EP1497348A1 - Cationically modified, anionic polyurethane dispersions - Google Patents

Abstract

The invention relates to cationically modified, particulate anionic polyurethanes having a particle size ranging from 10 nm to 10 ñm, whereby the particulate polyurethanes are cationically modified by covering their surface with cationic polymers. Preferred cationic polymers are: polymers containing vinylamine units; polymers containing vinylimidazole units; polymers containing quaternary vinylimidazole units; condensates that consist of imidazole and of epichlorohydrin; cross-linked polyamidoamines; cross-linked polyamidoamines grafted with ethylene imine; polyethylene imines; alkoxylated polyethylene imines; cross-linked polyethylene imines; amidated polyethylene imines; alkylated polyethylene imines; polyamines; amine-epichlorohydrin polycondensates; alkoxylated polyamines; polyallylamines; polydimethyldiallylammonium chlorides; polymers containing alkaline (meth)acrylamide units or (meth)acrylester units; polymers containing alkaline quaternary (meth)acrylamide units or (meth)acrylester units, and; lysine condensates.

Description

 Cationically modified anionic polyurethane dispersions

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. For example, 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, on the other hand, 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 μm, 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. In addition, 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. Such polyurethane dispersions with a predominantly anionic character are referred to below as 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 μm 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 μm, 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 μm.

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.

Surprisingly, 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

- while maintaining their desired film-forming, surface-modifying properties

- To the surface to be treated, for example the surface of a textile fiber, increased to such an extent that the polyurethane particles are readily obtained from highly dilute aqueous solutions

Apply treatment liquors to the surface.

A Aqueous polyurethane dispersions The aqueous anionic polyurethane dispersions are expediently prepared by reacting

a) polyvalent isocyanates with 4 to 30 carbon atoms,

b) diols, of which

bl) 10 to 100 mol%, based on the total amount of diols (b), have a molecular weight of 500 to 5000, and

b2) 0 to 90 mol%, based on the total amount of diols (b), have a molecular weight of 62 to 500 g / mol,

c) optionally further polyvalent compounds with reactive groups which differ from the diols (b) and which are alcoholic hydroxyl groups or primary or secondary amino groups, and

d) monomers different from the monomers (a), (b) and (c) with at least one isocyanate group or at least one reactive towards isocyanate groups

A group which additionally carries at least one hydrophilic group I or a potentially hydrophilic group, which brings about the water dispersibility of the polyurethanes.

to a polyurethane.

Suitable monomers (a) are the polyisocyanates customarily used in polyurethane chemistry.

Particular mention should be made of 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. Examples of such diisocyanates are 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-α, α, α ', α'-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.

The 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. Furthermore, the 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.

As compounds (a) it is also possible to use isocyanates which, in addition to the free isocyanate groups, contain further blocked isocyanate groups, e.g. Wear uretdione or urethane groups.

If necessary, 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-α, α-dimethylbenzyl isocyanate (TMI) are suitable for this.

To make polyurethanes with some degree of branching or crosslinking, e.g. trivalent and tetravalent isocyanates are used. Such 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.

With regard to good film formation and elasticity, 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. Instead of the free polycarboxylic 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,

Glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimeric fatty acids. 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.

Examples of polyhydric alcohols are 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.

In addition, there are also 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. Instead of the polymers of lactones, the corresponding chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones can also be used.

In addition, 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.

The 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).

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. .

Also suitable are 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.

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. 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).

Furthermore, for chain termination in minor quantities, i.e. 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.

In order to achieve the water dispersibility of the polyurethanes, in addition to components (a), (b) and (c), the polyurethanes 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. In the following text, the term "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.

Particularly suitable 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.

Potentially 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.

As potentially cationic monomers (d), above all 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. In addition, there are 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. Such polyethers generally have a molecular weight between 500 and 6000 g / mol.

These 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. 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. In particular, compounds of the general formula

COOH

HO - R - R - OH

¹ 3

R ³

in which 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.

Corresponding dihydroxysulfonic acids and

Dihydroxyphosphonic acids such as 2,3-dihydroxypropanephosphonic acid.

Otherwise suitable are 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, β-alanine, the adducts of aliphatic diprimeric diamines with α, β-unsaturated carboxylic acids and sulfonic acids mentioned in DE-A 20 34 479. Such compounds obey, for example, the general formula I.

H ₂ NR-NH-R * -X (I) in which 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.

If 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.

It is generally known in the field of polyurethane chemistry how the molecular weight of the polyurethanes can be adjusted by choosing the proportions of the monomers reactive with one another and the arithmetic mean of the number of reactive functional groups per molecule.

Components (a), (b), (c) and (d) and their respective molar amounts are normally chosen so that the ratio A: B with

A) the molar amount of isocyanate groups and

B) the sum of the molar amount of the hydroxyl groups and the molar amount of the functional groups which can react with isocyanates in an addition reaction,

0.5: 1 to 2: 1, preferably 0.8: 1 to 1.5, particularly preferably 0.9: 1 to 1.2: 1. The ratio A: B is very particularly preferably as close as possible to 1: 1.

In addition to components (a), (b), (c) and (d), 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.

To accelerate the reaction of the diisocyanates, 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.

If the reaction is carried out in bulk, extruders, in particular self-cleaning multi-screw extruders, are particularly suitable due to the usually high viscosities and the usually short reaction times.

Most of the time, the dispersions are produced by one of the following processes:

According to the "acetone process", 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. In this case, isocyanate groups are hydrolyzed to amine groups, which react with remaining isocyanate groups of the prepolymers with chain extension. Usually, if a solvent was used in the production of the polyurethane, 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 .

B Cationic polymers

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. Examples of such 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 (meth) acrylamide or ester units, and / or lysine condensates.

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)

from, in which R and R may be the same or different and represent hydrogen and - to C ₆ alkyl. Suitable monomers are, for example, N-vinylformamide (R ^{1 =} R ^{2 =:} H in formula I), N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N -Vinyl-N-methylpropionamide and N- vinyl propionamide. To prepare the polymers, 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. Further 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.

Further 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. Other suitable comonomers are 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.

Other 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. Butyl acrylamide and basic (meth) acrylamides, such as dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminopropyl methacrylamide and diethylaminopropyl methacrylamide.

Also suitable as comonomers are N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazole and substituted N-vinylimidazoles such as N-vinyl-2-methylimidazole, N-vinyl- 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. In addition to the free bases, 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.

In addition, 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

0.01 to 99 mol%, preferably 0.1 to 95 mol% of other monoethylenically unsaturated monomers copolymerizable therewith

in polymerized form.

In order to prepare polymers containing vinylamine units, one preferably starts from homopolymers of N-vinylformamide or from copolymers which are obtained by copolymerizing

N-vinylformamide with

- Vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile, Ν-vinyl caprolactam, Ν-vinyl urea, acrylic acid, Ν-vinyl pyrrolidone or Ci to C ₆ alkyl vinyl ethers

and subsequent hydrolysis of the homo- or of the copolymers to form vinylamine units from the polymerized Ν-vinylformamide units, the degree of hydrolysis being z. B. is 0.1 to 100 mol%.

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

- c - R ² (H)

O

where R ^{2 has} the meaning given for it in formula (I), polymers, the vinylamine units of the formula (III)

CH ₂ - CH

I (III)

Ν '

/ \ _Λ HR ¹ contain in which 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. For example, 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. Also suitable are 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, dihexamethylenetriamine,

Aminopropylethylenediamine and bis-aminopropylethylenediamine. The dicarboxylic acids and polyalkylene polyamines 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. For example, 0.8 to 1.4 moles of a polyalkylene polyamine are used per mole of a dicarboxylic acid.

Other 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.

Further examples of cationic polymers containing amino and / or ammonium groups are polydiallyldimethylammonium chlorides. Polymers of this type are also known.

Other suitable cationic polymers are copolymers of, for example, 1 to

99 mol%, preferably 30 to 70 mol% of acrylamide and / or methacrylamide and / or 1-

Vinyl pyrrolidone and 99 to 1 mol%, preferably 70 to 30 mol% cationic

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,

N-Trimethylarrrmoniumethylmethacrylamidchlorid,

N-Trimethylanimoniumethylmethacrylesterclilorid,

N-trimethylammonium ethyl acrylate chloride, trimethylammonium ethyl acrylamide methosulfate,

Trimethylammoniumethylmethacrylamidmethosulfat,

N-Ethyldimethylammoniumethylacrylamidethosulfat,

N-Ethyldimethylammoniumethylmethacrylamidethosulfat,

Trimethylammonium propyl acrylamide chloride, trimethylammonium propyl methacrylamide chloride,

Trimethylammoniumpropylacrylamidmethosulfat,

Trimethylammoniumpropylmethacrylamidmethosulfatund

N-Ethyldimethylammoniumpropylacrylamidethosulfat.

Trimethylammonium propyl methacrylamide chloride is preferred.

Other suitable cationic monomers for the production of (meth) acrylamide copolymers are diallyldimethylammonium halides and basic (meth) acrylates. For example, 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:

• Copolymers of 50% vinyl pyrrolidone and 50% trimethylammonium ethyl methacrylate methosulfate, M _w from 1000 to 500,000;

• Copolymers of 30% acrylamide and 70% trimethylammonium ethyl methacrylate methosulfate, M _w from 1000 to 1,000,000;

• Copolymers of 70% acrylamide and 30% dimethylaminoethyl methacrylamide, M _w from 1000 to 1,000,000;

• Copolymers of 50% hydroxyethyl methacrylate and 50% 2-dimethylaminoethyl methacrylamide, M _w from 1000 to 500,000;

Polylysines with M _w of 250 to 250,000, preferably from 500 to 100,000, and lysine cocondensates with molar masses M _w of 250 to 250,000, where, for example, amines, polyamines, Uses ketene dimers, lactams, alcohols, alkoxylated amines, alkoxylated alcohols and / or non-proteinogenic amino acids,

Vinylamine homopolymers, 1 to 99% hydrolyzed polyvinylformamides, copolymers of vinylformamide and vinyl acetate, vinyl alcohol,

Vinyl pyrrolidone or acrylamide with molecular weights from 3,000 to 500,000,

• 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. % 1-vinylpyrrolidone with Mw = 50,000, copolymer of 50% by weight 3-methyl-1-vinylimidazolium chloride and 50% by weight 1 -vinylpyrrolidone with Mw = 75,000,

Polyethyleneimines, crosslinked polyethyleneimines or amidated polyethyleneimines with molecular weights from 500 to 3,000,000, for example polyethyleneimine with molecular weights 25,000 or high molecular weight polyethyleneimines with molecular weights 2,000,000.

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.

• Polymers containing basic (meth) acrylamide or ester units, polymers containing basic quaternary (meth) acrylamide or ester units with molecular weights from 10,000 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. Furthermore, it is also possible to polymerize in to a minor extent (<10% by weight) of anionic comonomers, for example acrylic acid, methacrylic acid, vinylsulfonic acid or alkali metal salts of the acids mentioned.

Surface treatment agents

The modification of the properties of textile and non-textile surfaces with polymer dispersions is important in many commercial and technical applications in everyday domestic life. It is not always possible to modify the surfaces using impregnation, spraying and coating processes with concentrated dispersions. It is often desirable to modify the surface by rinsing the surface with a highly diluted liquor containing an active substance. It is often desirable to combine the modification of the surface in connection with washing, cleaning and / or care or impregnation of the surface. In particular, surfaces of textile materials such as cotton fabrics and cotton blends, but also hard surfaces come into consideration.

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 μm 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. In addition, 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.

Surfaces of 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. In particular, 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:

(a) 0.1 to 50% by weight, preferably 0.5 to 25% by weight, of the cationically modified, particulate anionic polyurethanes,

(b) 0 to 60% by weight of 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,

Light stabilizers, dyes, solvents, hydrotropes, thickeners and / or alkanolamines,

(c) 0 to 99.9% by weight of water,

the sum of components (a) to (c) being 100% by weight.

The invention also relates to a textile treatment composition containing

a) 0.1 to 40% by weight, preferably 0.5 to 25% by weight, of the cationically modified, particulate anionic polyurethanes,

b) 0 to 30% by weight of silicones, c) 0 to 30% by weight of cationic and / or nonionic surfactants,

d) 0 to 60% by weight of further ingredients such as further wetting agents, plasticizers, lubricants, water-soluble, film-forming and adhesive polymers, fragrance and

Dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion protection additives, bactericides,

Preservatives and spray aids, and

e) 0 to 99.9% by weight of water,

the sum of components a) to e) being 100% by weight.

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. -

If the textile treatment agent is sprayed onto the textile material, the textile treatment agent can additionally contain a spraying aid. In some cases it may also be advantageous to add alcohols such as ethanol, isopropanol, ethylene glycol or propylene glycol to the formulation. 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

a) 0.05 to 20% by weight of the cationically modified, particulate anionic polyurethanes,

b) 0 to 20% by weight of silicones,

c) 0.1 to 40% by weight of nonionic and / or anionic surfactants,

d) 0 to 50% by weight of inorganic builders,

e) 0 to 10% by weight of organic cobuilders,

f) 0 to 60% by weight of other customary ingredients, such as setting agents, enzymes, perfume,

Complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleaching catalysts, cationic surfactants, color transfer inhibitors,

Graying inhibitors, soil release polyesters, dyes, bactericides,

Resolution improvers and / or disintegrants,

the sum of components a) to f) being 100% by weight.

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

a) 0.05 to 20% by weight of the cationically modified, particulate anionic polyurethanes,

b) 0 to 20% by weight of silicones,

c) 0.1 to 40% by weight of nonionic and / or anionic surfactants,

d) 0 to 20% by weight of inorganic builders, e) - 0 to 10% by weight of organic cobuilders,

f) 0 to 60% by weight of other 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,

g) 0 to 99.85% by weight of water,

the sum of components a) to g) being 100% by weight.

Suitable silicones b) are the silicones mentioned above.

Suitable anionic surfactants c) are in particular:

(Fat) alcohol sulfates of (fatty) alcohols with 8 to 22, preferably 10 to 18 carbon atoms, for example C to Cπ alcohol sulfates, C ₁₂ to C ₁₄ alcohol sulfates,

C ₁₂ -C ₁₈ alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate;

- sulfated 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;

- Linear or branched C ₈ - to C ₂₀ -alkylbenzosulfonates (LAS), preferably linear C - to Co-alkylbenzenesulfonates and -alkyltoluenesulfonates; Alkanesulfonates such as C ₈ to C ₂₄ , preferably C ₁₀ to C ₁₈ alkanesulfonates;

- Soaps such as the Na and K salts of C ₈ - to C ₂ -carboxylic acids.

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. Here, 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.

These preferably contain ethylene oxide as the alkylene oxide. The alcohols preferably have 10 to 18 carbon atoms. Depending on the type of alkoxylation catalyst used in the preparation, 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

5 to 30 alkylene oxide units;

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;

- N-alkyl 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:

- Crystalline or amorphous aluminosilicates with ion-exchanging properties such as, 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;

- Crystalline silicates such as, in particular, disilicates or layered silicates, for example δ-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

silicates;

amorphous silicates such as sodium metasilicate or amorphous disilicate;

- carbonates and hydrogen carbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Na, Li and Mg carbonates or bicarbonates are preferred, in particular sodium carbonate and / or sodium bicarbonate;

- Polyphosphates such as pentasodium triphosphate; 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, 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-

Hydroxyethyl) iminodiacetic acid, ethylenediaminedisuccinic acid and methyl- and ethylglycinediacetic acid;

- 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 α-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

Sodium salt used.

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.

Phtlialimidopercapronsäure.

Suitable bleach activators are, for example, N, N, N ', N'-tetraacetylethylene diamine (TAED), sodium p-nonanoyloxybenzenesulfonate or N-methylmorpholinium acetonitrile methyl sulfate.

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. The 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

a) 0.05% to 40% by weight of the cationically modified, particulate anionic polyurethanes,

b) 0 to 20% by weight of silicones, c) 0.1 to 40% by weight of cationic surfactants,

d) 0 to 30% by weight of nonionic surfactants and

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

f) 0 to 99.85% by weight of water,

the sum of components a) to f) being 100% by weight.

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 Cπ 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 Cπ- to C ₂₂ -alk (en) ylcarbonyloxytrimethylen radical, on the central carbon atom form a Cπ- 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 Cπ to C ₂₂ alk (en) ylcarbonylamino (mono- to trimethylene) radical, a Cπ 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.

The invention is illustrated by the examples below.

Examples

Preparation of anionic dispersions I and II

example 1

Dispersion I

400 g (0.200 mol) of a polyester polyol from adipic acid, neopentyl glycol and hexanediol with OH number 56 were placed in a stirred kettle at 50 ° C. To this were added 36.1 g (0.1624 mol) of isophorone diisocyanate, 42.9 g (0.1624 mol) of bis (4-isocyanatocyclohexyl) methane and 80 g of acetone. After stirring at 90 ° C. for 60 minutes, 0.15 g of dibutyltin dilaurate was added. The mixture was stirred for a further 120 min. The mixture was then diluted with 500 g of acetone and simultaneously cooled to 50 ° C. The NCO content of the solution was 0.99% (calculated 0.94%). After the addition of 22.5 g (0.0534 mol) of a 50% strength by weight aqueous solution of the sodium salt of aminoethylaminoethanesulfonic acid, dispersion was carried out over the course of 5 minutes by adding 800 g of water. After the end of the dispersion, a solution of 3.9 g (0.0379 mol) of diethylenetriamine and 1.8 g (0.0106 mol) of isophoronediamine in 50 g of water was added. After the acetone had been distilled off, a finely divided aqueous anionic PU dispersion with a solids content of approximately 40% was obtained. Example 2

Dispersion II

400 parts of a propylene glycol with an OH number of 56 were dewatered in a flask equipped with an agitator at 130 ° C. and 20 torr for 30 minutes. The polyether was cooled, dissolved in 50 parts of N-methylpyrrolidone and mixed with 26.8 parts of dimethylolpropionic acid. Then, 95.7 parts of tolylene diisocyanate (isomer ratio 2.4 / 2.6 = 80/20) were stirred at 110 ° C. for 120 minutes. The mixture was then diluted with 400 parts of acetone and cooled to 50 ° C. 16 parts of triethylamine and, after 10 minutes, 900 parts of water were added dropwise to the solution thus obtained, and then the acetone was distilled off under reduced pressure. A very finely divided, stable anionic dispersion with a solids content of 40% was obtained.

Production of cationically modified dispersions III, IV and V

The following cationic polymers were used:

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.

Example 3

Dispersion III

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.

Example 4 Dispersion IV

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.

Example 5

Dispersion V

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.

With the help of electrophoretic measurements, the assignment of the anionic PU particles to the cationic polymer could be demonstrated. The coating reversed the direction of migration of the particles in the electric field.

Measurement of the dry crease recovery angle

Examples 6 to 8 and Comparative Examples VI to V3

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. In an analogous manner, 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.

Table 1

The results demonstrate the superior effect of the cationically modified polyurethane dispersions II, IV and V compared to the unmodified anionic polyurethane dispersions I and II.

Use of the dispersions in the rinse cycle.

Examples 9 to 12 and comparative examples V4 to V6

White flat cotton fabric (size: 30 cm x 50 cm) with a weight per unit area of 130 g. In the ² , washing was carried out at a water hardness of 3 mmol / l in the presence of ballast fabric (load 1.5 kg). The washing process consisted of a main wash (Ariel® hydractiv as a detergent, colored wash program 40 ° C) and a subsequent fabric softener. The fabric softener contained

a) 1000 ppm of a commercially available fabric conditioner (Downy from Lenor®)

b) 1000 ppm Downy from Lenor + 100 ppm dispersion I, III or IV (active material)

c) 200 ppm dispersion I, III or IV (active material)

The liquor ratio was 1:10. 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.

The results are shown in Table 2.

Table 2

The results show that the cationically modified dispersions III and IV perform significantly better than the anionic dispersion I.

Claims

claims

1. Cationically modified, particulate anionic polyurethanes with a particle size of 10 nm to 10 μm, the particulate polyurethanes being cationically modified by coating their surface with cationic polymers.

2. Cationically modified, particulate anionic polyurethanes according to claim 1, characterized in that the particulate polyurethanes contain anionic and cationic and / or nonionic hydrophilic groups.

3. Cationically modified, particulate anionic polyurethanes according to claim 1 or 2, characterized in that polymers containing vinylamine units and vinylimidazole units are used as cationic polymers

Polymeric quaternary vinylimidazole units-containing polymers, condensates of imidazole and epichlorohydrin, crosslinked polyamidoamines, ethyleneimine-grafted crosslinked polyamidoamines, polyethyleneimines, alkoxylated polyethyleneimines, crosslinked polyethylenimines, amidated polyethylenimines, alkylated polyethylenimines, polyamines, amine-epichlorohydrin polycondensates, alkoxylated polyamines, polyallylamines, polydimethyldiallylammonium chlorides , polymers containing basic (meth) acrylamide or ester units, basic polymers containing quaternary (meth) acrylamide or ester units and / or lysine condensates.

4. Cationically modified, aqueous anionic polyurethane dispersions containing cationically modified, particulate anionic polyurethanes according to one of claims 1 to 3.

5. A method for modifying the surface of textile and non-textile materials, in which cationically modified, particulate anionic polyurethanes according to one of claims 1 to 3 are applied from an aqueous dispersion to the surface of the materials and the materials are dried.

6. The method according to claim 5, characterized in that the polyurethanes are applied to the surface from an aqueous dispersion having a polyurethane content of <5% by weight. ,

7. Use of cationically modified, particulate anionic polyurethanes, as defined in one of claims 1 to 3, as a surface-modifying additive in detergents, dishwashing agents, care products or cleaning agents.

8. Use of cationically modified, aqueous anionic polyurethane dispersions, as defined in claim 4, as washing, rinsing or cleaning liquors.

9. Surface treatment compositions containing

(a) 0.1 to 50% by weight of cationically modified, particulate anionic polyurethanes according to one of claims 1 to 3,

(b) 0 to 60% by weight of 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, light stabilizers, dyes, solvents, hydrotropes, thickeners and / or alkanolamines,

(c) 0 to 99.9% by weight of water,

the sum of components (a) to (c) being 100% by weight.

10. Textile treatment agent containing

a) 0.1 to 40% by weight of the cationically modified, particulate anionic polyurethanes according to one of claims 1 to 3,

b) 0 to 30% by weight of silicones,

c) 0 to 30% by weight of cationic and / or nonionic surfactants

d) 0 to 60% by weight of further ingredients such as further wetting agents,

Plasticizers, lubricants, water-soluble, film-forming and adhesive polymers, fragrances and dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, Corrosion protection additives, bactericides, preservatives and spray aids, and

e) 0 to 99.9% by weight of water,

the sum of components a) to e) being 100% by weight.

11. Containing solid detergent formulation

a) 0.05 to 20% by weight of the cationically modified, particulate anionic polyurethanes according to one of claims 1 to 3,

b) 0 to 20% by weight of silicones,

c) 0.1 to 40% by weight of nonionic and / or anionic surfactants,

d) 0 to 50% by weight of inorganic builders,

e) 0 to 10% by weight of organic cobuilders,

f) 0 to 60% by weight of other conventional ingredients such as bulking agents, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, cationic surfactants, bleaching catalysts, color transfer inhibitors, graying inhibitors, soil release polyesters, dyes, bactericides, dissolution improvers and or disintegrants .

the sum of components a) to f) being 100% by weight.

12. Containing liquid detergent formulation

a) 0.05 to 20% by weight of the cationically modified, particulate anionic polyurethanes, according to one of claims 1 to 3,

b) 0 to 20% by weight of silicones, c) 0.1 to 40% by weight of nonionic and / or anionic surfactants,

d) 0 to 20% by weight of inorganic builders,

e) 0 to 10% by weight of organic cobuilders,

f) 0 to 60% by weight of other 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,

g) 0 to 99.85% by weight of water,

the sum of components a) to g) being 100% by weight.

13. Laundry detergent containing

a) 0.05% to 40% by weight of the cationically modified, particulate anionic polyurethanes according to one of claims 1 to 3,

b) 0 to 20% by weight of silicones,

c) 0.1 to 40% by weight of cationic surfactants, *

d) 0 to 30% by weight of nonionic surfactants,

e) 0 to 30 wt .-% other common ingredients such as silicones, other lubricants, wetting agents, film-forming polymers, fragrance and

Dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion protection additives, bactericides and preservatives, and

f) 0 to 99.85% by weight of water,

the sum of components a) to f) being 100% by weight.