for example, acrylamide, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, vinylphosphonic acid, allylphosphonic acid, acrylonitrile, methacrylonitrile, dimethylaminoethyl acrylate, diethylaminoethylacrylate, diethylaminoethyl methacrylate, n-vinylazolonyl, nylon-vinylazolonyl, n-vinylpyronidyl, n-vinylpyronidyl, n-vinylpyronidyl, n-vinylpyronidyl, n-vinylpyroni
  • Those monomers in this group which contain acid groups can be used in the copolymerization in the form of the free acids or else in a form partially or completely neutralized with alkali metal bases or ammonium bases.
  • the basic acrylates such as diethylaminoethyl acrylate, are neutralized or quaternized with acids and then subjected to the copolymerization.
  • the monomers e) make up 0 to 30, preferably 0 to 20, mol% of the copolymers. They only serve to modify the copolymers.
  • the sum of the data in mol% of components a) to e) is always 100.
  • the copolymerization is carried out in an aqueous medium, preferably in a purely aqueous medium. It can be done according to different process variants, e.g. the monomers a) to e) can be polymerized batchwise in the form of aqueous solutions.
  • the polymerization temperatures range from 20 to 200 ° C. At temperatures above 100 ° C, pressure equipment is used.
  • the polymerization temperature is preferably 50 to 150 ° C.
  • At least 0.5 mol of a compound of component b1) is used per mole of compounds b2).
  • the temperature during the reaction is preferably 50 to 150 ° C.
  • the reaction is carried out to such an extent that there is practically a quantitative conversion of component b2).
  • Component b1) which is usually used in excess, can remain in the reaction mixture after the comonomer preparation has ended.
  • the comonomer can be dissolved in a monoethylenically unsaturated C 3 -C e -monocarboxylic acid according to a) and then subjected to the copolymerization together with the unreacted part of component b1) and the other monomers.
  • the comonomer b) initially prepared which still contains excess dicarboxylic anhydride, can also remain in the reaction mixture in which it was produced and can first be dissolved therein by adding water or dilute aqueous sodium hydroxide solution.
  • the dicarboxylic anhydride still present is hydrolyzed here.
  • This monomer mixture is then copolymerized by adding the other comonomers.
  • the copolymerization of the monomers a) to e) is carried out at a pH of the aqueous solution of 2 to 9, preferably 3 to 7.
  • the monomers a), b) and c), which each contain carboxylic acid groups, can be copolymerized in the form of the free carboxylic acids or in neutralized, preferably in partially neutralized form, the degree of neutralization being 0 to 100, preferably 40 to 90 mol%.
  • the neutralization is preferably carried out with alkali metal or ammonium bases.
  • sodium hydroxide solution, potassium hydroxide solution, soda, potash or ammonium bases such as ammonia, C 1 -C 8 -alkylamines, dialkylamines such as dimethylamine, din-butylamine, dihexylamine, tertiary amines such as trimethylamine, triethylamine, tributylamine, triethanolamine and quaternized nitrogen bases, for example to understand tetramethylammonium hydroxide, trimethyllaurylammonium hydroxide and trimethylbenzylammonium hydroxide.
  • Sodium hydroxide solution, potassium hydroxide solution or ammonia are preferably used for neutralization. However, the neutralization can also be carried out with alkaline earth metal bases, for example Ca hydroxide or MgC0 3 .
  • Water-soluble radical-forming compounds are preferably used as polymerization initiators, e.g. Hydrogen peroxide, peroxidisulfates and mixtures of hydrogen peroxide and peroxidisulfates.
  • Suitable peroxydisulfates are, for example, lithium, sodium, potassium and ammonium peroxydisulfate.
  • any ratio can be set, preferably hydrogen peroxide and peroxydisulfate in a weight ratio of 3: to 1: 3.
  • Mixtures of hydrogen peroxide and sodium peroxydisulfate are preferably used in a weight ratio of 1: 1.
  • water-soluble polymerization initiators can optionally also be used in combination with reducing agents, e.g. Iron 11-sulfate, sodium sulfite, sodium hydrogen sulfite, sodium dithionite, triethanolamine and ascorbic acid can be used in the form of the so-called redox initiators.
  • reducing agents e.g. Iron 11-sulfate, sodium sulfite, sodium hydrogen sulfite, sodium dithionite, triethanolamine and ascorbic acid
  • Suitable water-soluble organic peroxides are, for example, acetylacetone peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide and cumene hydroperoxide.
  • the water-soluble organic peroxides can also be used with the reducing agents mentioned above.
  • Other water-soluble polymerization initiators are azo starters, e.g.
  • 2,2'-azobis (2-amidinopropane) dihydrochloride 2,2'-azobis (N, N'-dimethylene) isobutyramidine dihydrochloride, 2- (carbamoylazo) isobutyronitrile and 4,4'-azo-bis- ( 4-cyanovaleric acid).
  • the polymerization can also be started with water-insoluble initiators, such as dibenzoyl peroxide, dicyclohexyl peroxidicarbonate, dilauryl peroxide or azodiisobutyronitrile.
  • the initiators are used in amounts of 0.1 to 15, preferably 0.5 to 10,% by weight, based on the sum of the monomers used in the polymerization.
  • the polymerization initiators can be added continuously or batchwise to the mixture to be polymerized either together with the monomers or separately in the form of aqueous solutions.
  • the copolymerization can optionally also be carried out in the presence of regulators.
  • water-soluble compounds are preferably used which are either miscible with water in any ratio or dissolve more than 5% by weight therein at a temperature of 20.degree.
  • Compounds of this type are, for example, aldehydes having 1 to 4 carbon atoms, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, hydroxylammonium salts, in particular hydroxylammonium sulfate, compounds containing SH groups with up to 6 carbon atoms, such as thioglycolic acid, mercapto such as mercaptoethanol, mercaptopropanol, mercaptobutanols and mercaptohexanol, mono- and polyhydric alcohols with up to 6 carbon atoms, such as isopropano
  • Preferred regulators are water-soluble mercaptans, ammonium formate and hydroxylammonium sulfate.
  • the regulators are used in amounts of 0 to 25% by weight, based on the sum of the monomers used in the polymerization.
  • the particularly effective regulators, which are preferably used, are used in amounts of up to at most 15% by weight. If work is carried out in the presence of regulators, the minimum amount used is 0.2% by weight, based on the monomers to be polymerized.
  • the copolymerization of monomers a) to e) gives aqueous polymer solutions which have a polymer content of up to 70% by weight. It is of course also possible to use very dilute e.g. To produce 1% aqueous solutions, but the copolymerization is carried out for economic reasons so that at least 20% by weight aqueous copolymer solutions are prepared. After the copolymerization, the solutions can be adjusted to a pH in the range from 6.5 to 7, provided that the polymerization has not been carried out in this range anyway.
  • the copolymers can be obtained by evaporating the aqueous solutions. They have a low residual monomer content and are surprisingly biodegradable.
  • the biodegradability of the copolymers according to the invention is up to 100% in accordance with DIN 38 412, part 24, static test (L25), and is generally between 20 and 95%.
  • the copolymers are water-soluble. If they do not dissolve in water in the free acid form, they can be converted into a water-soluble form by partial or complete neutralization with NaOH, KOH, ammonia or amines. Copolymers, their alkali or ammonium salts, of which at least 20 g per liter of water dissolve at a temperature of 20 ° C, are referred to in the present context as water-soluble.
  • the copolymers surprisingly have the advantage that, in the range of low polymer concentrations, they show no precipitation in the aqueous solutions containing Ca and / or Mg ions. It is therefore possible to prepare stable solutions of the copolymers in drinking water without the alkaline earth salts of the copolymers being precipitated.
  • the K value of the copolymers is in the range from 8 to 120, preferably 12 to 100.
  • the K values of the copolymers are in each case on the sodium salt in aqueous solution at 25 ° C., a pH of 7 and a polymer concentration of the sodium salt of Copolymer determined from 1 wt.%. If the copolymers are in the form of other salts or free acids, they must first be converted into the sodium salts before the K value is determined.
  • copolymers described above are used according to the invention as additives to detergents and cleaning agents. They can be added in powder or liquid formulations.
  • the detergent and cleaning agent formulations are usually based on surfactants and, if appropriate, builders. Builders are usually not used for pure liquid detergents.
  • Suitable surfactants are, for example, anionic surfactants such as C 3 to C 12 alkylbenzenesulfonates, C 12 to C 18 alkanesulfonates, C 12 to C 16 alkyl sulfates, C 2 to C 16 alkyl sulfosuccinates and sulfated ethoxylated C 12 to C 16 alkanols, furthermore nonionic surfactants, such as C 8 to C 12 alkylphenol ethoxylates, C 12 -C 20 alkanol alkoxylates, and block copolymers of ethylene oxide and propylene oxide.
  • the end groups of the polyalkylene oxides can optionally be closed.
  • the nonionic surfactants also include C 4 -C 18 -alkyl glucosides and the alkoxylated products obtainable therefrom by alkoxylation, in particular those which can be prepared by reacting alkyl glucosides with ethylene oxide.
  • the surfactants that can be used in detergents can also have a zwitterionic character and represent soaps.
  • the surfactants are generally present in an amount of 2 to 50, preferably 5 to 45,% by weight of the detergents and cleaners.
  • Builders contained in the detergents and cleaning agents are, for example, phosphates, e.g. orthophosphate, pyrophosphate and especially pentasodium triphosphate, zeolites, soda, polycarboxylic acids, nitrilotriacetic acid, citric acid, tartaric acid, the salts of the acids mentioned and monomeric, oligomeric or polymeric phosphonates.
  • phosphates e.g. orthophosphate, pyrophosphate and especially pentasodium triphosphate
  • zeolites soda
  • polycarboxylic acids e.g. nitrilotriacetic acid
  • citric acid e.g. citric acid
  • tartaric acid e.g.
  • the biodegradable copolymers can also be used as an additive to liquid detergents.
  • Liquid detergents usually contain, as a mixing component, liquid or solid surfactants which are soluble or at least dispersible in the detergent formulation.
  • Suitable surfactants for this are the products which are also used in powder detergents, and liquid polyalkylene oxides or polyalkoxylated compounds.
  • Detergent formulations can also contain corrosion inhibitors, such as silicates, as further additives.
  • Suitable silicates are, for example, sodium silicate, sodium disilicate and sodium metasilicate.
  • the corrosion inhibitors can be present in the detergent and cleaning agent formulation in amounts of up to 25% by weight.
  • Other common additives for detergents and cleaning agents are bleaches, which can be present in an amount of up to 30% by weight.
  • Suitable bleaching agents are, for example, perborates or chlorine-releasing compounds, such as chloroisocyanurates.
  • Another group of additives, which can optionally be contained in detergents, are graying inhibitors.
  • Known substances of this type are carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose and graft polymers of vinyl acetate onto polyalkylene oxides with a molecular weight of 1000 to 15 000.
  • Graying inhibitors can be present in the detergent formulation in amounts of up to 5%.
  • Other common additives for detergents, which may or may not be included, are optical brighteners, enzymes and perfume.
  • the powder detergents can also contain up to 50% by weight of an adjusting agent, such as sodium sulfate.
  • the detergent formulations can be anhydrous or small amounts, e.g. contain up to 10% by weight of water. Liquid detergents usually contain up to 80% by weight of water. Usual detergent formulations are described in detail, for example, in DE-OS 35 14 364, to which express reference is made.
  • the biodegradable copolymers described above can be added to all detergent and cleaning agent formulations.
  • the amounts used for this are between 0.5 and 25, preferably between 1 and 15% by weight, based on the overall formulation.
  • the amounts of biodegradable copolymers used are in most cases preferably 2 to 10% by weight, based on the detergent and cleaning agent mixture.
  • the use of the additives to be used according to the invention in phosphate-free and low-phosphate washing and cleaning agents is of particular importance.
  • the low-phosphate formulations contain up to a maximum of 25% by weight of pentasodium triphosphate or pyrophosphate. Because of the biodegradability, the copolymers to be used according to the invention are preferably used in phosphate-free formulations
  • the biodegradable copolymers to be used according to the invention can be used in detergent formulations together with non-biodegradable copolymers of acrylic acid and maleic acid or homopolymers of acrylic acid.
  • the last-mentioned biodegradable polymers have hitherto been used as incrustation inhibitors in detergent formulations.
  • copolymers of C 3 to C e mono- and dicarboxylic acids or maleic anhydride and C 1 to C 4 -alkyl vinyl ethers are also suitable.
  • the molecular weight of the homopolymers and copolymers is 1000 to 100,000.
  • these incrustation inhibitors can be used in detergents in an amount of up to 10% by weight, based on the overall formulation, in addition to the biodegradable copolymers to be used according to the invention.
  • the known incrustation inhibitors based on the above-mentioned polymers are not biodegradable, they can nevertheless be removed from the waste water in sewage treatment plants together with the activated sludge to which they are adsorbed.
  • the biodegradable copolymers can be added to detergent formulations both in the form of the free acids, in completely neutralized form or in partially neutralized form.
  • K k-10 3.
  • the measurements were in all cases on the sodium salt in aqueous solution at 25 ° C, a pH of 7 and a polymer concentration of the sodium salt of 1% by weight.
  • the copolymerization is carried out at a temperature of 90 ° C within 5 hours by taking the amount of sodium acrylate shown in Table 1 as a 35% aqueous solution, the melt of the comonomers (from maleic anhydride and polyhydric alcohol and unreacted maleic anhydride) and over a period of 6 Hours, starting with the monomer feed, can also continuously run in 90 g of 30% hydrogen peroxide in 100 ml of water. A viscous, aqueous solution is obtained which is polymerized at a temperature of 90 ° C. for 1 hour after the addition of the initiator has ended. After cooling with 25% aqueous sodium hydroxide solution, the aqueous solution is adjusted to a pH of 6.5.
  • the starting materials, the K values, the residual maleic acid content and the data on the biodegradability of the copolymers are given in Table 1.
  • Polyethylene glycol with a molecular weight of 400 was used to prepare the copolymers 11 to 13.
  • the precipitation behavior at pH 7.5 was tested in aqueous solutions which contained 10 to 10,000 mgll of Ca ions (in the form of CaCl 2 ).
  • the following Ca ion concentrations were tested: 10, 50, 75, 100, 150, 500, 1000 and 10,000 mg / l.
  • the copolymer concentrations were varied from 0.1 to 7 mg / l (the following concentrations were tested: 0.1; 0.5; 1.0; 2; 3; 4 and 7 mg copolymer water).
  • the biodegradability of the copolymers was also demonstrated by bacterial growth tests.
  • an enrichment medium was prepared on solid nutrient media and solidified with 18 g / l agar.
  • the enrichment medium had the following composition: (produced according to I. Bauchop and SR Elsden i J. gen. Hikrobiol. 23, 457-469 (1960).
  • copolymers described in Table 1 under Nos. 1 to 16 were added to the nutrient media in each case in concentrations of 10 g / l.
  • Soil samples were either placed in liquid medium and shaken there for 7 days at 30 ° C, or placed as an aqueous suspension directly on solid culture media and also incubated at 30 ° C.
  • the enrichment cultures in liquid medium were transferred to solid culture media after 7 days. Colonies that were growing well were vaccinated from these plates and checked for uniformity in the separating smear.
  • biodegradable copolymers to be used according to the invention in washing and cleaning agents is explained in the following examples.
  • the effect of the biodegradable copolymers as a builder is due to the properties of these polymers to inhibit incrustations on the laundry, to increase the washing power of the detergents and to reduce the graying of white test material when washing in the presence of dirty fabric.
  • test fabrics are subjected to multiple washes in detergent formulations with a wide variety of builder structures, the detergent formulations once containing the biodegradable copolymer to be used according to the invention and, for comparison with the prior art, a copolymer of acrylic acid and maleic acid previously used.
  • the last three washes in a series were carried out with the addition of standard soiling fabric.
  • the reduction in whiteness of the test fabric is a measure of the graying.
  • the increase in whiteness of the dirty fabric is a measure of the washing power of the detergent used and is determined photometrically as a percent reflectance
  • Incrustation values are obtained by ashing the polyester / cotton blend or the cotton terry fabric after the test.
  • the ash content is given in percent by weight. The more effective the polymer contained in the detergent, the lower the ash content of the test fabric.
  • different amounts of use of the biodegradable copolymers to be used according to the invention are necessary.
  • the photometric measurement of the reflectance in% was carried out in the present case on the Elrepho 2000 (Datacolor) at the wavelength of 460 nm (barium primary white standard according to DIN 5033).
  • Table 5 shows that the copolymers to be used according to the invention, which were used in Examples 22, 23 and 24, have a better primary washing action than the copolymer 17 (copolymer according to the prior art) in the comparable detergent formulations according to Comparative Examples 40 to 45 demonstrate.

Claims (6)

1. Utilisation de copolymères solubles dans l'eau, qui contiennent, incorporés par polymérisation,
a) 99,5 à 15% molaires d'au moins un acide monocarboxylique en C3 à Ce, à insaturation monoéthylénique,
b) 0,5 à 20% molaires d'au moins un comonomère présentant au moins deux doubles liaisons éthylé- niquement insaturées et non conjuguées, qui comporte au moins un radical -CO-OX où X représente un atome d'hydrogène, de métal alcalin ou de métal alcalino-terreux, ou un groupe ammonium,
c) 0 à 84,5% molaires d'au moins un acide dicarboxylique en C4 à Ce, à insaturation monoéthylénique,
d) 0 à 20% molaires d'un ou plusieurs esters hydroxyalkyliques, à radical hydroxyalkyle qui comporte de 2 à 6 atomes de carbone, d'acides carboxyliques en C3 à Ce, à insaturation monoéthylénique et
e) 0 à 30% molaires d'autres monomères à insaturation monoéthylénique, solubles dans l'eau, copo- lymérisables avec a), b), c) et d),
avec la condition que la somme des pourcentages molaires a) à e) soit toujours égale à 100 et qui possèdent une valeur K de 8 à 120 (déterminée sur le sel de sodium des copolymères selon H. Fikentscher, en solution aqueuse, à 25°C, un pH de 7 et une concentration en polymère du sel de sodium de 1% en poids),
à titre d'additif pour des détergents et des produits de nettoyage, lavage ou rinçage, en une proportion de 0,5 à 25% en poids.
2. Détergents et produits de rinçage, nettoyage ou lavage, à base de substances tensio-actives ou sur- factives, caractérisés par une teneur en copolymères qui contiennent, incorporés par polymérisation,
a) 99,5 à 15% molaires d'au moins un acide monocarboxylique en C3 à Ce, à insaturation monoéthylénique,
b) 0,5 à 20% molaires d'au moins un comonomère présentant au moins deux doubles liaisons éthylé- niquement insaturées et non conjuguées, qui comporte au moins un radical -CO-OX où X représente un atome d'hydrogène, de métal alcalin ou de métal alcalino-terreux, ou un groupe ammonium,
c) 0 à 84,5% molaires d'au moins un acide dicarboxylique en C4 à Cg, à insaturation monoéthylénique,
d) 0 à 20% molaires d'un ou plusieurs esters hydroxyalkyliques, à radical hydroxyalkyle qui comporte de 2 à 6 atomes de carbone, d'acides carboxyliques en C3 à Ce, à insaturation monoéthylénique et
e) 0 à 30% molaires d'autres monomères à insaturation monoéthylénique, solubles dans l'eau, copo- lymérisables avec a), b), c) et d),
avec la condition que la somme des pourcentages molaires a) à e) soit toujours égale à 100 et qui possèdent une valeur K de 8 à 120 (déterminée sur le sel de sodium des copolymères selon H. Fikentscher, en solution aqueuse, à 25°C, un pH de 7 et une concentration en polymère du sel de sodium de 1% en poids).
3. Détergents et agents de nettoyage, rinçage ou lavage suivant la revendication 2, caractérisés par une teneur de 0,5 à 25% en poids en copolymères solubles dans l'eau, qui contiennent, incorporés par polymérisation,
a) 99,5 à 80% molaires d'au moins un acide monocarboxylique en C3 à Ce, à insaturation monoéthylénique et
b) 0,5 à 20% molaires d'au moins un comonomère que l'on peut obtenir par la réaction de
b1) l'anhydride maléique, l'anhydride itaconique, l'anhydride citraconique, ou leurs mélanges, avec b2) des alcools comportant de 2 à 6 atomes de carbone, polyfonctionnels, des polyalkylèneglycols solubles dans l'eau ou insolubles dans l'eau, d'un poids moléculaire allant jusqu'à 400, des polyalkylèneglycols solubles dans l'eau d'un poids moléculaire supérieur à 400 et s'étendant jusqu'à 10.000, des polyglycérines d'un poids moléculaire allant jusqu'à 2.000, des polyamines, des polyalkylènepolyami- nes, des polyéthylèneimines, des aminoalcools, des acides hydroxyamino- ou diaminocarboxyliques, des copolymères d'oxyde d'alkylène et de dioxyde de carbone, un alcool polyvinylique d'un poids moléculaire allant jusqu'à 10.000, l'alcool allylique, l'allylamine, des esters hydroxyalkyliques à radical hydroxyalkyle qui comporte de 2 à 6 atomes de carbone, d'acides carboxyliques en C3 à Ce, à insaturation monoéthylénique, ou des acides hydroxycarboxyliques en C3 à Ce saturés, ou leurs mélanges, les copolymères présentant une valeur K de 8 à 120.
4. Détergents et agents de nettoyage, rinçage ou lavage selon la revendication 2, caractérisés par une teneur en copolymères solubles dans l'eau, qui contiennent, incorporés par polymérisation,
a) 99 à 15% molaires d'au moins un acide monocarboxylique en C3 à Cg, à insaturation monoéthylénique,
b) 0,5 à 15% molaires d'au moins un comonomère présentant au moins deux doubles liaisons éthylé- niquement insaturées et non conjuguées, qui comporte au moins un radical -CO-OX où X représente un atome d'hydrogène, de métal alcalin ou de métal alcalino-terreux ou un radical ammonium et
c) 0,5 à 84,5% molaires d'au moins un acide dicarboxylique en C4 à Ce, à insaturation monoéthylénique, avec la condition que la somme des pourcentages molaires a) à c) soit toujours égale à 100 et qui possèdent une valeur K de 12 à 100 (déterminée sous forme du sel de sodium des copolymères selon H.
Fikentscher en solution aqueuse, à 25°C, un pH de 7 et une concentration en polymère du sel de sodium de 1% en poids).
5. Détergents et agents de nettoyage, rinçage ou lavage selon l'une des revendications 2 à 4, caractérisés par une teneur de 1 à 15% en poids de copolymères, qui contiennent, à titre de monomère b), en incorporation polymérique, au moins un composé de la formule
Figure imgb0017
ou
Figure imgb0018
où X représente un atome d'hydrogène, de métal alcalin ou un radical ammonium,
n a une valeur qui varie de 1 à 120 et
m a une valeur qui varie de 0 à 4.
6. Détergents et agents de nettoyage, rinçage ou lavage selon l'une des revendications 2 à 5, caractérisés en ce qu'ils sont dépourvus de phosphates et contiennent au moins un copolymère en une proportion de 2 à 10% en poids.
EP88107406A 1987-05-16 1988-05-07 Utilisation de copolymerisates solubles dans l'eau contenant des monomères ayant au moins deux liaisons insaturées éthyléniques dans les agents de lavage et de nettoyage Expired - Lifetime EP0291808B1 (fr)

Priority Applications (1)

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AT88107406T ATE61395T1 (de) 1987-05-16 1988-05-07 Verwendung von wasserloeslichen copolymerisaten, die monomere mit mindestens zwei ethylenisch ungesaettigten doppelbindungen einpolymerisiert enthalten,in wasch- und reinigungsmitteln.

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DE19873716543 DE3716543A1 (de) 1987-05-16 1987-05-16 Verwendung von wasserloeslichen copolymerisaten, die monomere mit mindestens zwei ethylenisch ungesaettigten doppelbindungen einpolymerisiert enthalten, in wasch- und reinigungsmitteln
DE3716543 1987-05-16

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EP0291808B1 true EP0291808B1 (fr) 1991-03-06

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AU601578B2 (en) 1990-09-13
EP0291808A1 (fr) 1988-11-23
CA1307437C (fr) 1992-09-15
DE3716543A1 (de) 1988-11-24
JPS63305199A (ja) 1988-12-13
US4897220A (en) 1990-01-30
DE3861903D1 (de) 1991-04-11
ATE61395T1 (de) 1991-03-15
AU1614788A (en) 1988-11-17
ES2020589B3 (es) 1991-08-16

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