WO1991019778A1 - Utilisation de copolymeres greffes dans des produits de lavage et de nettoyage - Google Patents

Utilisation de copolymeres greffes dans des produits de lavage et de nettoyage Download PDF

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Publication number
WO1991019778A1
WO1991019778A1 PCT/EP1991/000976 EP9100976W WO9119778A1 WO 1991019778 A1 WO1991019778 A1 WO 1991019778A1 EP 9100976 W EP9100976 W EP 9100976W WO 9119778 A1 WO9119778 A1 WO 9119778A1
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weight
polyvalent
acid
carboxylic acids
graft copolymers
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PCT/EP1991/000976
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German (de)
English (en)
Inventor
Alexander Kud
Dieter Boeckh
Heinrich Hartmann
Richard Baur
Paul Diessel
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Basf Aktiengesellschaft
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Publication of WO1991019778A1 publication Critical patent/WO1991019778A1/fr

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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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • 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
    • C11D3/3788—Graft polymers

Definitions

  • the invention relates to the use of graft copolymers which can be obtained by grafting alkylene glycols, polyalkylene glycols, glycerol and / or polyglycerols with ethylenically unsaturated carboxylic acids, as an additive to phosphate-free or low-phosphate detergents and cleaning agents and detergents and cleaning agents containing such additives.
  • EP-PS 25 551 discloses the use of copolymers of mono-ethylenically unsaturated monocarboxylic acids, such as acrylic acid, and mono-ethylenically unsaturated dicarboxylic acids, such as maleic acid, as incrustation inhibitors in detergents.
  • the copolymers described therein are phosphate substitutes. They are used in amounts of up to 10% by weight in the detergent formulations and enable the production of phosphate-free or low-phosphate detergents.
  • EP-PS 98803 discloses water-soluble or water-dispersible graft polymers which are prepared by grafting polyalkylene glycols which have been modified with hydrophobic substituent end groups with ethylenically unsaturated polymerizable sulfonic acids or carboxylic acids or their anhydrides. These graft polymers are used for various purposes, including as a builder and as a detergent. In detergents, they primarily act as graying inhibitors and have a positive influence on the primary washing effect.
  • the present invention has for its object to provide other additives for detergents and cleaning agents.
  • Suitable graft bases a) for the preparation of the graft copolymers are alkylene glycols which have 2 to 6 carbon atoms, for example ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, hexanediol- 1.6 and mixtures of the alkylene glycols mentioned.
  • Polyalkylene glycols with a molecular weight (number average) of up to 50,000 are also suitable.
  • Such compounds are based on alkylene oxides with 2 to 4 carbon atoms or tetrahydrofuran as monomer units.
  • Polyethylene glycols with molar masses of 106, ie diethylene glycol, up to 6000 are preferred.
  • adducts of propylene oxide or butylene oxide with C 2 - to C - alkylene glycols or with mixtures of different alkylene oxides for example ethylene oxide, propylene oxide and butylene oxide with alkylene glycols or with mono- or polyhydric C 1 -C 6 -alcohols.
  • the alkoxides can be present in the adducts in the form of blocks or in statistically polymerized form.
  • glycerol and polyglycerols up to a molar mass of 2000. These are understood to mean diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexane glycerol, octaglycerol and decaglycerol.
  • the above-mentioned compounds of component a) can optionally be chain extended. This should be understood to mean the reaction of these compounds with polyvalent carboxylic acids or polyvalent isocyanates.
  • Suitable polyvalent carboxylic acids for this purpose are, for example, oxalic acid, succinic acid, adipic acid, terephthalic acid, phthalic acid, pyroellitic acid, citric acid and butanetetracarboxylic acid.
  • Suitable polyvalent isocyanates for chain extension are, for example, hexamethylene diisocyanate and tolylene diisocyanate. The molecular weight (number average) of the chain-extended products is at most 50,000.
  • the compounds a especially the homopolymers of ethylene oxide and their oligoesters with polyvalent aliphatic or aromatic carboxylic acids, optionally chain-extended copolymers of ethylene oxide with propylene oxide, butylene oxide and / or isobutylene oxide are highlighted. Particularly preferred is the use of ethylene glycol and Ho opolymerisquestioned of ethylene oxide and copoly erisquestioned of ethylene oxide and propylene oxide, which contain 40 to 99 wt .-% ethylene oxide and have a molar mass (number average) of 116 to 6000.
  • Monoethylenically unsaturated C3 to C ⁇ carboxylic acids are used as component b).
  • Suitable carboxylic acids are, for example, acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, vinyl acetic acid, maleic acid, itaconic acid and mixtures of these compounds.
  • Part of the free groups of the graft base a) can react to form the esters. Thereafter, however, a graft reaction of maleic anhydride takes place on the graft base a) modified in this way.
  • acrylic acid methacrylic acid, maleic acid, itaconic acid or mixtures of the compounds mentioned are preferably used.
  • Mixtures of 40 to 99% by weight of acrylic acid and 60 to 1% by weight of maleic acid are particularly preferably used as monomers in the graft copolymerization of the graft base according to a).
  • the graft copolymerization can take place with the free acids or anhydrides, their mixtures or also with the alkali metal or ammonium salts of the monomers b) which can be obtained by partial or complete neutralization.
  • the non-neutralized monomers are preferably used.
  • graft copolymers can optionally also be used.
  • monomers referred to as c) are, for example, esters of ethylenically unsaturated C 3 - to Cio-carboxylic acids with C 1 ⁇ to C 22 ⁇ alcohols, for example methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, isopropyl acrylate, ethylhexyl acrylate, stearyl acrylate, methyl methacrylate , Ethyl ethacrylate, isopropyl ethacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, stearyl methacrylate, maleic acid diethyl ester, maleic acid diethyl ester, maleic acid diethyl ester, maleic acid diethyl ester, maleic acid diethy
  • amides of ethylenically unsaturated carboxylic acids such as acrylic id or methacrylamide or diamides are used, which are derived from monoethylenically unsaturated C 3 - to C ⁇ -carboxylic acids and Ci- to C 2 2 -mono- or dialkylamines.
  • vinyl esters of saturated C 2 -C 20 -carboxylic acids for example vinyl acetate, vinyl propionate and vinyl butyrate.
  • Suitable initiators which form free radicals are the starters commonly used in polymerizations, e.g. organic peroxides, such as diacetyl peroxide, dibenzyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl permaleinate, cumene hydroperoxide, diisopropyl peroxidicarbamate, bis (o-toluolyl) peroxide Didecanoyl peroxide, dilauroyl peroxide, tert-butyl hydroperoxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide and mixtures of the initiators mentioned.
  • organic peroxides such as diacetyl peroxide, dibenzyl peroxide
  • azo starters come into consideration, e.g. 2,2'-azo-bis- (2-amidinopropane) dihydrochloride, 2,2'-azo-bis- (N, N'-dimethylene) - iso-butyramidine dihydrochloride, 2- (carbamoylazo) isobutyronitrile, 4,4 '- azo-bis (4-cyanovaleric acid), 4,4-dimethyl-2 (phenylazo) valeronitrile, 4-methoxy-2,4-dimethyl-2- (phenylazo) valeronitrile, 1, l'-azo-bis- (cyclohexane-1-carbonitrile), 2,2'-azo-bis- (isobutyronitrile) and / or 2,2'-azo-bis- (2,4-dimethylvaleronitrile).
  • Hydrogen peroxide, sodium peroxydisulfate, potassium peroxydisulfate and ammonium peroxydisulfate are also suitable
  • the peroxidic initiators can also be used in combination with reducing agents such as iron-II-sulfate, sodium sulfite, sodium hydrogen sulfite,
  • Sodium dithionite, triethanolamine and ascorbic acid can be used in the form of the so-called redox initiators.
  • the polymerization can also be initiated by adding a photoinitiator and irradiation with UV light or by exposure to high-energy radiation.
  • sodium or potassium peroxodisulfate is preferably used, while the bulk polymerization or the polymerization is carried out in organic solution with starters soluble therein, e.g. with organic peroxides.
  • the free radical initiators are used in conventional amounts, e.g. in amounts of 0.2 to 20% by weight, based on the monomers. Amounts of 1.0 to 10% by weight, based on the monomers, are preferably used.
  • graft copolymers Based on 1 part by weight of at least one compound a), 0.25 to 5.0, preferably 0.5 to 3.5 parts by weight of at least one onoethylenically unsaturated carboxylic acid b) and 0 to 2.0 parts by weight are used Parts of another monoethylenically unsaturated compound c).
  • the graft copolymers are prepared by known methods, cf. eg EP-A-0 353 071. The graft copolymerization can be carried out in bulk or in In the presence of inert solvents.
  • Suitable inert solvents are, for example, water, monohydric C 1 -C 4 -alcohols such as methanol, ethanol, n-propanol, isopropanol and butanols, esters of saturated C 2 -C 6 -carboxylic acids with monohydric C 1 -C 4 -alcohols , such as methyl acetate, ethyl acetate, n-propyl acetate, butyl acetate, methyl propionate and ethyl propionate, ethers such as diethyl ether, dioxane or tetrahydrofuran, ethylene glycol diethyl ether, tert-butyl methyl ether and ethylene glycol diethyl ether. Water and mixtures of water and methanol, ethanol and / or isopropanol and tetrahydrofuran are preferably used as solvents.
  • the graft copolymerization can be carried out, for example, by mixing at least one compound of component a) with at least one monomer of component b), adding an initiator and heating the mixture to temperatures in the range from 40 to 180 ° C. in which the graft copolymerization takes place.
  • the graft copolymerization can also be carried out semi-continuously, in which part, e.g. 10% of the mixture to be polymerized from components a) and b) and optionally c) and the initiator, heated to the polymerization temperature and after the polymerization has started, adds the rest of the mixture to be polymerized to the extent that the polymerization takes place , so that the heat of polymerization can be removed in a controlled manner.
  • the remaining polymerizable mixture can be added either continuously or batchwise.
  • the graft copolymers are also obtainable by placing the compounds of component a) in a reactor, heating them therein to the polymerization temperature and separately at least one monomer from group b) and optionally c) and the polymerization initiator either all at once, batchwise or preferably adds continuously, so that the polymerization proceeds in a controllable manner. If an inert solvent is used in the graft copolymerization, the amounts used are such that the concentration of components a), b) and optionally c) is 20 to 99, preferably 40 to 95,% by weight.
  • the graft polymerization can take place in an acidic or partially or completely neutralized state.
  • the base can be added to the reaction batch or continuously.
  • Preferred bases are sodium hydroxide solution and potassium hydroxide solution.
  • amines and amino alcohols can also be used for neutralization.
  • small amounts of monomers containing at least two ethylenically unsaturated double bonds can also be added in amounts of up to 1% by weight, based on the sum of the monomers, for further modification of the graft copolymers.
  • Suitable compounds of this type are, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, and also the diesters of polyalkylene glycols with molecular weights from 106 to 2000 with acrylic acid, methacrylic acid or maleic acid, di-, tri- and tetra (meth) acrylates or maleinates of alkoxylated polyvalent ones Alcohols such as glycerin and pentaerythritol. For further modification it may be necessary to carry out the graft copolymerization in the presence of regulators.
  • Suitable regulators are, for example, mercaptoethanol, mercaptopropanol, mercaptobutanols, thioglycolic acid, mercaptoacetic acid, mercaptopropionic acid and mercapto-butyric acid. If regulators are also used in the graft copolymerization, the amounts used are 0.1 to 1.0% by weight, based on the monomers used.
  • the graft copolymers thus obtainable have K values from 15 to 100, preferably from 20 to 88 (determined according to H. Fikentscher) in aqueous solution at 25 ° C. and a polymer concentration of 2.0% by weight. They are water-soluble or water-dispersible. The alkali and ammonium salts of the graft copolymers are generally more soluble in water than the free acids.
  • the graft copolymers are used as an additive to low-phosphate or phosphate-free powdery or liquid detergents and cleaners in amounts of 0.1 to 15, preferably 0.5 to 10% by weight. They act as a builder, contribute to a washing activation of the surfactants of the detergents and cleaning agents, bring about a reduction in the incrustation on the washed textile goods and make a significant contribution to dispersing dirt in the washing liquor.
  • the graft copolymers to be used according to the invention have the advantage that they combine a good dispersing action in the case of mineral dirt, such as clay, with a strong reduction in the incrustations of the laundry.
  • composition of detergent formulations can be very different. The same applies to the composition of cleaning agent 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) is tabulated and in Ull ann's Encyclopedia of Industrial Chemistry, Verlag Chemie, Weinheim 1983, 4th edition, pages 63-160.
  • Detergent formulations are powdery or liquid.
  • the powdered detergents can have different compositions depending on the region and the particular application.
  • the detergents and cleaning agents are usually based on surfactants and, if necessary, builders. In the case of pure liquid detergents, in order to be able to obtain homogeneous formulations, builders are often not used. By adding anionic polymers, the washing effect of the surfactants can be increased by reducing the negative effects of the hardness in water (such as the deactivation of soaps).
  • the graft copolymers on polyalkylene oxides which are stable to an alkaline medium (in contrast to structures containing ester groups), make them well suited as wash-activating additives to liquid detergents and cleaning agents.
  • Suitable surfactants are for example anionic surfactants such as C ⁇ - to Cj-2 alkyl benzene sulfonates, C12 to C ⁇ 6-alkanesulfonates, C ⁇ 2 are - C ⁇ 6 to alkyl sulfate, C12 to Ci ⁇ -alkyl sulfosuccinates and sulfated ethoxylated C12 to C ⁇ 6-alkanols, also nonionic surfactants, such as C ⁇ ⁇ to C ⁇ 2 - alkylphenol hoxylates, C12- to C2o ⁇ alkanol alkoxylates, and block copolymers of ethylene oxide and propylene oxide.
  • the end groups of the polyalkylene oxides can optionally be closed. This is to be understood to mean that the free OH groups of the polyalkylene oxides can be etherified, esterified, acetalized and / or initiated.
  • the nonionic surfactants also include C4- to Ci ⁇ -alkylglucosides and the alkoxylated products obtainable therefrom by alkoxylation, in particular those which can be prepared by reacting alkylglucosides with ethylene oxide.
  • 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 isothionates, can also be used in liquid detergents.
  • the anionic surfactants can be in the form of the sodium, potassium and ammonium salts and also as legible salts of organic bases, such as mono-, di- or triethanolamine or other substituted amines.
  • the surfactants that can be used in detergents can also have a zwitterionic character and can be 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 (for example orthophosphate, pyrophosphate and above all 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 for example orthophosphate, pyrophosphate and above all pentasodium triphosphate
  • zeolites soda
  • polycarboxylic acids for example orthophosphate, pyrophosphate and above all pentasodium triphosphate
  • zeolites soda
  • polycarboxylic acids for example orthophosphate, pyrophosphate and above all pentasodium triphosphate
  • nitrilotriacetic acid for example orthophosphate, pyrophosphate and above all pentasodium triphosphate
  • zeolites soda
  • low-phosphate detergents are understood to mean detergents which have a phosphate content, calculated as pentasodium metriphosphate, of at most 25% by weight.
  • the copolymers to be used according to the invention can either function as the sole builder in detergents or can also be used in a mixture with other conventional builders, e.g. in a mixture with zeolite, soda, nitrile triacetic acid, ethylenediaminetetraacetate, phosphonate etc.
  • the liquid detergents can be water-containing or water-free.
  • they can optionally contain known builders. If the graft copolymers to be used according to the invention do not dissolve in the liquid detergent formulation, they can be finely divided therein and stabilized in the liquid detergent formulation with the aid of a dispersant.
  • the percentages in the examples mean percent by weight.
  • the molar masses given in the examples represent the number average molar masses determined by osmometry. Production of the graft copolymers.
  • 150 g of component a) to be grafted are placed in a 1 1 three-necked flask together with 150 ml of deionized water under nitrogen and heated to 95-100 ° C.
  • the amount of acrylic acid given in Table 1 is metered in over 3 h, and a solution of the amount of sodium peroxodisulfate (initiator) in 50 g of 10 water given in Table 1 is added within 3.5 h.
  • the mixture is cooled, adjusted to pH 6.8 with sodium hydroxide solution and the solids content given in Table 1 is adjusted.
  • component a) to be grafted are each added as a 40% solution in deionized water in a 2 liter glass reactor with stirrer, inert gas feed and two feed vessels
  • the reactor is flushed with inert gas and the monomer solution (component b) is metered in in 3 h, the initiator solution (hydrogen peroxide, 11.3 percent in water) in 3.5 h.
  • the composition and amount of the solutions are noted in Table 2. After the end of the feed, the mixture is kept at 95 ° C. for a further 2 h and, after cooling with sodium hydroxide solution
  • This graft copolymer was prepared in accordance with synthesis example 2 of EP-PS 98 803 by grafting 15 g of the adduct from 10 mol of ethylene oxide onto 1 mol of nonylphenol with 35 g of acrylic acid.
  • This graft copolymer was synthesized according to synthesis example 18 of EP-PS 98 803 by polymerizing 25 g of acrylic acid in the presence of 25 g of an adduct of 10 mol of ethylene oxide and 1 mol of nonylphenol.
  • This graft copolymer was prepared in accordance with synthesis example 21 of EP-PS 98 803 by polymerizing 10 g of acrylic acid in the presence of 40 g of an adduct of 10 mol of ethylene oxide and 1 mol of nonylphenol.
  • the activity is given in% activity, where 0% activity corresponds to the ash content without incrustation inhibitor and 100% activity corresponds to the ash content of the fabric before washing.
  • the effect is then calculated from the ash content using a linear mathematical approach.
  • the ash content of the pure cotton fabric before washing is 0.08%, that of the terry fabric 0.1%.
  • the maximum ash content without inhibitor is: Detergent max. Ash cotton [%]
  • wash liquor 250 g, the water used has 4 mmol hardness per liter (molar ratio: calcium to magnesium equal to 4: 1)
  • Washing time 30 min. at 60 ° C (including heating-up time)
  • Test fabric 10 g each
  • Wash liquor 250 g, the water used has 3 mmol hardness per liter (molar ratio: calcium to magnesium equal to 6: 4)
  • Washing time 30 min. at 60 ° C (including heating-up time)
  • Test fabric WFK 20D
  • the polymers were incorporated into the liquid detergent formulation D and the dirty fabric was washed under the above-mentioned conditions.
  • the degree of whiteness of the washed fabric is used to assess the primary washing effect of the formulation.
  • the values are secured by repeated repetition and averaging.
  • the photometric measurement of the reflectance in% was measured in the present case on the Elrepho 2000 (Datacolor) at the wavelength of 460 nm (barium primary white standard according to DIN 5033).
  • the removal of particle dirt from tissue surfaces is supported by the addition of polyelectrolytes.
  • the stabilization of the dispersion formed after the particles are detached from the tissue surface is an important task of these polyelectrolytes.
  • the stabilizing influence of the anionic dispersants results from the fact that as a result of Adsorption of dispersant molecules on the solid surface whose surface charge is increased and the repulsive energy is increased.
  • Other influencing variables on the stability of a dispersion include steric effects, temperature, pH and the electrolyte concentration.
  • the dispersibility of various polyelectrolytes can be assessed in a simple manner using the clay dispersion test (CD test) described below.
  • Finely ground china clay SPS 151 is used as a model for particulate dirt.
  • 1 g of clay is intensively dispersed in a standing cylinder (100 ml) for 10 minutes with the addition of 1 ml of a 0.1% sodium salt solution of the polyelectrolyte in 89 ml of water.
  • a 2.5 ml sample is taken from the center of the standing cylinder and, after dilution to 25 ml, the turbidity of the dispersion is determined using a turbidimeter.
  • samples are taken again and the turbidity determined as above.
  • the turbidity of the dispersion is given in NTU (nephleometric turbidity units). The less the dispersion settles during storage, the higher the turbidity values, the more stable the dispersion.
  • the polyelectrolytes according to the invention give dispersions which, after standing for 60 minutes, have significantly higher turbidity values (NTU units) than the comparisons indicated. Together with the significantly higher dispersion constants, this means that the polyelectrolytes according to the invention can disperse clay better and at the same time allow the production of dispersions with improved storage stability.

Abstract

On utilise comme additifs dans des produits de lavage ou de nettoyage sans phosphates ou à teneur réduite en phosphates des copolymères greffés obtenus par: a) le greffage de glycols d'alcylène, de glycols de polyalcylène ayant des masses molaires égales à 50.000 au maximum, de polytétrahydrofurane, de glycérine, de polyglycérine, de produits d'addition d'oxydes d'alcylène ayant de 2 à 4 atomes de C sur des alcools monovalents ou polyvalents ayant de 1 à 6 atomes de C, ainsi que de produits de réaction à chaîne allongée des composés susmentionnés avec des acides carboniques polyvalents ou avec des isocyanates polyvalents, avec: b) des acides carboniques monoéthyléniquement insaturés ayant de 3 à 8 atomes de carbone et éventuellement avec: c) d'autres composés monoéthyléniquement insaturés, à des températures comprises entre 40 et 100 °C, en présence d'initiateurs formateurs de radicaux. L'invention concerne également des produits de lavage et de nettoyage qui contiennent entre 0,1 et 15 % en poids des copolymères greffés susmentionnés.
PCT/EP1991/000976 1990-06-19 1991-05-27 Utilisation de copolymeres greffes dans des produits de lavage et de nettoyage WO1991019778A1 (fr)

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DE19904019418 DE4019418A1 (de) 1990-06-19 1990-06-19 Verwendung von pfropfcopolymeren als zusatz zu phospatfreien oder phosphatarmen wasch- und reinigungsmitteln
DEP4019418.3 1990-06-19

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EP0543562A2 (fr) * 1991-11-19 1993-05-26 Rohm And Haas Company Compositions adoucissantes pour matières textiles
EP0639592A1 (fr) * 1993-08-18 1995-02-22 Nippon Shokubai Co., Ltd. Copolymères greffés soluble dans l'eau, et leur procédé de préparation
EP0945473A1 (fr) * 1998-03-24 1999-09-29 National Starch and Chemical Investment Holding Corporation Méthode du type "in situ" solvant-libre pour la production de copolymères greffés basés sur les anhydrides
WO2002018526A1 (fr) * 2000-08-30 2002-03-07 Basf Aktiengesellschaft Utilisation d'oxydes de polyalkylene greffes en tant que substances empechant les matieres textiles de grisailler lors du lavage
WO2021160851A1 (fr) * 2020-02-14 2021-08-19 Basf Se Polymères greffés biodégradables
WO2022263354A1 (fr) 2021-06-18 2022-12-22 Basf Se Polymères greffés biodégradables
WO2023017062A1 (fr) * 2021-08-12 2023-02-16 Basf Se Polymères greffés biodégradables

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US6835708B2 (en) * 2001-03-07 2004-12-28 Nippon Shokubai Co., Ltd. Graft polymer composition and its production process and uses
DE102005053064A1 (de) * 2005-11-04 2007-05-16 Basf Ag Verfahren zur Herstellung von Pfropfpolymerisaten
DE102012221198A1 (de) * 2012-11-20 2014-05-22 Henkel Ag & Co. Kgaa Anti-adhäsive Polymere zur mikrobiell-repulsiven Textilausrüstung

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EP0011833A1 (fr) * 1978-11-24 1980-06-11 Union Carbide Corporation Polyoxyalcoylènes carboxylés et méthode pour leur préparation
EP0098803A1 (fr) * 1982-07-06 1984-01-18 Ciba-Geigy Ag Polymères greffés solubles ou dispersables dans l'eau, leur fabrication et utilisation
US4521615A (en) * 1983-03-16 1985-06-04 Olin Corporation Preparation of carboxylic acid-containing monoether and polyether polyol addition products
EP0285037A2 (fr) * 1987-04-03 1988-10-05 BASF Aktiengesellschaft Utilisation de polymères greffés à base d'oxydes de polyalkylènes comme agents antirédéposants pendant le lavage et le post-traitement de matières textiles contenant des fibres synthétiques

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EP0011833A1 (fr) * 1978-11-24 1980-06-11 Union Carbide Corporation Polyoxyalcoylènes carboxylés et méthode pour leur préparation
EP0098803A1 (fr) * 1982-07-06 1984-01-18 Ciba-Geigy Ag Polymères greffés solubles ou dispersables dans l'eau, leur fabrication et utilisation
US4521615A (en) * 1983-03-16 1985-06-04 Olin Corporation Preparation of carboxylic acid-containing monoether and polyether polyol addition products
EP0285037A2 (fr) * 1987-04-03 1988-10-05 BASF Aktiengesellschaft Utilisation de polymères greffés à base d'oxydes de polyalkylènes comme agents antirédéposants pendant le lavage et le post-traitement de matières textiles contenant des fibres synthétiques

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0543562A2 (fr) * 1991-11-19 1993-05-26 Rohm And Haas Company Compositions adoucissantes pour matières textiles
EP0543562A3 (en) * 1991-11-19 1994-06-15 Rohm & Haas Fabric softening compositions
US5503767A (en) * 1991-11-19 1996-04-02 Rohm And Haas Company Anti-static rinse added fabric softener
EP0639592A1 (fr) * 1993-08-18 1995-02-22 Nippon Shokubai Co., Ltd. Copolymères greffés soluble dans l'eau, et leur procédé de préparation
EP0945473A1 (fr) * 1998-03-24 1999-09-29 National Starch and Chemical Investment Holding Corporation Méthode du type "in situ" solvant-libre pour la production de copolymères greffés basés sur les anhydrides
WO2002018526A1 (fr) * 2000-08-30 2002-03-07 Basf Aktiengesellschaft Utilisation d'oxydes de polyalkylene greffes en tant que substances empechant les matieres textiles de grisailler lors du lavage
US6946004B2 (en) 2000-08-30 2005-09-20 Basf Aktiengesellschaft Use of grafted polyalkylene oxides as greying inhibitors when washing
WO2021160851A1 (fr) * 2020-02-14 2021-08-19 Basf Se Polymères greffés biodégradables
WO2021160795A1 (fr) * 2020-02-14 2021-08-19 Basf Se Polymères greffés biodégradables
WO2022263354A1 (fr) 2021-06-18 2022-12-22 Basf Se Polymères greffés biodégradables
WO2023017062A1 (fr) * 2021-08-12 2023-02-16 Basf Se Polymères greffés biodégradables

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