EP1497348A1 - Dispersions polyurethane anioniques modifiees par voie cationique - Google Patents

Dispersions polyurethane anioniques modifiees par voie cationique

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Publication number
EP1497348A1
EP1497348A1 EP03724970A EP03724970A EP1497348A1 EP 1497348 A1 EP1497348 A1 EP 1497348A1 EP 03724970 A EP03724970 A EP 03724970A EP 03724970 A EP03724970 A EP 03724970A EP 1497348 A1 EP1497348 A1 EP 1497348A1
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European Patent Office
Prior art keywords
weight
cationically modified
polymers
particulate
anionic
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EP03724970A
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German (de)
English (en)
Inventor
Jürgen Detering
Karl Häberle
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3726—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00

Definitions

  • the invention relates to cationically modified particulate anionic polyurethanes, aqueous polyurethane dispersions containing them, the use of the particulate polyurethanes and the polyurethane dispersions, processes for treating surfaces and treatment agents therefor which contain the cationically modified particulate anionic polyurethanes.
  • Anionic polyurethane dispersions are used in the art to modify the properties of surfaces.
  • aqueous anionic polyurethane dispersions are used in concentrated form for finishing and coating textiles and textile substrates or for leather finishing.
  • the dispersions are made by common methods, e.g. Squeegee, brush, soak or impregnate applied to a substrate and then dried. The finely divided particles film and give the respective surface new properties.
  • washing, rinsing, cleaning and maintenance processes are usually carried out in a highly dilute aqueous liquor, the ingredients of the formulation used not remaining on the substrate, but rather being disposed of with the waste water.
  • the modification of surfaces with anionic polyurethane dispersions is only possible to an entirely unsatisfactory extent in dilute aqueous liquor due to the poor surface affinity of the polyurethane particles.
  • US 3,580,853 describes a detergent formulation which contains water-insoluble, finely divided substances such as biocides and certain cationic polymers which increase the deposition and retention of the biocides on the surface of the laundry.
  • No. 5,476,660 discloses the principle of using polymeric retention agents for cationic or zwitterionic dispersions of polystyrene or wax, which contain an active substance embedded in the dispersed particles. These dispersed particles are referred to as "carrier particles" because they adhere to the treated surface and release the active substance there, for example when used in formulations containing surfactants.
  • WO 01/94516 describes the use of cationically modified, particulate hydrophobic polymers based on ethylenically unsaturated monomers as additives for detergents or care products for textiles and as additives for detergents.
  • the particulate, hydrophobic polymers are preferably made up of water-insoluble, nonionic monomers such as alkyl acrylates.
  • the cationic modification is carried out by coating the hydrophobic polymer particles with cationic polymers.
  • WO 01/94517 describes the use of cationically modified, particulate hydrophobic polymers based on ethylenically unsaturated monomers as additives for dishwashing, cleaning and impregnating agents for hard surfaces.
  • the object of the invention is to provide treatment agents for textile and non-textile materials which can also be used in highly dilute aqueous liquor and which impart advantageous properties to the surfaces of the treated materials or the materials themselves.
  • the object is achieved by cationically modified, particulate anionic polyurethanes with a particle size of 10 nm to 10 ⁇ m, the particulate polyurethanes being cationically modified by coating their surface with cationic polymers, and by cationically modified, aqueous anionic polyurethane dispersions which modify the cationically modified, contain particulate anionic polyurethanes.
  • the object is further achieved by using the cationically modified, particulate anionic polyurethanes as a surface-modifying additive in detergents, dishwashing agents, care products or cleaning agents.
  • the object is further achieved by using the cationically modified, aqueous anionic polyurethane dispersions as rinsing, washing or cleaning liquors.
  • the particulate polyurethanes which are cationically modified by coating their surface, have anionic groups.
  • they can also have cationic groups, as long as the particles as a whole have a net anionic charge. This manifests itself in the fact that the polyurethane particles migrate to the anode in the electric field at a given pH value.
  • Both purely anionic and amphoteric polyurethane dispersions can thus be modified cationically as long as the anionic character of the polyurethane dispersions predominates, that is to say the molar proportion of the anionic units contained in the polymer is greater than the molar proportion of the Polymer contained cationic units.
  • anionic polyurethane dispersions with a predominantly anionic character are referred to below as anionic polyurethane dispersions.
  • anionic polyurethane dispersions By coating the particle surface of the anionic polyurethane particles with cationic polymers, it is possible to modify them cationically, so that the particles have a net cationic charge on their surface and their direction of migration in the electric field is reversed.
  • the surface-modified, particulate polyurethanes can be obtained, for example, by treating aqueous anionic polyurethane dispersions with polyurethane particles having a size of 10 nm to 10 ⁇ m with an aqueous solution or dispersion of a cationic polymer.
  • the easiest way to do this is to combine the aqueous anionic polyurethane dispersion, which contains particles with a particle size of 10 nm to 10 ⁇ m, with the aqueous solution or dispersion of the cationic polymer.
  • the cationic polymers are preferably used in the form of aqueous solutions. However, aqueous dispersions of cationic polymers are also suitable, the particles of the cationic polymers dispersed therein having an average diameter of up to 1 ⁇ m.
  • the aqueous anionic polyurethane dispersion and the solution or dispersion of the cationic polymers can be mixed at temperatures of, for example, 0 to 100.degree.
  • the amount of cationic polymers required for the cationic modification depends both on the net surface charge of the polyurethane particles and on the charge density of the cationic polymers at the pH which prevails during the coating of the polyurethane particles with the cationic polymers.
  • the weight ratio of dispersed polyurethane particles to cationic polymers is generally from 100: 0.5 to 100: 5.
  • the presence of the cationic polymers does not cause the - oppositely charged - anionic dispersion particles to coagulate, but rather stable dispersions of the cationically modified particles are obtained.
  • the affinity of the anionic polyurethane particles is reduced by the cationic modification
  • Aqueous polyurethane dispersions are expediently prepared by reacting
  • bl 10 to 100 mol%, based on the total amount of diols (b), have a molecular weight of 500 to 5000, and
  • Suitable monomers (a) are the polyisocyanates customarily used in polyurethane chemistry.
  • diisocyanates X (NCO) 2 where X represents an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic or aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms.
  • diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, l-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis (4-isocyanatocyclohexyl) propane,
  • Trimethylhexane diisocyanate 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanato-diphenylmethane, 2,4-diisocyanato-diphenylmethane, p-xylylene diisocyanate, m- and p- ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate (TMXDI), the isomers of bis (4-isocyanatocyclohexyl) methane such as trans / trans, cis / cis and cis / trans isomers and mixtures consisting of these compounds.
  • TXDI Trimethylhexane diisocyanate
  • 1,4-diisocyanatobenzene 2,4-diisocyanatotoluene,
  • mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanatodiphenylmethane are particularly important as mixtures of these isocyanates, and the mixture of 20 mol% 2.4 diisocyanatotoluene and 80 mol% 2,6-diisocyanatotoluene is particularly suitable.
  • mixtures of aromatic isocyanates such as 2,4 diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocyanates such as hexamethylene diisocyanate or IPDI are particularly advantageous, the preferred mixing ratio of the aliphatic to aromatic isocyanates being 4: 1 to 1: 4.
  • isocyanates which, in addition to the free isocyanate groups, contain further blocked isocyanate groups, e.g. Wear uretdione or urethane groups.
  • those isocyanates can also be used which carry only one isocyanate group. In general, their proportion is at most 10 mol%, based on the total molar amount of the monomers.
  • the monoisocyanates usually carry further functional groups such as olefinic groups or carbonyl groups and are used to introduce functional groups into the polyurethane which enable the polyurethane to be dispersed or crosslinked or further polymer-analogously converted.
  • Monomers such as isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate (TMI) are suitable for this.
  • isocyanates are e.g. obtained by reacting divalent isocyanates with one another by derivatizing part of their isocyanate groups to AUophanat or isocyanurate groups.
  • Commercially available compounds are, for example, the isocyanurate of hexamethylene diisocyanate.
  • diols (b) which can be considered are primarily higher molecular weight diols (b1) which have a molecular weight of about 500 to 5000, preferably of about 1000 to 3000 g / mol.
  • the diols (bl) are in particular polyester polyols, which are known, for example, from Ulimann's Encyclopedia of Industrial Chemistry, 4th edition, volume 19, pages 62 to 65. Polyester polyols are preferably used which are obtained by reacting dihydric alcohols with dihydric carboxylic acids.
  • the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or their mixtures can also be used to prepare the polyester polyols.
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and optionally substituted, for example by halogen atoms, and / or unsaturated.
  • Examples include: suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylene tefrahydrophthalic anhydride,
  • Dicarboxylic acids of the general formula HOOC- (CH 2 ) y -COOH are preferred, where y is a number from 1 to 20, preferably an even number from 2 to 20, for example succinic acid, adipic acid, dodecanedicarboxylic acid and sebacic acid.
  • polyhydric alcohols examples include ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butene-1,4-diol, butyne-1,4-diol, pentane-1 , 5-diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes such as 1,4-bis (hydroxymethyl) cyclohexane, 2-methyl-propane-1,3-diol, furthermore diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol , Dibutylene glycol and polybutylene glycols.
  • Alcohols of the general formula HO- (CH 2 ) x -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20. Examples of these are ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-l-, 8-diol and dodecane-l, 12-diol.
  • polycarbonate diols such as those e.g. can be obtained by reacting phosgene with an excess of the low molecular weight alcohols mentioned as synthesis components for the polyester polyols.
  • Lactone-based polyester diols are also suitable, these being homopolymers or copolymers of lactones, preferably addition products of lactones with terminal hydroxyl groups onto suitable difunctional starter molecules.
  • Preferred lactones are those which are derived from hydroxycarboxylic acids of the general formula HO- (CH 2 ) z -COOH, where z is a number from 1 to 20, preferably an odd number from 3 to 19, for example epsilon-caprolactone , ß-propiolactone, gamma-butyrolactone and / or methyl-epsilon-caprolactone and mixtures thereof.
  • Suitable starter components are, for example, the above Component for the polyester polyols called low molecular weight dihydric alcohols.
  • the corresponding polymers of epsilon-caprolactone are particularly preferred.
  • Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers.
  • the corresponding chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones can also be used.
  • polyether diols are suitable as monomers (b1). They are in particular by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF 3 or by addition of these compounds, if appropriate in a mixture or in succession, to starting components with reactive hydrogen atoms, such as alcohols or amines, for example Water, ethylene glycol, propane-l, 2-diol, propane-l, 3-diol, 2,2-bis (4-hydroxyphenyl) propane or aniline are available. Polytetrahydrofuran with a molecular weight of 2000 to 5000, and especially 3500 to 4500, is particularly preferred.
  • polyester diols and polyether diols can also be used as mixtures in a ratio of 0.1: 1 to 9: 1.
  • the hardness and the modulus of elasticity of the polyurethanes can be increased if, in addition to the diols (b1), low molecular weight diols (b2) with a molecular weight of about 50 to 500, preferably from 60 to 200 g / mol are used as the diols (b).
  • polyester polyols The structural components of the short-chain alkanediols mentioned for the production of polyester polyols are primarily used as monomers (b2), the unbranched diols having 2 to 12 carbon atoms and an even number of carbon atoms, and 1,5-pentanediol and neopentyl glycol being preferred.
  • the proportion of diols (bl), based on the total amount of diols (b), is preferably 10 to 100 mol% and the proportion of monomers (b2), based on the total amount of diols (b), 0 to 90 mol% %.
  • the ratio of the diols (bl) to the monomers (b2) is particularly preferably 0.2: 1 to 5: 1, particularly preferably 0.5: 1 to 2: 1.
  • the monomers (c), which are different from the diols (b), are generally used for crosslinking or chain extension. They are generally more than dihydric, non-aromatic alcohols, amines with 2 or more primary and / or secondary amino groups, and compounds which, in addition to one or more alcoholic hydroxyl groups, carry one or more primary and / or secondary amino groups. Alcohols with a higher valence than 2, which can serve to establish a certain degree of branching or crosslinking, are, for example, trimethylolpropane, glycerol or sugar. .
  • monoalcohols which, in addition to the hydroxyl group, carry a further group which is reactive toward isocyanates, such as monoalcohols having one or more primary and / or secondary amino groups, e.g. Monoethanolamine.
  • Polyamines with 2 or more primary and / or secondary amino groups are used above all if the chain extension or crosslinking is to take place in the presence of water, since amines generally react faster with isocyanates than alcohols or water. This is often necessary when aqueous dispersions of crosslinked polyurethanes or high molecular weight polyurethanes are desired. In such cases, the procedure is to prepare prepolymers with isocyanate groups, to disperse them rapidly in water and then to chain-lengthen or crosslink them by adding compounds having several isocyanate-reactive amino groups.
  • Amines suitable for this purpose are generally polyfunctional amines in the molecular weight range from 32 to 500 g / mol, preferably from 60 to 300 g / mol, which contain at least two primary, two secondary or one primary and one secondary amino groups.
  • Examples include diamines such as diaminoethane, diaminopropane, diaminobutane, diaminohexane, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane (isophorone diamine, IPDA), 4,4'-diaminodicyclohexylmethane, l , 4-diaminocyclohexane, -aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as diethylenetriamine or 1,8-diamino-4-aminomethyloctane.
  • diamines such as diamino
  • the amines can also be used in blocked form, for example in the form of the corresponding ketimines (see, for example, CA-1 129 128), ketazines (see, for example, US Pat. No. 4,269,748) or amine salts (see US Pat. No. 4,292,226) become.
  • Oxazolidines as are used, for example, in US Pat. No. 4,192,937, represent blocked polyamines which can be used for the chain extension of the prepolymers for the production of the polyurethanes according to the invention.
  • capped polyamines When such capped polyamines are used, they are generally mixed with the prepolymers in the absence of water and this mixture is then mixed with the dispersion water or part of the dispersion water, so that the corresponding polyamines are released hydrolytically.
  • Mixtures of di- and triamines are preferably used, particularly preferably mixtures of isophoronediamine and diethylenetriamine.
  • the polyurethanes preferably contain no polyamine or 1 to 10, particularly preferably 4 to 8 mol%, based on the total amount of components (b) and (c), of a polyamine with at least 2 amino groups reactive towards isocyanates as monomers (c).
  • Mono alcohols are preferably used in amounts of less than 10 mol%, based on components (b) and (c). Their function is generally similar to that of monoisocyanates, i.e. they mainly serve to functionalize the polyurethane. Examples are esters of acrylic or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl methacrylate.
  • the polyurethanes in addition to components (a), (b) and (c), contain monomers (d) which differ from components (a), (b) and (c) and which have at least one isocyanate group or carry at least one group which is reactive toward isocyanate groups and, in addition, at least one hydrophilic group or a group which can be converted into hydrophilic groups.
  • hydrophilic groups or potentially hydrophilic groups is abbreviated to "(potentially) hydrophilic groups”.
  • the (potentially) hydrophilic groups react with isocyanates much more slowly than the functional groups of the monomers, which are used to build up the main polymer chain.
  • the (potentially) hydrophilic groups can be nonionic or preferably ionic hydrophilic groups or potentially ionic hydrophilic groups.
  • the proportion of components with (potentially) hydrophilic groups in the total amount of components (a), (b), (c) and (d) is generally such that the molar amount of the (potentially) hydrophilic groups, based on the amount by weight of all monomers (a) to (b), 30 to 1000, preferably 50 to 500 and particularly preferably 80 to 300 mmol / kg.
  • nonionic hydrophilic groups are polyethylene glycol ethers composed of preferably 5 to 100, preferably 10 to 80, repeating ethylene oxide units.
  • the content of polyethylene oxide units is generally 0 to 10, preferably 0 to 6% by weight, based on the amount by weight of all monomers (a) to (d).
  • Preferred monomers with nonionic hydrophilic groups are polyethylene glycol and diisocyanates, which carry a terminally etherified polyethylene glycol residue. Such diisocyanates and processes for their preparation are specified in US Pat. Nos. 3,905,929 and 3,920,598.
  • Ionic hydrophilic groups are above all anionic groups such as the sulfonate, carboxylate and phosphate groups in the form of their alkali metal or ammonium salts, and cationic groups such as ammonium groups, in particular protonated tertiary amino groups or quaternary ammonium groups.
  • ionic hydrophilic groups are above all those which can be converted into the above-mentioned ionic hydrophilic groups by simple neutralization, hydrolysis or quaternization reactions, e.g. Carboxylic acid groups, anhydride groups or tertiary amino groups.
  • Ionic monomers (d) or potentially ionic monomers (d) are e.g. described in detail in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 19, pages 311-313 and, for example, in DE-A 1 495 745.
  • monomers with tertiary amino groups are of particular practical importance, for example: tris (hydroxyalkyl) amines, N, N'-bis (hydroxyalkyl) alkylamines, N-hydroxyalkyl dialkylamines, tris ( aminoalkyl) amines, N, N'-bis (aminoalkyl) alkylamines, N-aminoalkyl dialkylamines, the alkyl radicals and alkanediyl units of these tertiary amines independently of one another consisting of 2 to 6 carbon atoms.
  • polyethers containing tertiary nitrogen atoms preferably having two terminal hydroxyl groups, such as those e.g. by alkoxylation of two amines containing hydrogen atoms bonded to amine nitrogen, e.g. Methylamine, aniline, or N, N'-dimethylhydrazine, which are accessible in a conventional manner, into consideration.
  • polyethers generally have a molecular weight between 500 and 6000 g / mol.
  • tertiary amines are converted into the ammonium salts either with acids, preferably strong mineral acids such as phosphoric acid, sulfuric acid or hydrohalic acids, or by reaction with suitable quaternizing agents such as d- to C 6 -alkyl halides, for example bromides or chlorides.
  • acids preferably strong mineral acids such as phosphoric acid, sulfuric acid or hydrohalic acids
  • suitable quaternizing agents such as d- to C 6 -alkyl halides, for example bromides or chlorides.
  • Monomers with potentially anionic groups are usually aliphatic, cycloaliphatic, araliphatic or aromatic mono- and dihydroxycarboxylic acids which carry at least one alcoholic hydroxyl group or a primary or secondary amino group.
  • Dihydroxyalkylcarboxylic acids are preferred, especially those with 3 to 10 carbon atoms, as are also described in US Pat. No. 3,412,054.
  • R 1 and R 2 stand for a C ⁇ - to C 4 -alkanediyl unit and R 3 stands for a - to C 4 - alkyl unit, and especially dimethylolpropionic acid (DMPA) is preferred.
  • DMPA dimethylolpropionic acid
  • Dihydroxyphosphonic acids such as 2,3-dihydroxypropanephosphonic acid.
  • dihydroxyl compounds with a molecular weight above 500 to 10000 g / mol with at least 2 carboxylate groups, which are known from DE-A 4 140 486. They are by reacting dihydroxyl compounds with tetracarboxylic acid dianhydrides such as pyromellitic acid dianhydride or
  • Cyclopentantetracarboxylic acid dianhydride in a molar ratio of 2: 1 to 1.05: 1 available in a polyaddition reaction.
  • Particularly suitable dihydroxyl compounds are the monomers (b2) listed as chain extenders and the diols (b1).
  • Suitable monomers (d) with amino groups which are reactive toward isocyanates are amino carboxylic acids such as lysine, ⁇ -alanine, the adducts of aliphatic diprimeric diamines with ⁇ , ⁇ -unsaturated carboxylic acids and sulfonic acids mentioned in DE-A 20 34 479.
  • amino carboxylic acids such as lysine, ⁇ -alanine, the adducts of aliphatic diprimeric diamines with ⁇ , ⁇ -unsaturated carboxylic acids and sulfonic acids mentioned in DE-A 20 34 479.
  • Such compounds obey, for example, the general formula I.
  • R and R 'independently of one another are a C - to C 6 -alkanediyl unit, preferably ethylene, and X is COOH or SO 3 H.
  • Particularly preferred compounds of the formula I are N- (2-aminoethyl) -2-aminoethane carboxylic acid and the N- (2-aminoethyl) -2-aminoethane sulfonic acid or the corresponding alkali metal salts, Na being a particularly preferred counterion.
  • monomers with potentially ionic groups are used, they can be converted into the ionic form before, during, but preferably after the isocyanate polyaddition, since the ionic monomers are often difficult to dissolve in the reaction mixture.
  • the carboxylate groups are particularly preferably in the form of their salts with an alkali ion or an ammonium ion as counterion.
  • the monomers (d) and their proportions are chosen so that the resultant polyurethane dispersions have an overall anionic character.
  • the ratio A: B is very particularly preferably as close as possible to 1: 1.
  • monomers with only one reactive group are generally used in amounts of up to 15 mol%, preferably up to 8 mol%, based on the total amount of the components (a), (b), (c) and (d) used.
  • the polyaddition of components (a) to (d) is generally carried out at reaction temperatures of 20 to 180 ° C, preferably 50 to 150 ° C under normal pressure.
  • the required response times can range from a few minutes to a few hours. It is known in the field of polyurethane chemistry how the reaction time is influenced by a large number of parameters such as temperature, concentration of the monomers and reactivity of the monomers.
  • the customary catalysts such as dibutyltin dilaurate, stannous octoate or diazabicyclo (2,2,2) octane, can also be used.
  • Stirred kettles are suitable as polymerization apparatus, in particular if low viscosity and good heat dissipation are ensured by the use of solvents.
  • extruders in particular self-cleaning multi-screw extruders, are particularly suitable due to the usually high viscosities and the usually short reaction times.
  • the dispersions are produced by one of the following processes:
  • an anionic polyurethane is produced from components (a) to (d) in a water-miscible solvent that boils at normal pressure below 100 ° C. Sufficient water is added until a dispersion is formed in which water is the continuous phase.
  • the "prepolymer mixing process” differs from the acetone process in that it does not produce a fully reacted (potentially) anionic polyurethane, but first a prepolymer that carries isocyanate groups.
  • Components (a) to (d) are chosen so that the definition-based ratio A: B is greater than 1.0 to 3, preferably 1.05 to 1.5.
  • the prepolymer is first dispersed in water and then crosslinked by reaction of the isocyanate groups with amines which carry more than 2 amino groups reactive toward isocyanates or chain-extended with amines which carry 2 amino groups reactive with isocyanates. Chain extension also takes place when no amine is added.
  • isocyanate groups are hydrolyzed to amine groups, which react with remaining isocyanate groups of the prepolymers with chain extension.
  • amine groups which react with remaining isocyanate groups of the prepolymers with chain extension.
  • most of the solvent is removed from the dispersion, for example by distillation under reduced pressure.
  • the dispersions preferably have a solvent content of less than 10% by weight and are particularly preferably free from solvents.
  • the dispersions generally have a solids content of 10 to 75, preferably 20 to 65% by weight and a viscosity of 10 to 500 mPas, measured at a temperature of 20 ° C. and a shear rate of 250 s -1 .
  • All natural or synthetic cationic polymers which contain amino and / or ammonium groups and are water-soluble can be used as cationic polymers for modifying the aqueous anionic polyurethane dispersions.
  • cationic polymers are polymers containing vinylamine units, polymers containing vinylimidazole units, polymers containing quaternary vinylimidazole units, condensates of imidazole and epichlorohydrin, crosslinked polyamidoamines, crosslinked polyamidoamines grafted with ethyleneimine, polyethylemmines, alkoxylated polyethyleneimines, crosslinked polyethylemmines , alkylated polyethylemmines, polyamines, amine-epichlorohydrin polycondensates, alkoxylated polyamines, polyallylamines, polydimethyldiallylammonium chlorides, polymers containing basic (meth) acrylamide or ester units, polymers containing basic quaternary (me
  • Cationic polymers are also understood to mean amphoteric polymers which have a net cationic charge, i.e. the polymers contain both anionic and cationic monomers copolymerized, but the molar proportion of the cationic units contained in the polymer is greater than the molar proportion of the anionic units.
  • Polymers containing vinylamine units are prepared, for example, from open-chain N-vinylcarboxamides of the formula (I)
  • the monomers mentioned can be polymerized either alone, as a mixture with one another or together with other monoethylenically unsaturated monomers. Homopolymers or copolymers of N-vinylformamide are preferably used.
  • Polymers containing vinylamine units are known, for example, from US Pat. No. 4,421,602, EP-A-0 216 387 and EP-A-0 251 182. They are obtained by hydrolysis of polymers which contain the monomers of the formula (I) in copolymerized form with acids, bases or enzymes.
  • Suitable monoethylenically unsaturated monomers which are copolymerized with the N-vinylcarboxamides are all compounds which can be copolymerized therewith.
  • Examples include vinyl esters of saturated carboxylic acids with 1 to 6 carbon atoms such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate, and vinyl ethers such as - to C 6 -alkyl vinyl ether, for example methyl or ethyl vinyl ether.
  • Suitable comonomers are ethylenically unsaturated C 3 - to C 6 -carboxylic acids, for example acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid and vinyl ester acid as well as their alkali metal and alkaline earth metal salts, esters, amides and nitriles of the carboxylic acids mentioned, for example methyl acrylate, methyl methacrylate and ethyl acrylate ethyl methacrylate.
  • C 3 - to C 6 -carboxylic acids for example acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid and vinyl ester acid as well as their alkali metal and alkaline earth metal salts, esters, amides and nitriles of the carboxylic acids mentioned, for example methyl acrylate, methyl methacrylate and ethyl acrylate ethyl methacrylate.
  • suitable monoethylenically unsaturated monomers which are copolymerized with the N-vinylcarboxamides are carboxylic esters which are derived from glycols or polyalkylene glycols, only one OH group being esterified in each case, for example hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxypropyl methacrylate as well as acrylic acid monoesters of polyalkylene glycols with a molecular weight of 500 to 10,000.
  • esters of ethylenically unsaturated carboxylic acids with amino alcohols such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylamine methyl methacrylate, dimethylaminopropyl acrylate, Dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate and diethylaminobutyl acrylate.
  • the basic acrylates can be used in the form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or the sulfonic acids or in quaternized form.
  • Suitable quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride.
  • Suitable comonomers are amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids with alkyl radicals of 1 to 6 carbon atoms, e.g. N-methyl acrylamide, N, N-dimethylacrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-propylacrylamide and tert.
  • amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids with alkyl radicals of 1 to 6 carbon atoms, e.g. N-methyl acrylamide, N, N-dimethylacrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-propylacrylamide and tert.
  • Butyl acrylamide and basic (meth) acrylamides such as dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminopropyl methacrylamide and diethylaminopropyl methacrylamide.
  • N-vinylpyrrolidone N-vinylcaprolactam
  • acrylonitrile methacrylonitrile
  • N-vinylimidazole substituted N-vinylimidazoles
  • N-vinyl-2-methylimidazole N-vinyl- methylimidazole
  • N-vinyl-5-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 or organic acids, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride. Also come into question
  • Diallyldialkylammonium halides such as diallyldimemylammonium chlorides.
  • monomers containing sulfo groups such as vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid,
  • Styrenesulfonic acid the alkali metal or ammonium salts of these acids or 3-sulfopropyl acrylate in question, the content of amphoteric copolymers of cationic units exceeding the content of anionic units, so that the polymers as a whole have a cationic charge.
  • the copolymers contain, for example 99.99 to 1 mol%, preferably 99.9 to 5 mol% of N-vinylcarboxamides of the formula (I) and
  • polymers containing vinylamine units In order to prepare polymers containing vinylamine units, one preferably starts from homopolymers of N-vinylformamide or from copolymers which are obtained by copolymerizing
  • the polymers described above are hydrolysed by known processes by the action of acids, bases or enzymes. In this way, the copolymerized monomers of the formula (I) given above are formed by splitting off the grouping
  • R 2 has the meaning given for it in formula (I), polymers, the vinylamine units of the formula (III)
  • R 1 has the meaning given in formula (I). If acids are used as the hydrolysis agent, the units (III) are present as the ammonium salt.
  • the homopolymers of the N-vinylcarboxamides of the formula (I) and their copolymers can be hydrolyzed to 0.1 to 100, preferably 70 to 100, mol%. In most cases, the degree of hydrolysis of the homo- and copolymers is 5 to 95 mol%. The degree of hydrolysis of the homopolymers is synonymous with the vinylamine units in the polymers. In the case of copolymers which contain vinyl esters in copolymerized form, in addition to the hydrolysis of the N-vinylformamide units, hydrolysis of the ester groups can occur with formation of vinyl alcohol units. This is particularly the case when the copolymers are hydrolysed in the presence of sodium hydroxide solution.
  • Polymerized acrylonitrile is also chemically changed during the hydrolysis. This creates, for example, amide groups or carboxyl groups.
  • the homo- and copolymers containing vinylamine units may optionally contain up to 20 mol% of amidine units which can be obtained by reacting formic acid with two adjacent amino groups or by intramolecular reaction of an amino group with a neighboring amide group e.g. of polymerized N-vinylformamide.
  • the molar masses of the polymers containing vinylamine units are, for example 1000 to 10 million, preferably 10,000 to 5 million (determined by light scattering). This molar mass range corresponds, for example, to K values of 5 to 300, preferably 10 to 250 (determined according to H. Fikentscher in 5% aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 0.5% by weight).
  • the polymers containing vinylamine units are preferably used in salt-free form.
  • Salt-free aqueous solutions of polymers containing vinylamine units can be prepared, for example, from the salt-containing polymer solutions described above with the aid of ultrafiltration on suitable membranes at separation limits of, for example, 1000 to 500,000 daltons, preferably 10,000 to 300,000 daltons.
  • the aqueous solutions of other polymers containing amino and / or ammonium groups described below can also be obtained with the aid of ultrafiltration in a salt-free form.
  • Polyethyleneimines are also suitable as cationic polymers.
  • Polyethylemmines are produced, for example, by polymerizing ethyleneimine in aqueous solution in the presence of acid-releasing compounds, acids or Lewis acids.
  • polyethyleneimines have molecular weights of up to 2 million, preferably from 200 to 500,000. Polyethyleneimines with molecular weights of 500 are particularly preferred used up to 100,000.
  • water-soluble crosslinked polyethyleneimines which can be obtained by reacting polyethyleneimines with crosslinking agents such as epichlorohydrin or bischlorohydrin ethers of polyalkylene glycols having 2 to 100 ethylene oxide and / or propylene oxide units.
  • Amidic polyethyleneimines which are obtainable, for example, by amidating polyethyleneimines with - to C 22 monocarboxylic acids are also suitable.
  • Other suitable cationic polymers are alkylated polyethyleneimines and alkoxylated polyethyleneimines. In the alkoxylation, 1 to 5 ethylene oxide or propylene oxide units are used, for example, per NH unit in polyethylenimine.
  • Suitable polymers containing amino and / or ammonium groups are also polyamidoamines, which can be obtained, for example, by condensing dicarboxylic acids with polyamines.
  • Suitable polyamidoamines are obtained, for example, by reacting dicarboxylic acids with 4 to 10 carbon atoms with polyalkylene polyamines which contain 3 to 10 basic nitrogen atoms in the molecule.
  • Suitable dicarboxylic acids are, for example, succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. Mixtures of dicarboxylic acids can also be used in the preparation of the polyamidoamines, as can mixtures of several polyalkylene polyamines.
  • Suitable polyalkylene polyamines are, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetri
  • Aminopropylethylenediamine and bis-aminopropylethylenediamine are heated to higher temperatures to produce the polyamidoamines, e.g. to temperatures in the range of 120 to 220, preferably 130 to 180 ° C.
  • the water generated during the condensation is removed from the system.
  • Lactones or lactams of carboxylic acids having 4 to 8 carbon atoms can optionally also be used in the condensation.
  • 0.8 to 1.4 moles of a polyalkylene polyamine are used per mole of a dicarboxylic acid.
  • polymers containing amino groups are polyamidoamines grafted with ethyleneimine. They can be obtained from the polyamidoamines described above by reaction with ethyleneimine in the presence of acids or Lewis acids such as sulfuric acid or boron trifluoride etherates at temperatures of, for example, 80 to 100.degree. Compounds of this type are described for example in DE-B-24 34 816.
  • the optionally crosslinked polyamidoamines which are optionally additionally grafted before crosslinking with emylenimine, also come in as cationic polymers Consideration.
  • the crosslinked polyamidoamines grafted with ethyleneimine are water-soluble and have, for example, an average molecular weight of 3000 to 1 million Daltons.
  • Typical crosslinkers are, for example, epichlorohydrin or bischlorohydrin ether of alkylene glycols and polyalkylene glycols.
  • cationic polymers containing amino and / or ammonium groups are polydiallyldimethylammonium chlorides. Polymers of this type are also known.
  • Suitable cationic polymers are copolymers of, for example, 1 to
  • Monomers such as dialkylaminoalkyl acrylamide, ester and / or methacrylamide and / or methacrylic ester.
  • the basic acrylamides and methacrylamides are also preferably in a form neutralized with acids or in quaternized form. Examples include: N-trimethylammonium ethyl acrylamide chloride,
  • Trimethylammonium propyl acrylamide chloride Trimethylammonium propyl methacrylamide chloride,
  • Trimethylammonium propyl methacrylamide chloride is preferred.
  • Suitable cationic monomers for the production of (meth) acrylamide copolymers are diallyldimethylammonium halides and basic (meth) acrylates.
  • copolymers of 1 to 99 mol%, preferably 30 to 70 mol% of acrylamide and / or methacrylamide and 99 to 1 mol%, preferably 70 to 30 mol% of dialkylaminoalkyl acrylates and / or methacrylates such as copolymers of acrylamide and N, N-dimethylaminoethyl acrylate or copolymers of acrylamide and dimethylaminopropyl acrylate.
  • Basic acrylates or methacrylates are preferably in neutralized form with acids or in quaternized form. The quaternization can take place, for example, with methyl chloride or with dimethyl sulfate.
  • Polyallylammers are also suitable as cationic polymers which have amino and / or ammonium groups.
  • Polymers of this type are obtained by homopolymerizing allylamine, preferably in acid-neutralized or quaternized form, or by copolymerizing allylamine with other monoethylenically unsaturated monomers described above as comonomers for N-vinylcarboxamides.
  • the cationic polymers have e.g. K values of 8 to 300, preferably 100 to 180 (determined according to H. Fikentscher in 5% aqueous saline solution at 25% and a polymer concentration of 0.5% by weight). At a pH of 4.5, for example, they have a charge density of at least 1, preferably at least 4 meq / g polyelectrolyte.
  • Examples of preferred cationic polymers are polydimethyldiallylammonium chloride, polyethyleneimine, polymers containing vinylamine units, copolymers of acrylamide or methacrylamide containing copolymerized basic monomers, polymers containing lysine units or mixtures thereof.
  • Examples of preferred cationic polymers are:
  • Vinylamine homopolymers 1 to 99% hydrolyzed polyvinylformamides, copolymers of vinylformamide and vinyl acetate, vinyl alcohol,
  • 1-vinylimidazole homopolymers 1-vinylimidazole copolymers with 1-vinylpyrrolidone, vinylformamide, acrylamide or vinyl acetate with molecular weights of 5,000 to 500,000 and their quaternary derivatives, for example copolymer of 75% by weight of 1-vinylimidazole and 25% by weight.
  • Amine-epichlorohydrin polycondensates which contain imidazole, piperazine, -Cs-alkylamines, -C-C 8 -dialkylamines and / or dimethylaminopropylamine as amine component and which have a molecular weight of 500 to 250,000,
  • Polydimethyldiallylammonium chloride Mw 2,000 to 2,000,000.
  • Polyethyleneimines, crosslinked polyethyleneimines, amidated polyethyleneimines, amine-epichlorohydrin polycondensates with imidazole or piperazine as the amine component, polymeric diallylammonium chlorides and polyvinylformamides with a degree of hydrolysis of 30 to 100% are particularly preferred.
  • anionic comonomers for example acrylic acid, methacrylic acid, vinylsulfonic acid or alkali metal salts of the acids mentioned.
  • the present invention also relates to a method for modifying the surface of textile and non-textile materials, in which cationically modified, particulate polyurethanes with a particle size of 10 nm to 100 ⁇ m are applied to the surface of the materials from an aqueous dispersion and the materials are dried ,
  • the cationically modified, particulate polyurethanes are preferably applied to the surface from an aqueous dispersion having a polyurethane content of ⁇ 5% by weight.
  • the modification of the surfaces of textile materials can consist, for example, of hydrophobization, soil release finish, dirt-repellent finish, reinforcement of the fiber composite, improved grip, protection against creasing and wrinkling and protection against chemical or mechanical influences and damage , Surfaces of textile materials such as cotton fabrics and cotton blended fabrics are particularly suitable.
  • carpets and furniture covers can be treated according to the invention.
  • the modification of the surfaces of non-textile materials can consist, for example, of hydrophobization, soil release finish, dirt-repellent finish and protection against chemical or mechanical influences and damage.
  • non-textile materials are, for example, the macroscopic, hard upper compartments of floor and wall coverings, exposed concrete, stone facades, plastered facades, glass, ceramics, metal, enamel, plastic and wood as well as the microscopic surfaces of porous bodies, foams, woods, and leather , porous building materials and cellulose fleeces.
  • the cationically modified, particulate anionic polyurethanes are used to modify surfaces of the above-mentioned materials as a surface-modifying additive in detergents or care products, washing or cleaning agents for textile and non-textile materials.
  • applications in the washing, cleaning and aftertreatment of textiles, leather, wood, floor coverings, glass, ceramics and other surfaces in the household and in the commercial sector come into question.
  • the cationically modified, particulate anionic polyurethanes are used as a dilute, predominantly aqueous dispersion.
  • the application is carried out by treating the surfaces with washing, cleaning and rinsing liquors, to which the polymers are added either directly or by means of a liquid or solid formulation, or by the finely divided application of a liquid formulation, e.g. by spraying.
  • the cationically modified, particulate anionic polyurethanes can be used, for example, as the sole active component in aqueous dishwashing detergents and care products and, depending on the composition of the polyurethane, facilitate the removal of dirt during subsequent washing, less dirt adhesion when using the textiles, and an improvement in the structure retention of Fibers, an improvement in the shape and structure retention of fabrics, a hydrophobization of the surface of the laundry and an improvement in the handle.
  • the concentration of the cationically modified, particulate polyurethanes when used in the rinsing or care bath, in the detergent liquor or in the cleaning bath is, for example, 0.0002 to 5% by weight, preferably 0.0005 to 1.0% by weight, particularly preferably 0.002 to 0.1% by weight.
  • the cationic modification of the particulate polyurethanes is preferably carried out before use in the aqueous treatment agents, but it can also be carried out in the preparation of the aqueous treatment agents by mixing aqueous dispersions of the particulate polyurethanes with the other constituents of the treatment agent in the presence of cationic polymers and optionally cationic Mixes surfactants.
  • the particulate polyurethanes or formulations containing them can also be added directly to the rinsing, washing or cleaning liquor if it is ensured that sufficient amounts of cationic polymers are present in dissolved form in the liquor.
  • Surface treatment agents can have, for example, the following composition:
  • At least one customary additive such as acids or bases, inorganic builders, organic cobuilders, surfactants, polymeric color transfer inhibitors, polymeric graying inhibitors, soil release polymers, enzymes, complexing agents, corrosion inhibitors, waxes, silicone oils,
  • customary additive such as acids or bases, inorganic builders, organic cobuilders, surfactants, polymeric color transfer inhibitors, polymeric graying inhibitors, soil release polymers, enzymes, complexing agents, corrosion inhibitors, waxes, silicone oils,
  • the invention also relates to a textile treatment composition containing
  • Preferred silicones b) are amino group-containing silicones, which are preferably in microemulsified form, alkoxylated, in particular ethoxylated silicones, polyalkylene oxide polysiloxanes, polyalkylene oxide aminopolydimethylsiloxanes, silicones with quaternary ammonium groups (silicone quats) and silicone surfactants.
  • Suitable plasticizers or lubricants are, for example, oxidized polyethylenes or waxes and oils containing paraffin.
  • Suitable water-soluble, film-forming and adhesive polymers are, for example, (co) polymers based on acrylamide, N-vinylpyrrolidone, vinylformamide, N-vinylimidazole, vinylamine, N, N'-dialkylaminoalkyl (meth) acrylates, N, N'-dialkylaminoalkyl (meth) acrylamides, (meth) acrylic acid, (meth) acrylic acid alkyl esters and / or vinyl sulfonate.
  • the basic monomers mentioned above can also be used in quaternized form. -
  • the textile treatment agent can additionally contain a spraying aid.
  • a spraying aid such as ethanol, isopropanol, ethylene glycol or propylene glycol
  • alcohols such as ethanol, isopropanol, ethylene glycol or propylene glycol
  • Other common additives are fragrances and dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion protection additives, bactericides and preservatives in the usual amounts.
  • the textile treatment agent can also generally be applied by spraying when the textile is ironed after washing. This not only makes ironing considerably easier, the textiles are also equipped with long-lasting crease and wrinkle protection.
  • the cationically modified, particulate inorganic polyurethanes can also be used when washing the textiles in the main washing cycle of the washing machine.
  • the invention also relates to a solid detergent formulation containing
  • Graying inhibitors soil release polyesters, dyes, bactericides,
  • a solid detergent formulation according to the invention is usually in powder or granule form or in extrudate or tablet form.
  • the invention further relates to a liquid detergent formulation
  • customary ingredients such as soda, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleaching catalysts, cationic surfactants, color transfer inhibitors, graying inhibitors, soil-release polyesters, dyes, bactericides, non-aqueous solvents, Solubilizers, hydrotropes, thickeners and / or alkanolamines,
  • Suitable silicones b) are the silicones mentioned above.
  • Suitable anionic surfactants c) are in particular:
  • C 12 -C 18 alcohol sulfates lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate;
  • alkoxylated C 8 to C 22 alcohols alkyl ether sulfates.
  • Compounds of this type are prepared, for example, by first alkoxylating a C 8 to C 2 , preferably a Cio to C 18 alcohol, for example a fatty alcohol, and then sulfating the alkoxylation product.
  • Ethylene oxide is preferably used for the alkoxylation;
  • LAS alkylbenzosulfonates
  • Alkanesulfonates such as C 8 to C 24 , preferably C 10 to C 18 alkanesulfonates
  • the anionic surfactants mentioned are preferably added to the detergent in the form of salts.
  • Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium ions and ammonium ions such as hydroxyethylammomum, di (hydroxyethyl) ammonium and tri (fryroxyethyl) ammomum.
  • Suitable nonionic surfactants c) are in particular: - Alkoxylated linear or branched C 8 - to C 22 alcohols such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. These can be alkoxylated with ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of one of the above-mentioned alkylene oxides added can be used as surfactants.
  • block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution.
  • the nonionic surfactants generally contain 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide per mole of alcohol.
  • alkylene oxide preferably contain ethylene oxide as the alkylene oxide.
  • the alcohols preferably have 10 to 18 carbon atoms.
  • the alkoxylates have a broad or narrow alkylene oxide homolog distribution; - Alkylphenol alkoxylates such as alkylphenol ethoxylates with C 6 - to C 14 -alkyl chains and
  • Alkyl polyglucosides having 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain and generally 1 to 20, preferably 1.1 to 5, glucoside units;
  • glucamides fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.
  • Suitable inorganic builders d) are in particular:
  • zeolites Suitable zeolites are in particular zeolites A, X, B, P,
  • MAP and HS in their Na form or in forms in which Na is partially replaced by other cations such as Li, K, Ca, Mg, or ammonium;
  • silicates such as, in particular, disilicates or layered silicates, for example ⁇ -Na 2 Si 2 O 5 or ß-Na 2 Si 2 O 5 .
  • the silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg
  • amorphous silicates such as sodium metasilicate or amorphous disilicate
  • Na, Li and Mg carbonates or bicarbonates are preferred, in particular sodium carbonate and / or sodium bicarbonate;
  • Suitable organic cobuilders e are in particular low molecular weight, oligomeric or polymeric carboxylic acids.
  • Suitable low molecular weight carboxylic acids are, for example, citric acid, hydrophobically modified citric acid such as. B. agaricic acid, malic acid,
  • Tartaric acid Tartaric acid, gluconic acid, glutaric acid, succinic acid, iminodisuccinic acid, oxydisuccinic acid, propane tricarboxylic acid, butanetetracarboxylic acid,
  • Cyclopentanetetracarboxylic acid alkyl and alkenyl succinic acids and aminopoly carboxylic acids such as e.g. Nifrilofriacetic acid, ß-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, N- (2-
  • Suitable oligomeric or polymeric carboxylic acids are, for example, homopolymers of acrylic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid, methacrylic acid, C 2 -C 22 olefins such as isobutene or long-chain ⁇ -olefins, vinyl alkyl ethers with Cj-Cs alkyl groups, vinyl acetate, vinyl propionate , (Meth) acrylic esters of - - alcohols and styrene.
  • the homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid are preferably used.
  • Polyaspartic acids are also suitable as organic cobuilders.
  • the oligomeric and polymeric carboxylic acids are in acid form or as
  • Suitable bleaching agents are, for example, adducts of hydrogen peroxide with inorganic salts such as e.g. Sodium perborate monohydrate, sodium perborate tetrahydrate or sodium carbonate perhydrate or percarboxylic acids such as e.g.
  • Suitable bleach activators are, for example, N, N, N ', N'-tetraacetylethylene diamine (TAED), sodium p-nonanoyloxybenzenesulfonate or N-methylmorpholinium acetonitrile methyl sulfate.
  • TAED N, N, N ', N'-tetraacetylethylene diamine
  • Enzymes preferably used in detergents are proteases, lipases, amylases, cellulases, oxidases or peroxidases.
  • Suitable color transfer inhibitors are, for example, homopolymers and copolymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-vinylpyridine-N-oxide. Homo- and copolymers of 4-vinylpyridine reacted with chloroacetic acid are also suitable as color transfer inhibitors.
  • a detailed description of the detergent ingredients mentioned can be found, for example, in WO 99/06524 or WO 99/04313 and in Liquid Detergents, Editor: Kuo-Yann Lai, Surfactant Sei. Ser., Vol. 67, Marcel Decker, New York, 1997, pp. 272-304. For typical ingredients, reference is also made to the chapter Detergents (Part 3, Detergent Ingredients, Part 4, Household Detergents and Part 5, Institutional Detergents) in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2000 Electronic Version 2.0.
  • the concentration of the cationically modified, particulate anionic polyurethanes in the wash liquor is, for example, 10 to 5000 ppm and is preferably in the range from 50 to 1000 ppm.
  • the textiles treated with the cationically modified particulate polyurethanes in the main washing cycle of the washing machine not only wrinkle significantly less than untreated textiles. They are also easier to iron, softer and smoother, more dimensionally and dimensionally stable and after washing several times they look less "used" due to their fiber and color protection, so they have less lint and knots and less color damage or fading.
  • the cationically modified, particulate anionic polyurethanes can be used in the so-called soft or conditioner rinse after the main wash cycle.
  • concentration of the particulate polyurethanes in the wash liquor is, for example, 10 to 5000 ppm and is preferably in the range from 50 to 1000 ppm.
  • Ingredients typical for a fabric softener or conditioner may possibly be present in the wash liquor.
  • the textiles treated in this way also have a very good crease protection after drying on a line or preferably in a tumble dryer, which is associated with the positive effects on ironing already described above.
  • the anti-crease can be significantly increased by briefly ironing the textiles after drying.
  • Treatment in a soft or conditioner cycle also has a positive effect on the shape stability of the textiles. Furthermore, the formation of knots and lint is inhibited and color damage is suppressed.
  • the invention also relates to a laundry detergent containing
  • e) 0 to 30% by weight of other conventional ingredients such as lubricants, wetting agents, film-forming polymers, fragrances and dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion protection additives, bactericides and preservatives, and
  • Suitable silicones b) are the silicones mentioned above.
  • Preferred cationic surfactants c) are selected from the group of the quaternary diesterammonium salts, the quaternary tetraalkylammonium salts, the quaternary diamidoammonium salts, the amidoamine esters and imidazolium salts. These are preferably contained in the laundry detergent in an amount of 3 to 30% by weight.
  • Examples are quaternary diester ammonium salts which have two C ⁇ to C 2 alk (en) yl carbonyloxy (mono- to pentamethylene) radicals and two to C 3 alkyl or hydroxyalkyl radicals on the quaternary N atom and, for example, as a counterion Wear chloride, bromide, methyl sulfate or sulfate.
  • Quaternary diesterammonium further include in particular those corresponding to the trimethylene group carries a C ⁇ - to C 22 -alk (en) ylcarbonyloxytrimethylen radical, on the central carbon atom form a C ⁇ - to C 22 -alk (en) ylcarbonyloxy radical, and have three Ci to C 3 alkyl or hydroxyalkyl radicals on the quaternary N atom and, for example, chloride, bromide, methyl sulfate or sulfate as counterions.
  • Quaternary tetraalkylammonium salts are in particular those which have two Ci to C 6 alkyl radicals and two C 8 - to C 24 -alk (en) yl radicals on the quaternary nitrogen atom and having, as counterion, chloride, bromide, methylsulfate, or sulfate wear.
  • Quaternary diamidoammonium are in particular those which have two C 8 - to C 4 - a substituent selected from hydrogen, methyl, ethyl and polyoxyethylene having up to 5 oxyethylene units alk (en) ylcarbonylaminoethylene residues, and as fourth radical have a methyl group on the quaternary N atom and carry, for example, chloride, bromide, methyl sulfate or sulfate as counterion.
  • Amidoamino esters are, in particular, tertiary amines which, as substituents on the N atom, have a C ⁇ to C 22 alk (en) ylcarbonylamino (mono- to trimethylene) radical, a C ⁇ to C 22 alk (en) ylcarbonyloxy (mono- to trimethylene) residue and a methyl group.
  • Imidazolinium salts are in particular those in which the 2-position of the heterocycle, a C 14 - to C 18 -alk (en) yl radical, the neutral N-atom form a C 14 - to C 18 -alk (en) ylcarbonyl (oxy or amino) carry the ethylene radical and hydrogen, methyl or ethyl on the N atom carrying the positive charge; counterions here are, for example, chloride, bromide, methyl sulfate or sulfate.
  • Polymer 1 polyethyleneimine with a molecular weight of 25,000
  • Polymer 2 high molecular weight polyethyleneimine with a molecular weight of 2,000,000
  • polymer 3 polydiallyldimethylammonium chloride with a molecular weight of 100,000.
  • dispersion I 50 g of dispersion I were metered in at room temperature and pH 7 to 50 g of a 0.8% strength by weight aqueous solution of polymer 1 within 10 minutes. A finely divided dispersion which was stable over several months was obtained.
  • dispersion I 50 g of dispersion I were metered in at room temperature and pH 7 to 100 g of a 0.8% strength by weight aqueous solution of polymer 2 within 10 minutes. A finely divided dispersion which was stable over several months was obtained.
  • dispersion II 50 g of dispersion II were metered in at room temperature and pH 7 to 50 g of a 1.2% strength by weight aqueous solution of polymer 3 within 10 minutes. A finely divided dispersion which was stable over several months was obtained.
  • Dispersion III was diluted with water (pH 7.1 mmol / l water hardness) to a solids content of 0.02% by weight.
  • a white cotton fabric (10 g) was suspended in the stirred liquor (600 ml) for 30 minutes. The cotton fabric was then removed and dried. On the dry tissue, the crease recovery (de-crease) was determined according to DLN 53890. The greater the crease recovery angle after the loss of the force acting on the tissue, the more effective the dispersion.
  • white cotton fabric was treated with dispersions IV and V and, for the purpose of comparison, with unmodified dispersions I and II, and the crease recovery angle was determined. The results are shown in Table 1.
  • the liquor ratio was 1:10.
  • the fabric softener / conditioner After the fabric softener / conditioner, the fabric was removed and dried in a tumble dryer (cupboard dry program). After drying, the flat tissue samples were visually graded based on AATCC test method 124, where grade 1 means that the fabric is very creased and has many folds, while grade 5 is given for crease-free and wrinkle-free fabric.

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  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne des polyuréthanes anioniques particulaires, modifiés par voie cationique, de grandeur particulaire comprise entre 10 nm et 10 mu m, lesdits polyuréthanes particulaires étant modifiés par voie cationique par revêtement de leur surface avec des polymères cationiques. Les polymères cationiques ayant la préférence sont des polymères contenant des unités vinylamine, des polymères contenant des unités vinylimidazol, des polymères contenant des unités vinylimidazol quaternaires, des polymères contenant : des condensats d'imidazol et d'épichlorhydrine, des polyamidoamines réticulées, des polyamidoamines réticulées et greffées par éthylène-imine, des polyéthylène-imines, des polyéthylène-imine alcoxylées, des polyéthylène-imine réticulées, des polyéthylène-imine amidées, des polyéthylène-imine alkylées, des polyamines, des polycondensats d'amine-épichlorhydrine, des polyamines alcoxylées, des polyallylamines, des chlorures de polydiméthyldiallylammomium, des unités (méth)acrylamide ou ester basiques, des polymères contenant des unités (méth)acrylamide ou ester quaternaires basiques et des condensats de lysine.
EP03724970A 2002-04-09 2003-04-07 Dispersions polyurethane anioniques modifiees par voie cationique Withdrawn EP1497348A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10215522A DE10215522A1 (de) 2002-04-09 2002-04-09 Kationisch modifizierte anionische Polyurethandispersionen
DE10215522 2002-04-09
PCT/EP2003/003604 WO2003085020A1 (fr) 2002-04-09 2003-04-07 Dispersions polyurethane anioniques modifiees par voie cationique

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EP1497348A1 true EP1497348A1 (fr) 2005-01-19

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US (1) US20050153865A1 (fr)
EP (1) EP1497348A1 (fr)
AU (1) AU2003227572A1 (fr)
DE (1) DE10215522A1 (fr)
MX (1) MXPA04009073A (fr)
WO (1) WO2003085020A1 (fr)

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AU2003227572A1 (en) 2003-10-20
WO2003085020A1 (fr) 2003-10-16
US20050153865A1 (en) 2005-07-14
DE10215522A1 (de) 2003-10-30
MXPA04009073A (es) 2004-12-06

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