WO2002018526A1 - Verwendung von gepfropften polyalkylenoxiden als vergrauungsinhibitoren beim waschen - Google Patents
Verwendung von gepfropften polyalkylenoxiden als vergrauungsinhibitoren beim waschen Download PDFInfo
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- WO2002018526A1 WO2002018526A1 PCT/EP2001/010000 EP0110000W WO0218526A1 WO 2002018526 A1 WO2002018526 A1 WO 2002018526A1 EP 0110000 W EP0110000 W EP 0110000W WO 0218526 A1 WO0218526 A1 WO 0218526A1
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- graft polymers
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Classifications
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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
- C11D3/3788—Graft polymers
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
Definitions
- the invention relates to the use of graft polymers which are obtainable by polymerizing
- polymer B) 5 to 90% by weight of at least one polymer B) selected from polyalkylene oxides which contain at least 3 units of a C to C 1 alkylene oxide, and polytetrahydrofurans which contain at least 3 tetramethylene oxide units, and mixtures thereof,
- the invention relates to the use of the graft polymers mentioned as a graying-inhibiting additive in detergent, and to detergents which contain these graft polymers.
- Graying occurs primarily in fabrics that contain synthetic fibers, especially in textiles that contain polyester fibers. Phosphates as essential detergent ingredients have a water-softening effect and also act as graying inhibitors. Legislative measures in many countries require that the content of phosphorus greatly reduce phates in detergents or offer phosphate-free detergents. The absence of the phosphates leads to greater graying.
- graft polymers as coating or binding agents in pharmaceutical dosage forms such as tablets, capsules, etc.
- the graft polymers are obtained by polymerizing vinyl esters of C 1 -C 4 -carboxylic acids and possibly N-vinyl lactams in the presence of polyethers. The use as a graying inhibitor in detergents is not described.
- EP-A-219 048 discloses the use of graft polymers as graying inhibitors in the washing and aftertreatment of textile goods which contain synthetic fibers.
- the graft polymers are obtained by grafting polyalkylene oxides with vinyl acetate.
- the object was to provide polymers which, while maintaining the good graying inhibition, have better soil release, i.e. the improved soil release properties should not be achieved at the expense of graying inhibition.
- the graft polymers can be obtained by polymerizing graft monomers A) in the presence of polymers B). Accordingly, it is a graft polymerization in which the graft monomers A) are grafted onto the polymers B).
- the proportion of graft monomers A) is 10 to 95, preferably 20 to 80,% by weight, based on the total mass of monomers A) and polymers B). Accordingly, the proportion of polymers B) is 5 to 90, preferably 20 to 80,% by weight, based on the total mass mentioned.
- the graft monomers A) contain, based on A),
- Suitable vinyl esters a) are, for example, vinyl esters of saturated carboxylic acids having 1 to 20, in particular 1 to 6, carbon atoms. Examples are vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate. Preferably used "acetate and vinyl propionate, in particular vinyl acetate. There may be a Vinylester alone or a mixture of several Vinylester be used.
- N-vinyl lactams b) are N-vinyl lactams with 5 to 13 carbon atoms in the lactam ring. Examples are N-vinylbutyrolactam, N-vinylcaprolactam, N-vinylvalerolactam and N-vinyllaurolactam. N-Vinylcaprolactam is preferably used. There can be an N-
- Vinyl lactam alone or a mixture of several N-vinyl lactams can be used.
- the graft monomers A) can also optionally
- copolymerizable monomers c) are used, the amount preferably used is 5 to 80, in particular 10 to 60% by weight, based on the graft monomers A).
- Suitable copolymerizable monomers c) are, for example, vinylcarboxamides such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-methylpropionamide and N-vinyl propionamide.
- N-vinylformamide is preferably used.
- the polymerized monomer units can be partially or completely hydrolyzed.
- Suitable comonomers c) are the esters, amides and nitriles of monoethylenically unsaturated C 3 to Cg carboxylic acids.
- Suitable amides are, for example, acrylamide, methacrylamide and N-alkyl mono- and diamides with alkyl radicals of 1 to 6 carbon atoms, such as N-methyl acrylamide, N, N-dimethylacrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-propylacrylamide and tert.
- crylamides such as dimethylaminoethyl acrylate, id, dimethylaminoethyl ethacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dirnethylaminopropylmethacrylamide and diethylamine.
- Suitable comonomers c) are the esters of the monoethylenically unsaturated carboxylic acids with C] . -to C 6 alcohols, such as methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate or with glycols or polyglycols, where in each case only one OH group of the glycols and polyglycols with one ethylenic unsaturated carboxylic acid is esterified, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, as well as the acrylic acid monoesters of polyalkylene glycols with a molecular weight of 1500 to 10,000.
- esters of ethylenically unsaturated alkylaminoethylaminoalkylamines are also suitable , Dirnethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, diethylaminobutylacrylate, dimethylaminopethylamylateylate dimethylaminopethylamino acrylate.
- the basic acrylates and Acryla ide are used in the form of the free bases, the salts with mineral acids, such as hydrochloric acid, sulfuric acid and nitric acid, or in quaternized form.
- Suitable uaternizing agents are, for example, dimethyl sulfate, methyl chloride, ethyl chloride, benzyl chloride or diethyl sulfate.
- Suitable comonomers c) are also monoethylenically unsaturated mono- and dicarboxylic acids (anhydrides) having 3 to 6 atoms, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid (anhydride), fumaric acid, itaconic acid (anhydride) and citraconic acid (anhydride).
- anhydrides monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 6 atoms, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid (anhydride), fumaric acid, itaconic acid (anhydride) and citraconic acid (anhydride).
- comonomers c) are N-vinylpyrrolidone,
- N-vinylimidazole and substituted N-vinylimidazoles, such as N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole, and N Vinylimidazolines, such as N-vinylimidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-ethylimidazoline.
- N-vinylimidazoles and N-vinylimidazolines are also used in neutralized or in quaternized form with mineral acids, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, benzyl chloride, methyl chloride or ethyl chloride.
- suitable comonomers c) are monomers containing sulfo groups, such as vinylsulfonic acid, allylsulfonic acid, methlylsulfonic acid, styrene sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate and 2-acrylamido-2-methylpropanesulfonic acid.
- the compounds having acid groups can be used in the form of the free acids, the ammonium, alkali metal and alkaline earth metal salts in the graft polymerization.
- comonomers c acrylonitrile, N-vinylpyrrolidone and acrylic acid are preferred. It is understood that mixtures of several comonomers c) can also be used.
- a modification of the graft copolymers can be achieved by copolymerizing the monomers a) and b) and optionally c) with a monomer d) having at least two ethylenically unsaturated non-conjugated double bonds in the molecule in the presence of the polymers B).
- the monomers d) are usually used as crosslinkers in copolymerizations.
- the use of the crosslinking monomers d) generally results in an increase in the K values of the copolymers.
- crosslinking monomers d) are used, the amount preferably used is 0.05 to 2% by weight, based on the graft monomers A).
- Suitable crosslinking monomers d) are, for example, methylene bisacrylamide, esters of acrylic acid and methacrylic acid with polyhydric alcohols, e.g. Glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, as well as polyols esterified at least twice with acrylic acid or methacrylic acid, such as pentaerythritol and glucose.
- Suitable crosslinkers are also divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose.
- Preferred crosslinking monomers d) are water-soluble monomers, such as glycol diacrylate or glycol diacrylates of polyethylene glycols having a molecular weight (number average) from 300 to 10,000.
- the graft monomers A) are polymerized in the presence of at least one polymer B) which is selected from
- Such polyalkylene oxides i) and polytetrahydrofurans ii) are known.
- the homopolymers and copolymers of C 2 -C 4 -alkylene oxides are of particular interest. They are produced, for example, by homo- or copolymerization of ethylene oxide, propylene oxide, n-butylene oxide and / or isobutylene oxide.
- the copolymers can either be statistical copolymers if one polymerizes mixtures of at least 2 alkylene oxides or block copolymers if one first polymerizes an alkylene oxide, for example ethylene oxide, and then polymerizes another alkylene oxide, for example propylene oxide.
- the block copolymers can be assigned, for example, to types AB, ABA or BAB, where A is for example a polyethylene oxide block and B is a polypropylene oxide block. These copolymers may optionally also contain copolymerized n-butylene oxide and / or isobutylene oxide.
- the polyalkylene oxides i) contain at least 3 alkylene oxide units in the molecule.
- the polyalkylene oxides can contain, for example, up to 50,000 alkylene oxide units in the molecule. Those polyalkylene oxides which have 3 to 1000 alkylene oxide units in the molecule are preferred.
- the polytetrahydrofurans ii) contain at least 3 tetramethylene oxide units in the molecule, for example 3 to 200, preferably 3 to 100 tetramethylene oxide units.
- Polymers B) which are preferably used are homo- or block copolymers of ethylene oxide and propylene oxide and random copolymers of ethylene oxide and propylene oxide which can be obtained by copolymerizing a mixed gas of ethylene oxide and propylene oxide.
- Homopolymers of ethylene oxide are used particularly preferably, in particular those with a number average molecular weight of 200 to 15,000.
- polyalkylene oxides are also taken to mean addition products of C- to C 4 -alkylene oxides with alcohols, carboxylic acids, phenols and amines. These addition products are obtained by reacting the C - to C 4 -alkylene oxides with the corresponding alcohols, carboxylic acids, phenols or amines.
- Suitable alcohols for the reaction with the alkylene oxides have, for example, 1 to 30 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, n-octanol, 2-ethylhexanol, decanol, dodecanol, palmityl alcohol, cetyl alcohol and stearyl alcohol.
- alcohol obtainable by the oxo process, for example C 0 alcohols, C 3 oxo alcohols or native alcohols such as C 0 / Ci 8 tallow fatty alcohols.
- dihydric and polyhydric alcohols for example glycol, glycerin, erythritol, pentaerythritol and sorbitol.
- the alcohols are usually reacted in a molar ratio of 1: 3 to 1: 200 with at least one C to C 4 alkylene oxide.
- Carboxylic acids suitable for the reaction with the alkylene oxides are, in particular, fatty acids, preferably those having 8 to 10 carbon atoms in the molecule. Examples are lauric acid, myristic acid, stearic acid, palmitic acid, coconut fatty acid, tallow fatty acid and oleic acid.
- Suitable phenols for the reaction with the alkylene oxides are, for example, C 1 -C 2 -alkylphenols, such as n-decylphenol, n-octylphenol, isobutylphenol and methylphenol.
- Amines suitable for the reaction with the alkylene oxides are, for example, secondary C 2 - to C 3 o-amines, such as di-n-butylamine, di-n-octylamine, dimethylamine and distearylamine.
- the molar ratio of amine to at least one alkylene oxide is generally 1: 3 to 1: 200 and is preferably in the range from 1: 3 to 1: 100.
- the alkylene oxides can be added to the abovementioned compounds in the form of a mixed gas, or the reaction can be carried out first with ethylene oxide and then with propylene oxide. It is also possible first to add propylene oxide and then ethylene oxide to the compounds mentioned. In addition to ethylene oxide and propylene oxide, isobutylene oxide and / or n-butylene oxide can optionally also be added in each case. Block copolymers are formed during the successive addition of the alkylene oxides.
- the free OH groups of the alkoxylation products may also be advantageous to seal with an end group.
- the end groups can be sealed, for example, with an alkyl radical to form an ether group.
- the alkoxylation products can be reacted with alkylating agents such as dimethyl sulfate.
- the terminal ones OH groups can optionally also be esterified by reaction with carboxylic acids, for example acetic acid or stearic acid.
- a mixture of several polymers B) " can also be used.
- the polymerization of the graft monomers A) onto the polymers B) can be carried out in the presence or in the absence of inert solvents or inert diluents. Since the polymerization in the absence of inert solvents or diluents usually leads to non-uniform polymers, polymerization in an inert solvent or diluent is preferred.
- concentration of components A) and B) in the graft polymerization in the presence of inert solvents or inert diluents is 10 to 80, preferably 20 to 70,% by weight.
- inert solvents or diluents in which the polymers B) can be suspended and which dissolve the graft monomers A) are suitable.
- the graft polymers are in suspended form after the polymerization and can easily be isolated by filtration in solid form.
- Suitable inert diluents are, for example, toluene, xylene, o-, m-, p-xylene and isomer mixtures, ethylbenzene, aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, nonane, dodecane, cyclohexane, cyclooctane, methylcyclohexane, and mixtures of the hydrocarbons mentioned and gasoline fractions that do not contain polymerizable monomers.
- Chlorinated hydrocarbons such as chloroform, carbon tetrachloride, hexachloroethane, dichloroethane and tetrachloroethane are also suitable.
- the polymers B) are preferably used in anhydrous form.
- a preferred way of producing the graft polymers is solution and suspension polymerization, the polymers B), the graft monomers A) and the graft polymer formed being at least dispersed, preferably in dissolved form.
- inert solvents such as methanol, ethanol, isopropanol, n-propanol, n-butanol, sec-butanol, tetrahydrofuran, dioxane, water and mixtures of the inert solvents mentioned are suitable for solution polymerization.
- Components A) and B) are usually graft-polymerized in an inert gas atmosphere with the exclusion of atmospheric oxygen. Good mixing of the reactants is generally ensured during the polymerization.
- the reactants which are preferably present in an inert diluent, can be copolymerized discontinuously by heating the reaction mixture to the polymerization temperature and then allowing the reaction to proceed. These temperatures are usually in the range from 40 to 180 ° C.
- the order of addition of the monomers a) to d) is arbitrary. For example, all or some of the monomers can be added simultaneously or one after the other. So you can e.g. add the vinyl ester a) and the N-vinyl lactam b) together or first the vinyl ester a) and then the N-vinyl lactam b) or vice versa first the N-vinyl lactam b) and then the vinyl ester a).
- the addition can be discontinuous (e.g. as a single dose or batchwise in several portions in the course of the polymerization) or continuous.
- a continuous inflow can be considered over the inflow time, e.g. be constant over time (linear), increasing or decreasing, the increase or decrease e.g. can be linear, exponential, obey a staircase function, or some other mathematical function.
- the monomers a) to d) are added continuously or batchwise to the polymerizing mixture at the desired polymerization temperature to the extent that the polymerization is readily controllable in the desired temperature range .
- a mode of addition of the monomers a) to d) is preferred, in which the polymers B) or at least some of the polymers B) are initially introduced into the polymer in the polymer reactor and heated therein to the desired polymerization temperature with stirring.
- the monomers a) and b) and, if appropriate, c) and / or d) and the initiator and, if appropriate, a regulator are added over a period of, for example, about 1 to 10, preferably 2 to 8 hours.
- a procedure is used, for example, when polymerizing components A) and B) in an inert diluent in which component B) is suspended, and also used in the polymerization carried out in solution.
- the procedure is such that at least some of the polymers B) are initially introduced into an aqueous medium and the monomers a) to d) are added continuously or batchwise to the polymerizing reaction mixture.
- the polymerization reaction can be carried out continuously or batchwise.
- the temperatures are usually in the range from 40 to 180 ° C., preferably 50 to 150 ° C. and in particular 60 to 110 ° C.
- the polymerization is advantageously carried out under pressure.
- the graft polymers can be prepared in the customary polymerization devices.
- stirred kettles are used which are equipped with an anchor, blade, impeller or multi-stage impulse countercurrent stirrer.
- it can be advantageous to carry out the polymerization in kneaders. It may also be necessary to polymerize in a kneader when working at high concentrations.
- the graft monomers A) are preferably polymerized by free radicals in the presence of polymers B). Free-radical initiators are also used for this.
- Suitable radical initiators are preferably all those compounds which have a half-life of less than 3 hours at the polymerization temperature chosen in each case. If 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 using an initiator which already decomposes at a lower temperature to start the polymerization and then to complete the main polymerization with an initiator that decomposes at a higher temperature. Water-soluble and water-insoluble initiators or mixtures of water-soluble and Use water-insoluble initiators. The water-insoluble initiators are then soluble in the organic phase.
- Acetylcyclohexanesulfonyl peroxide diacetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, tert. - Butyl perneodecanoate, 2,2'-azobis (4-methoxy-2, 4-dimethylvalonitrile), 2, 2 '-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2, 2' -azobis - (2-methylpropion-amidine) dihydrochloride.
- Dibenzoyl peroxide tert. -Butylper-2-ethylhexanoate, tert. -Butylpermaleinate, 2, 2 '-azobis (isobutyronitrile), dimethyl-2, 2' -azobisisobutyrate, sodium persulfate, potassium persulfate, ammonium persulfate.
- salts or complexes of heavy metals for example copper, cobalt, manganese, iron, vanadium, nickel and chromium salts, or organic compounds such as benzoin, dimethylaniline or ascorbic acid are used, the half-lives can be increased of the radical initiators indicated are reduced. So you can, for example, tert.
- the reducing component of redox catalysts can also be formed, for example, from compounds such as sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and hydrazine. Based on the monomers a) to d) used in the polymerization, 0.01 to 20, preferably 0.05 to 10,% by weight of a polymerization initiator or a mixture of several polymerization initiators is generally used. 5
- the redox components used are 0.01 to 15% by weight, based on the total mass of monomers A) and polymers B), of the compounds having a reducing action.
- the heavy metals mentioned are used in the range from 0.1 to 100 ppm, preferably 0.5 to 10 10 ppm, based on the total mass mentioned.
- the graft polymerization of the graft monomers A) can also be carried out by the action of ultraviolet radiation, if appropriate in the presence of UV initiators.
- UV radiation if appropriate in the presence of UV initiators.
- the polymerization is advantageously carried out in the presence of regulators.
- Suitable regulators are, for example, organic compounds containing sulfur in bound form. These include, for example, mercapto compounds such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercapto-propionic acid, butyl mercaptan and dodecyl mercaptan.
- mercapto compounds such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercapto-propionic acid, butyl mercaptan and dodecyl mercaptan.
- Aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, propionic acid, hydrazine sulfate and butenols. If the polymerization is carried out in the presence of regulators, one needs
- Graft polymers are obtained which, insofar as they are soluble in water, preferably have K values of 5 to 150, preferably 10 to 150 45 and in particular 10 to 50 (determined according to H. Fikentscher, Cellulosechemie, Volume 13. 58-64 and 71-74 (1932) on a 1 wt .-% solution in acetone at 25 ° C).
- the graft polymers which can be prepared by the processes given above are usually colorless to brownish-colored products. When polymerizing in an aqueous medium, they are present as dispersions or polymer solutions. Depending on the particular composition of the graft polymers, these are generally low-viscosity to pasty aqueous solutions or aqueous dispersions.
- the grafted-on vinyl esters a) of the graft polymer can be at least partially hydrolyzed.
- the graft polymer is accordingly optionally subjected to at least partial hydrolysis.
- the ester groups of the grafted vinyl esters a) are hydrolyzed. If a hydrolysis takes place, preferably 1 to 100, in particular 1 to 50 and particularly preferably 5 to 20 mol% of the ester groups are hydrolyzed.
- the hydrolysis leads to graft polymers containing vinyl alcohol units.
- the hydrolysis can be carried out, for example, by adding a base, such as sodium hydroxide solution or potassium hydroxide solution, or else by adding acids, such as mineral acids (for example hydrochloric, sulfuric or phosphoric acid), methanesulfonic acid, formic acid or lactic acid, and optionally heating the mixture.
- a base such as sodium hydroxide solution or potassium hydroxide solution
- acids such as mineral acids (for example hydrochloric, sulfuric or phosphoric acid), methanesulfonic acid, formic acid or lactic acid, and optionally heating the mixture.
- the bases or acids mentioned are used in conventional amounts, so that further details are unnecessary.
- the graft polymers are used according to the invention for washing and aftertreating textile goods, in particular textile goods that contain synthetic fibers.
- synthetic fibers are polyester fibers, polyamide fibers, polyacrylic fibers and other conventional synthetic fibers.
- the graft polymers are used as graying-inhibiting additives in detergents. They are used in particular as an additive to powdery or liquid detergents in amounts of usually 0.05 to 15, preferably 0.1 to 5% by weight, based on the detergent formulations.
- the detergent fleet act as graying inhibitors and as an additive that promotes soil release (soil release).
- the polymers according to the invention as additives in phosphate-free and reduced-phosphate powder Detergents and in liquid detergents as well as in laundry aftertreatment agents, eg fabric softeners.
- Reduced phosphate detergents contain less than 25% by weight phosphate.
- the graft polymers can be added to the detergent formulation in the form of granules, a paste, a highly viscous mass, as a dispersion or as a solution in a solvent.
- the graft polymers can also be applied to the surface of adjusting agents, e.g. Sodium sulfate, or builders (e.g. zeolites) and other solid additives in the detergent formulation can be adsorbed.
- the phosphate content is below 25 wt .-%, or detergent, are in general free of phosphate, contain as an essential ingredient surfactants, for example C 8 to C ⁇ 2 alkylphenol ethoxylates, from C i2 to C 20 - Alkanol ethoxylates, as well as block copolymers of ethylene oxide and propylene oxide.
- the polyalkylene oxides are solid substances at room temperature up to temperatures of 50 to 60 ° C. and are readily soluble or dispersible in water. These are linear or branched reaction products of ethylene oxide with propylene oxide and / or isobutylene oxide, which have a block structure or which can also have a statistical structure.
- the end groups of the polyalkylene oxides can optionally be closed. This is understood to mean that the free OH groups of the polyalkylene oxides can be etherified and / or esterified and / or aminated and / or reacted with isocyanates.
- Anionic surfactants such as C 8 to C 2 alkylbenzenesulfonates, C 2 to C 6 alkanesulfonates, C 2 to C 6 alkyl sulfates, C 2 to C 1 alkyl sulfosuccinates and are also suitable as constituents of powdered detergents sulfated ethoxylated C] _ to Ci 6 ⁇ alkanols.
- Powder detergents usually contain 5 to 20% by weight of a surfactant or a mixture of surfactants.
- the powder detergents may also optionally contain polycarboxylic acids or their salts, for example tartaric acid or citric acid.
- incrustation inhibitors are, for example, homopolymers of acrylic acid, methacrylic acid and maleic acid or copolymers, for example copolymers of maleic acid and acrylic acid, copolymers of maleic acid and methacrylic acid or copolymers of I) acrylic acid and / or methacrylic acid with II) acrylic acid esters , Methacrylic acid esters, vinyl esters, allyl esters, itaconic acid esters, Itaconic acid, methylene malonic acid, methylene malonic acid esters, crotonic acid and crotonic acid esters.
- homopolymers of acrylic acid, methacrylic acid and maleic acid or copolymers for example copolymers of maleic acid and acrylic acid, copolymers of maleic acid and methacrylic acid or copolymers of I) acrylic acid and / or methacrylic acid with II) acrylic acid esters , Methacrylic acid esters, vinyl esters, allyl esters, itaconic acid
- copolymers of olefins and C 1 -C 4 -alkyl vinyl ethers are suitable.
- the molecular weight of the homopolymers and copolymers is 1,000 to 100,000.
- the incrustation inhibitors are used in an amount of 0.5 to 10% by weight in detergents.
- detergents can also include corrosion inhibitors, monomeric, oligomeric and polymeric phosphonates, ether sulfonates based on unsaturated fatty alcohols, e.g. Oleyl alcohol ethoxylate butyl ether and its alkali salts.
- Powder detergents may also contain zeolites, e.g. in an amount of 5 to 30% by weight.
- the detergent formulations can also contain bleaching agents. If bleaching agents are used, the amounts usually used are 3 to 25% by weight. The best known bleach is, for example, sodium perborate.
- the detergent formulations may also contain bleach activators, plasticizers, defoamers, perfumes, optical brighteners and enzymes. Detergents, such as sodium sulfate, can optionally be present in an amount of 10 to 30% by weight.
- the graft polymers described can also be used as an additive to liquid detergents.
- the liquid detergents contain, as a mixing component, liquid or solid surfactants which are soluble or at least dispersible in the detergent formulation.
- the surfactant content of liquid detergents is usually in the range from 15 to 50% by weight.
- the products which can also be used in powder detergents, as well as liquid polyalkylene oxides or polyalkoxylated compounds, can be considered as a side effect.
- a small amount of solubilizers e.g. Water or a water-miscible organic solvent, e.g. Make isopropanol, methanol, ethanol, glycol, diethylene glycol or triethylene glycol, a homogeneous mixture.
- the graft polymers are also suitable as an additive in the aftertreatment of textile goods, in particular textile goods containing synthetic fibers.
- they are added to the last rinsing bath of a washing machine cycle, the addition either being carried out together with a fabric softener usually used at this point or — if a fabric softener is not desired — alone instead of the fabric softener.
- the amounts used are 0.01 to 0.3 g / 1 wash liquor.
- the Use of the graft polymers in the last rinsing bath of a washing machine cycle has the advantage that the laundry is soiled much less by detached dirt particles which are present in the washing liquor during the next washing cycle than without the addition of the graying inhibitor in the previous washing.
- the graft polymers used in accordance with the invention are distinguished by the fact that the graying is effectively reduced and the dirt is detached well (good soil release).
- the compounds of the prior art do not have this combination of properties.
- The% given in the examples are% by weight.
- the K values of the graft polymers were measured according to H. Fikentscher, Cellulosechemie, Vol. 13, 58-64 and 71-74 (1932) in acetone at a temperature of 25 ° C. and a polymer concentration of 1% by weight.
- the polyethylene glycol used had a number average molecular weight of from 6000. It was Pluriol® ® E 6000 from BASF was used.
- the graying-inhibiting effect of the graft polymers was tested as follows: Polyester test fabric was subjected to a series of 3 washes together with a standard soiled fabric. The dirty fabric was renewed after each wash, the test fabric becoming more soiled after each wash. The measure of graying was the whiteness of the white test fabrics before and after washing. The whiteness of the test fabric after the 3rd wash was used to assess the degree of soiling. The degree of whiteness was determined by photometric measurement of the reflectance on an Elrepho 2000 photometer (Datacolor) at the wavelength of 460 nm (barium primary white standard according to DIN 5033). The values were secured by repeated repetition and averaging.
- Datacolor Elrepho 2000 photometer
- the test detergent used in the tests was a powder detergent and had the following composition.
- TED Tetraacetylethylenediamine
- the washing conditions were as follows:
- Tester Launder-O-meter water hardness: 3.0 mmol / 1
- Table 1 summarizes the results.
- a graft copolymer according to EP-A 219 048, column 5, example 8 in table 1 was used.
- the graft polymers according to the invention were examined for their dirt-removing effect.
- polyester test fabrics were washed three times with the test detergent, to which 1.0% by weight of the graft polymers according to the invention was added.
- the fabrics pretreated in this way were dried and soiled by dropping 0.2 g of used motor oil (waste oil).
- the test fabrics were without and with addition the graft polymers washed.
- the measure of the dirt-removing properties was the whiteness of the test fabrics before and after washing.
- the degree of whiteness was determined by photometric measurement of the reflectance as described above under No. 2 on the Elrepho 2000 photometer. The values were secured by repeated repetition and averaging.
- test detergent used in the tests was identical to the detergent described in No. 2.
- the washing conditions were identical to the conditions under No. 2, but no dirt fabric and 5 g polyester 854 (standard test fabric of the Krefeld laundry research institute) was used as the test fabric.
- the graying inhibitors of the prior art can effectively reduce graying (example 2V), but have only an insufficient dirt-removing effect (example 4V).
- the graft polymers used according to the invention are notable for the fact that the graying is effectively reduced and the dirt is detached well. The improvement of the soil release could therefore be achieved while maintaining the good graying inhibition.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2001284043A AU2001284043A1 (en) | 2000-08-30 | 2001-08-30 | Use of grafted polyalkylene oxides as greying inhibitors when washing |
JP2002524029A JP2004507610A (ja) | 2000-08-30 | 2001-08-30 | 洗濯の際の灰化抑制剤としてのグラフト化ポリアルキレンオキシドの使用 |
MXPA03001264A MXPA03001264A (es) | 2000-08-30 | 2001-08-30 | Uso de oxidos de polialquileno injertados como inhibidores del agrisado en el lavado. |
CA002420938A CA2420938A1 (en) | 2000-08-30 | 2001-08-30 | Use of grafted polyalkylene oxide as graying inhibitors in laundering |
US10/362,360 US6946004B2 (en) | 2000-08-30 | 2001-08-30 | Use of grafted polyalkylene oxides as greying inhibitors when washing |
EP01962983A EP1315789A1 (de) | 2000-08-30 | 2001-08-30 | Verwendung von gepfropften polyalkylenoxiden als vergrauungsinhibitoren beim waschen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10042815.0 | 2000-08-30 | ||
DE10042815A DE10042815A1 (de) | 2000-08-30 | 2000-08-30 | Verwendung von gepfropften Polyalkylenoxiden als Vergrauungsinhibitoren beim Waschen |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002018526A1 true WO2002018526A1 (de) | 2002-03-07 |
Family
ID=7654449
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2001/010000 WO2002018526A1 (de) | 2000-08-30 | 2001-08-30 | Verwendung von gepfropften polyalkylenoxiden als vergrauungsinhibitoren beim waschen |
Country Status (8)
Country | Link |
---|---|
US (1) | US6946004B2 (de) |
EP (1) | EP1315789A1 (de) |
JP (1) | JP2004507610A (de) |
AU (1) | AU2001284043A1 (de) |
CA (1) | CA2420938A1 (de) |
DE (1) | DE10042815A1 (de) |
MX (1) | MXPA03001264A (de) |
WO (1) | WO2002018526A1 (de) |
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WO2006132385A1 (en) * | 2005-06-06 | 2006-12-14 | Nippon Shokubai Co., Ltd. | Water-soluble polymer, production method thereof, and application thereof |
WO2007051742A1 (de) * | 2005-11-04 | 2007-05-10 | Basf Se | Verfahren zur herstellung von pfropfpolymerisaten |
WO2007059857A1 (de) * | 2005-11-26 | 2007-05-31 | Allessachemie Gmbh | Polymerdispersionen, verfahren zu deren herstellung und verwendung |
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EP1945183B1 (de) * | 2005-11-04 | 2016-03-23 | Basf Se | Verwendung von copolymeren als solubilisatoren für in wasser schwerlösliche verbindungen |
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2000
- 2000-08-30 DE DE10042815A patent/DE10042815A1/de not_active Withdrawn
-
2001
- 2001-08-30 JP JP2002524029A patent/JP2004507610A/ja active Pending
- 2001-08-30 CA CA002420938A patent/CA2420938A1/en not_active Abandoned
- 2001-08-30 WO PCT/EP2001/010000 patent/WO2002018526A1/de active Application Filing
- 2001-08-30 US US10/362,360 patent/US6946004B2/en not_active Expired - Fee Related
- 2001-08-30 AU AU2001284043A patent/AU2001284043A1/en not_active Abandoned
- 2001-08-30 MX MXPA03001264A patent/MXPA03001264A/es active IP Right Grant
- 2001-08-30 EP EP01962983A patent/EP1315789A1/de not_active Withdrawn
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004101827A1 (de) * | 2003-05-13 | 2004-11-25 | Basf Aktiengesellschaft | Verwendung von copolymerisaten als hilfsmittel für die lederherstellung |
WO2006132385A1 (en) * | 2005-06-06 | 2006-12-14 | Nippon Shokubai Co., Ltd. | Water-soluble polymer, production method thereof, and application thereof |
WO2007051742A1 (de) * | 2005-11-04 | 2007-05-10 | Basf Se | Verfahren zur herstellung von pfropfpolymerisaten |
EP1945183B1 (de) * | 2005-11-04 | 2016-03-23 | Basf Se | Verwendung von copolymeren als solubilisatoren für in wasser schwerlösliche verbindungen |
WO2007059857A1 (de) * | 2005-11-26 | 2007-05-31 | Allessachemie Gmbh | Polymerdispersionen, verfahren zu deren herstellung und verwendung |
US7951768B2 (en) | 2007-06-29 | 2011-05-31 | The Procter & Gamble Company | Laundry detergent compositions comprising amphiphilic graft polymers based on polyalkylene oxides and vinyl esters |
WO2011121477A1 (en) * | 2010-03-30 | 2011-10-06 | Basf Se | Use of copolymer for increasing activity of pesticide |
WO2014072211A1 (de) * | 2012-11-07 | 2014-05-15 | Henkel Ag & Co. Kgaa | Polymere mit polaren gruppen als schmutzablösevermögende wirkstoffe |
Also Published As
Publication number | Publication date |
---|---|
EP1315789A1 (de) | 2003-06-04 |
CA2420938A1 (en) | 2003-02-27 |
MXPA03001264A (es) | 2003-06-24 |
JP2004507610A (ja) | 2004-03-11 |
US20030186833A1 (en) | 2003-10-02 |
DE10042815A1 (de) | 2002-03-14 |
US6946004B2 (en) | 2005-09-20 |
AU2001284043A1 (en) | 2002-03-13 |
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