EP1379724A1

EP1379724A1 - Hydrophilically modified polyisocyanates and polyurethanes for crease-proofing textiles containing cellulose

Info

Publication number: EP1379724A1
Application number: EP01993721A
Authority: EP
Inventors: Jürgen Detering; Peter Neumann; Bernd Bruchmann
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2000-11-13
Filing date: 2001-11-09
Publication date: 2004-01-14
Anticipated expiration: 2021-11-09
Also published as: DE50106600D1; WO2002038852A1; CA2426058A1; ATE298379T1; AU2002217018A1; US20040010858A1; EP1379724B1; ES2241899T3; BR0115302A; MXPA03003147A; CN1474891A; JP2004513261A; DE10056163A1

Abstract

The invention relates to a method for crease-proofing textiles containing cellulose by treating the textiles with a finishing agent and drying the treated textiles, said finishing agent containing (A) one or more hydrophilically modified polyisocyanates and/or (B) one or more polyurethanes in a dissolved or dispersed form.

Description

Hydrophilically modified polyisocyanates and polyurethanes for anti-creasing textiles containing cellulose

The invention relates to methods for anti-wrinkle finishing of cellulose-containing textiles, finishing agents for anti-wrinkle finishing which contain hydrophilically modified polyisocyanates and / or polyurethanes, the use of the finishing agents and the polyisocyanates and polyurethanes, as well as textile treatment agents, solid and liquid detergent formulations and laundry detergents containing them.

Textiles containing cellulose are easy to care for, for example, by treatment with condensation products made from urea, glyoxal and formaldehyde. The equipment takes place during the manufacture of the textile materials. Other additives such as plasticizing compounds are often used in the finishing. The textiles finished in this way have the advantage over the untreated cellulose textiles after the washing process that they have fewer creases and folds, are easier to iron and are softer and smoother.

WO 92/01773 discloses the use of microemulsified aminosiloxanes in fabric softeners to reduce the formation of creases and wrinkles during the washing process (TF anti-crease finish). At the same time, ironing should be made easier by using the aminosiloxanes.

A method for pretreating textile materials is known from WO 98/4772, a mixture of a polycarboxylic acid and a cationic plasticizer being applied to the textile materials. Anti-crease is achieved.

From EP-A 0 300 525, fabric softeners based on crosslinkable ammofunctionalized silicones are known which bring about a crease protection or an easy ironing effect for the textiles treated with them.

Formulations are known from WO 99/55953 which cause an anti-creasing effect in the treated textiles. The formulations consist of lubricants, Polymers that ensure the dimensional and dimensional stability of the textiles, lithium salts and optionally other ingredients such as plasticizers, ionic and nonionic surfactants, odor-binding substances and bactericides. The formulation is preferably applied to the textile material by spraying.

EP-A 0 978 556 describes a mixture of a plasticizer and a crosslinking component with cationic properties as an agent for providing textiles with anti-crease and wrinkle protection, and a method for anti-wrinkling finishing of textiles.

The object of the invention is to provide a further process for the anti-crease treatment of cellulose-containing textiles as well as further finishing agents for the anti-crease treatment of such textiles.

The object is achieved by a process for anti-creasing cellulose-containing textiles by treating the textiles with an finishing agent and drying the treated textiles, characterized in that the finishing agent (A) one or more hydrophilically modified polyisocyanates and / or (B) one or more polyurethanes contains in dissolved or dispersed form.

The object is also achieved by an finishing agent for anti-wrinkle finishing of cellulose-containing textiles, which contains the hydrophilically modified polyisocyanates and / or polyurethanes.

Hydrophilically modified polyisocyanates

The finishing agent according to the invention can contain (A) one or more hydrophilically modified polyisocyanates.

The basis for the hydrophilically modified polyisocyanates used according to the invention are customary diisocyanates and / or customary higher-functionality polyisocyanates with an average NCO functionality of 2.0 to 4.5. These components can be present alone or in a mixture. Examples of common diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane),

Octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanate-ocyclohexane, 4,4'-di (isocyanatocyanocyclohexyl) 3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate) or 2,4- or 2,6-diisocyanato-1-methylcyclohexane as well as aromatic diisocyanates such as 2,4- or 2,6-tolylene diisocyanate, tetramethylxylylene diisocyanate, p -Xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane, 1,3- or 1,4-phenylene diisocyanate, l-chloro-2,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4 '- diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate or diphenyl ether-4,4'-diisocyanate. Mixtures of the diisocyanates mentioned can also be present. Of these, aliphatic diisocyanates, in particular hexamethylene diisocyanate and isophorone diisocyanate, are preferred.

Triisocyanates such as 2,4,6-triisocyanatotoluene or 2,4,4'-triisocyanatodiphenyl ether or the mixtures of di-, tri- and higher polyisocyanates obtained by phosgenation of corresponding aniline / formaldehyde condensates are suitable as customary higher-functional polyisocyanates are and represent methylene bridges polyphenyl polyisocyanates.

Common aliphatic higher functional polyisocyanates of the following groups are of particular interest:

(a) Isocyanurate group-containing polyisocyanates of aliphatic and / or cycloaliphatic diisocyanates. The corresponding isocyanate isocyanurates based on hexamethylene diisocyanate and isophorone diisocyanate are particularly preferred. The present isocyanurates are, in particular, simple tris-isocyanatoalkyl- or triisocyanatocycloalkyl-

Isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologues containing more than one isocyanurate ring. The isocyanato-isocyanurates generally have an NCO content of 10 to 30% by weight, in particular 15 to 25% by weight, and an average NCO functionality of 2.6 to 4.5. (b) Polyisocyanates containing uretdione groups with aliphatic and / or cycloaliphatic bound isocyanate groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdiones are cyclic dimers of two NCO groups.

(c) Polyisocyanates containing biuret groups with aliphatically bound isocyanate groups, in particular tris (6-isocyanatohexyl) biuret, or mixtures thereof with its higher homologues. These polyisocyanates containing biuret groups generally have an NCO content of 18 to 25% by weight and an average NCO functionality of 3 to 4.5.

(d) Polyisocyanates containing urethane and / or allophanate groups with aliphatically or cycloaliphatically bound isocyanate groups, such as, for example, by reacting excess amounts of hexamethylene diisocyanate or isophorone diisocyanate with simple polyhydric alcohols such as

Trimethylolpropane, glycerol, 1,2-dihydroxypropane or mixtures thereof can be obtained. These polyisocyanates containing urethane and / or allophanate groups generally have an NCO content of 12 to 20% by weight and an average NCO functionality of 2.5 to 3.

(e) Polyisocyanates containing oxadiazinetrione groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such polyisocyanates containing oxadiazinetrione groups can be prepared from diisocyanate and carbon dioxide.

(f) Uretonimine-modified polyisocyanates.

For the use according to the invention, the described diisocyanates and / or higher functionalized polyisocyanates for conversion into non-ionically hydrophilically modified polyisocyanates, which are particularly preferred for the use according to the invention, are reacted with NCO-reactive compounds which have hydrophilicizing structural elements with non-ionic groups or with polar groups that cannot be converted into ion groups. The diisocyanate or polyisocyanate is present in a stoichiometric excess so that the resulting hydrophilically modified polyisocyanate still has free NCO groups. Hydroxylgrappentπniiiierte polyethers of the general formula I in particular come as such NCO-reactive compounds with hydrophilic structural elements

R - E— (DO) - H (I)

in the

R ⁸ represents C 1 to C ₂₀ alkyl, in particular C 1 to C ₄ alkyl, or C ₂ to C ₀ alkenyl, cyclopentyl, cyclohexyl, glycidyl, oxethyl, phenyl, tolyl, benzyl, furfuryl or tetrahydrofurfuryl,

E denotes sulfur or in particular oxygen,

D means propylene or, above all, ethylene, it also being possible for ethoxylated and propoxylated compounds to be mixed in particular in blocks, and

n stands for a number from 5 to 120, in particular 10 to 25,

into consideration.

The use of non-ionically hydrophilically modified polyisocyanates, which contain the polyether I incorporated, is therefore also a preferred embodiment.

This is particularly preferred in order to Ci- to C ₄ - alkanol started ethylene oxide or propylene oxide polyethers having average molecular weights of from 250 to 7000, in particular from 450 to 1,500.

The diisocyanates and / or higher functionalized polyisocyanates described can also first be obtained by reaction with a deficit of hydroxyl-terminated polyesters, on other hydroxyl-terminated polyethers or on polyols, e.g. Generate ethylene glycol, trimethylolpropane or butanediol, prepolymers and then implement these prepolymers either subsequently or simultaneously with the polyethers I in deficit to the hydrophilically modified polyisocyanates with free NCO groups.

It is also possible to use non-ionically hydrophilically modified polyisocyanates of diisocyanate or polyisocyanate and polyalkylene glycols of the formula HO- (DO) _n -H, in which D and n are the have meanings mentioned above. Both terminal OH groups of the polyalkylene glycol react with isocyanate.

The enumerated types of non-ionically hydrophilically modified polyisocyanates are in the documents DE-A 24 47 135, DE-A 26 10 552, DE-A 29 08 844, EP-A 0 13 112, EP-A 019 844, DE-A 40 36 927, DE-A 41 36 618, EP-B 206 059, EP-A 464781 and EP-A 516 361.

The described diisocyanates and / or higher functionalized polyisocyanates are reacted with NCO-reactive compounds for conversion into anionically hydrophilically modified polyisocyanates which contain hydrophilic anionic groups, in particular acid groups such as carboxyl groups, sulfonic acid groups or phosphonic acid groups. The diisocyanate or polyisocyanate is present in a stoichiometric excess so that the resulting hydrophilically modified polyisocyanate still has free NCO groups.

Particularly useful NCO-reactive compounds with anionic groups are hydroxycarboxylic acids such as 2-hydroxyacetic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid or hydroxylpivalic acid and 2,2-bis- and 2,2,2-tris (hydroxymethyl) alkanoic acids, e.g. 2,2-bis (hydroxymethyl) acetic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid or 2,2,2-tris (hydroxymethyl) acetic acid. The carboxyl groups can be partially or completely neutralized by a base in order to be in a water-soluble or water-dispersible form. The base used here is preferably a tertiary amine, which is known to be inert to isocyanate.

The described diisocyanates and / or more highly functionalized polyisocyanates can also be reacted with a mixture of nonionically hydrophilically modifying and anionically hydrophilically modifying compounds which are added in succession or simultaneously, for example with a deficit of the polyethers I and the described hydroxycarboxylic acids.

The enumerated types of anionically hydrophilically modified polyisocyanates are described in more detail in the documents DE-A 40 01 783, DE-A 41 13 160 and DE-A 41 42 275.

The described diisocyanates and / or higher functionalized polyisocyanates are converted into cationically hydrophilic modified polyisocyanates with NCO-reactive Compounds implemented that contain chemically incorporated alkylatable or protonatable functions to form a cationic center. In particular, such functions are tertiary nitrogen atoms, which are known to be inert to isocyanate and are easily quaternized or protonated. When diisocyanate or polyisocyanate is reacted with these NCO-reactive compounds, the former are in excess, so that the resulting hydrophilically modified polyisocyanate still has free NCO groups.

Such NCO-reactive compounds with tertiary nitrogen atoms are preferably amino alcohols of the general formula II

in the

R ⁹ and R ^{10 are} linear or branched C 1 to C ₂₀ alkyl, in particular C 1 to C ₅ alkyl, or together with the N atom form a five- or six-membered ring which is also an O atom or a tertiary one N atom can contain, in particular a piperidine, morpholine, piperazine, pyrrolidine oxazoline or dihydrooxazine ring, where the radicals R ⁹ and R ¹⁰ can additionally carry hydroxyl groups, in particular in each case one hydroxyl group, and

R ¹¹ denotes a C ₂ to C ₁₀ alkylene group, in particular a C to C ₆ alkylene group, which can be linear or branched,

into consideration.

Particularly suitable amino alcohols II are N-methyldiethanolamine, N-methyldi (iso) propanolamine, N-butyldiethanolamine, N-butyldi (iso) propanolamine, N-stearyldiethanolamine, N-stearyldi (iso) propanolamine, N, N-dimethylethanolamine, N , N-dimethyl (iso) propanolamine, N, N-diethylethanolamine, N, N-die yl (iso) prop-molamine, N, N-dibutylethanolamine, N, N-dibutyl (iso) propanolamine, triethanolamine,

Tri (iso) propanolamine, N- (2-hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpholine, N- (2-hydroxyethyl) piperidine, N- (2-hydroxypropyl) piperidine, N-methyl-N '- ( 2 hydroxyethyl) piperazine, N-methyl-N '- (2-hydroxypropyl) piperazine, N-methyl-N' - (4-hydroxybutyl) ρiperazine, 2-hydroxyethyloxazoline, 2-hydroxypropyloxazoline, 3-hydroxypropyloxazoline, 2-hydroxyethyldihydrooxazine, 2- Hydroxypropyl dihydrooxazine or 3-hydroxypropyl dihydrooxazine.

Furthermore, such NCO-reactive compounds with tertiary nitrogen atoms are preferably diamines of the general formula purple or IIIb

(IIIb)

in which R ⁹ to R ^{11 have} the meanings given above and R ¹² denotes - to Cs-alkyl or forms a five- or six-membered ring, in particular a piperazine ring, with R ⁹ .

N, N-dimethyl-ethylenediamine, N, N-diethyl-ethylenediamine, N, N-dimethyl-1, 3-diamino-2,2-dimethylpropane, N, N-diethyl-1, 3 are particularly suitable as diamines purple - Propylenediamine, N- (3-aminopropyl) morpholine, N- (2-aminopropyl) morpholine, N- (3-aminopropyl) piperidine, N- (2-aminopropyl) piperidine, 4-amino-1- (, N-diethylamino ) pentane, 2-Ammo-l- (N, N-dimemylamino) propane, 2-Amino-l- (N, N-diethylamino) propane or 2-Ammo-l- (N, N-die ylamino) -2- methylpropane.

Particularly suitable diamines IIIb are N, N, N'-trimethylethylenediamine, N, N, N'-triethylethylenediamine, N-methylpiperazine or N-ethylpiperazine.

Furthermore, polyether (poly) ols with built-in tertiary nitrogen atoms, which can be prepared by propoxylation and / or ethoxylation of starter molecules containing amine nitrogen, can also be used as NCO-reactive compounds. Such polyether (poly) oles are, for example, the propoxylation and ethoxylation products of ammonia, ethanolamine, diethanolamine, ethylenediamine or N-methylaniline.

Other NCO-reactive compounds which can be used are polyester and polyamide resins having tertiary nitrogen atoms, polyols containing urethane groups and tertiary nitrogen atoms, and polyhydroxy polyacrylates having tertiary nitrogen atoms. The described diisocyanates and / or higher functionalized polyisocyanates can also be reacted with a mixture of non-ionically hydrophilically modifying and cationically hydrophilically modifying compounds which are added in succession or simultaneously, for example with a deficit of the polyethers I and the amino alcohols II or the Diamonds purple or lllb. Mixtures of nonionically hydrophilically modifying and anionically hydrophilically modifying compounds are also possible.

The enumerated types of cationically hydrophilically modified polyisocyanates are described in more detail in the documents DE-A 42 03 510 and EP-A 531 820.

Since the hydrophilically modified polyisocyanates (A) mentioned are generally used in aqueous media, the polyisocyanates must be sufficiently dispersible. Within the group of the hydrophilically modified polyisocyanates described, certain reaction products of di- or polyisocyanates and hydroxyl-terminated polyethers (polyether alcohols) such as the compounds I preferably act as emulsifiers for this purpose.

The good results achieved with the hydrophilically modified polyisocyanates (A) in aqueous media are all the more surprising since it was to be expected that isocyanates would decompose rapidly in an aqueous medium. Nevertheless, the polyisocyanates used according to the invention have a pot life of several hours in the aqueous liquor, i.e. the present polyisocyanate dispersions are stable within the usual processing time. A dispersion is said to be stable if its components remain dispersed within one another without separating into discrete layers. The term "pot life" means the time during which the dispersions remain processable before they gel and set. Aqueous isocyanate dispersions gel and set because a reaction takes place between the water and the isocyanate, producing a polyurea.

Polyurethane

The finishing agent according to the invention can contain (B) one or more polyurethanes. Polyurethanes are understood to be systems composed of polyisocyanates (hereinafter also referred to as monomers I) and compounds which are reactive towards polyisocyanates and have at least one hydroxyl group and, if appropriate, compounds having at least one primary or secondary amino group. As a rule, the polyurethanes no longer have any free isocyanate groups.

The polyisocyanates used to produce the polyurethanes (B) contained in the finishing agent are conventional diisocyanates and / or customary higher-functional polyisocyanates, as described for the hydrophilically modified polyisocyanates (A). Here too, aliphatic diisocyanates and aliphatic higher-functional polyisocyanates are preferred.

The other structural components of the polyurethane are initially polyols with a molecular weight of 400 to 6000 g / mol, preferably 600 to 4000 g / mol (monomers II).

Polyether polyols or polyester polyols are particularly suitable.

The polyester diols are in particular the known reaction products of 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, aromatic or heterocyclic and optionally, e.g. by halogen atoms, substituted and / or unsaturated. Examples include: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophydic anhydride, tetrachlorophthalic anhydride,

Endomethylene tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimeric fatty acids. Polyhydric alcohols include, for example, ethylene glycol, propylene glycol (1, 2) and - (1,3), butanediol (1,4,), (1,3), butenediol (1,4), butynediol (1, 4), pentanediol- (l, 5), hexanediol- (l, 6), octanediol- (l, 8), neopentylglycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-l, 3-propanediol, Pentanediol (l, 5), further diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol in question. Lactone-based polyester diols are also suitable, these being homopolymers or copolymers of lactones, preferably addition products of lactones or lactone mixtures having terminal hydroxyl groups, such as, for example, ε-caprolactone, β-propiolactone, γ-butyrolactone and / or methyl ε-caprolactone to suitable difunctional starter molecules, for example the low molecular weight, dihydric alcohols mentioned above as structural components for the polyester polyols. The corresponding polymers of ε-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.

The polyether diols, which may also be used in a mixture with polyester diols, 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, optionally in a mixture or in succession, on starting components available with reactive hydrogen atoms, such as alcohols or amines, for example water, ethylene glycol, propylene glycol (1,3) or - (1,2), 4,4'-dihydroxydiphenylpropane and aniline.

The proportion of the monomer II described above is generally 0.1 to 0.8 gram equivalent, preferably 0.2 to 0.7 gram equivalent of the hydroxyl group of the monomer II based on 1 gram equivalent of isocyanate of the polyisocyanate.

Further structural components of the polyurethane are chain extenders or crosslinkers with at least two groups that are reactive toward isocyanate, selected from hydroxyl groups, primary or secondary amino groups.

Polyols, in particular diols and triols, with a molecular weight below 400 g / mol to 62 g / mol (monomers III) may be mentioned.

In particular, the diols and triols listed above which are suitable for the production of the polyester polyols, and also higher than ixifunctional alcohols, such as pentaerythritol or sorbitol, are suitable.

The proportion of the monomers III is generally 0 to 0.8, in particular 0 to 0.7 gram equivalent, based on 1 gram equivalent of isocyanate. The optionally used monomers IV are at least difunctional amine chain extenders or crosslinkers in the molecular weight range from 32 to 500 g / mol, preferably from 60 to 300 g / mol, which have at least two primary, two secondary or one primary and one contain secondary amino group.

Examples include diamines, such as diaminoethane, diaπünopropane, diaminobutane, diaminohexane, piperazine, 2,5-dimethylpiperazine, amino-3-amine yI-3,5,5-trimethylcyclohexane (isophorone diamine, IPDA), 4,4'-diaminodicyclohexylmethane , 1,4-diamino-cyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as diethylenetriamine or 1,8-diarnino-4-aminomethyloctane. The chain extenders containing amino groups can also be in blocked form, e.g. in the form of the corresponding ketimines (see e.g. CA-1 129 128), ketazines (see e.g. U.S.-A-4,269,748) or amine salts (see U.S.-A-4,292,226). Oxazolidines, as are used, for example, in US Pat. No. 4,192,937, are masked 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 as an intermediate hydrolysis.

Mixtures of di- and triamines are preferably used, particularly preferably mixtures of isophoronediamine and diethylenetriamine.

The monomers V, which may also be used as chain extenders, are amino alcohols with a hydroxyl and a primary or secondary amino group such as ethanolamine, isopropanolamine, methylethanolamine or aminoethoxyethanol.

The proportion of the monomers IV or V is in each case preferably 0 to 0.4, particularly preferably 0 to 0.2 gram equivalent, based on 1 gram equivalent of isocyanate of the polyisocyanate.

Compounds which contain at least one, preferably two, groups which are reactive toward isocyanate groups, that is to say hydroxyl, primary or secondary amino groups, and moreover in contrast to those, can be used as a further structural component Monomers described above have ionic groups or potentially ionic groups which can be converted into ionic groups by a simple neutralization or quaternization reaction. (Monomers VI). By introducing the monomers VI, the polyurethanes themselves become dispersible, ie in this case no dispersing aids such as protective colloids or emulsifiers are required when dispersing in water.

The cationic or anionic groups can be introduced by also using (potential) cationic or (potential) anionic groups having compounds with hydrogen atoms which are capable of isocyanate. These groups of compounds include e.g. 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, are accessible in a conventional manner. Such polyethers generally have a molecular weight between 500 and 6000 g / mol.

However, the ionic groups are preferably introduced by using comparatively low molecular weight compounds with (potential) ionic groups and groups which are reactive toward isocyanate groups. Examples of these are given in US-A 3,479,310 and 4,056,564 and GB-1,455,554. Dihydroxyphosphonates, such as the sodium salt of 2,3-dihydroxypropanephosphonic acid ethyl ester or the corresponding sodium salt of non-esterified phosphonic acid, can also be used as an ionic structural component.

Preferred (potential) ionic monomers VI are N-A-dialkanolamines, e.g. N-methyldiethanolamine, N-ethyldiethanolamine, diaminosulfonates, such as the Na salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid, dihydroxysulfonates, dihydroxycarboxylic acids such as dimethylolpropionic acid, diaminocarboxylic acids or carboxylates such as lysine or the Na salt of N- ( 2-aminoethyl) -2-aminoethane carboxylic acid and diamines with at least one additional tertiary amine nitrogen atom, for example N-methyl-bis- (3-aminopropy flamin.

Diamino- and dihydroxycarboxylic acids are particularly preferred, in particular the adduct of ethylenediamine with sodium acrylate or dimethylolpropionic acid. The conversion of the potential ionic groups, if any, which are initially initially incorporated into the polyaddition product, at least partially into ionic groups, takes place in a conventional manner by neutralization of the potential anionic or cationic groups or by quaternization of tertiary amine nitrogen atoms.

For the neutralization of potential anionic groups, e.g. Carboxyl groups, inorganic and / or organic bases are used, such as alkali metal hydroxides, carbonates or hydrogen carbonates, ammonia or primary, secondary and particularly preferably tertiary amines such as triemylamine or dimethylaminopropanol.

To transfer the potential cationic groups, e.g. the tertiary amine groups into the corresponding cations, e.g. Ammonium groups are inorganic or organic acids, e.g. Hydrochloric, phosphoric, formic, acetic, fumaric, maleic, lactic, tartaric or oxalic acid or as quaternizing agents, e.g. Methyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, benzyl chloride, chloroacetic acid ester or bromoacetamide are suitable. Other neutralizing or quaternizing agents are e.g. in US-A 3,479,310 column 6.

This neutralization or quaternization of the potential ion groups can take place before, during, but preferably after the isocyanate polyaddition reaction.

The amounts of the monomers VI, in the case of potential components containing ion groups, taking into account the degree of neutralization or quaternization, should suitably be chosen so that the polyurethanes have a content of 0.05 to 2 meq / g polyurethane, preferably 0.07 to 1.0 and particularly preferably from 0.1 to 0.7 meq / g of polyurethane have ionic groups.

If appropriate, monofunctional amine or hydroxyl compounds are also used as structural components (monomers VII). They are preferably monohydric polyether alcohols with a molecular weight in the range from 500 to 10,000 g / mol, preferably from 800 to 5,000 g / mol. Monohydric polyether alcohols can be obtained, for example, by alkoxylation of monohydric starter molecules, such as, for example, methanol, ethanol or n-butanol, ethylene oxide or mixtures of ethylene oxide with other alkylene oxides, in particular propylene oxide, being used as the alkoxylating agent. If alkylene oxide mixtures are used, however, these preferably contain at least 40, particularly preferably at least 65 mol% of ethylene oxide. The monomers VII can thus, if appropriate, incorporate polyethylene oxide segments which are present in terminally arranged polyether chains and which, in addition to the ionic groups, influence the hydrophilic character in the polyurethane and ensure or improve dispersibility in water.

The compounds of the type mentioned are preferred, if use is made of them, in such amounts that from 0 to 10, preferably from 0 to 5,% by weight of polyethylene oxide units are introduced into the polyurethane.

Further examples of compounds which can be used as monomers I to VII in the production of the polyurethanes described are e.g. in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology", by Saunders-Frisch, Interscience Publishers, New York, London, Volume 1, 1962, pages 32 to 42 and pages 44 to 54 and Volume II, pages 5 to 6 and 198 to 199.

Suitable monomers VIII, which, in contrast to the above monomers, contain ethylenically unsaturated groups, are, for example, esters of acrylic or methacrylic acid with polyols, at least one OH group of the polyol remaining unesterified. Hydroxyalkyl (meth) acrylates of the formula HO (CH ₂ ) _m OOC (R ¹² ) C = CH ₂ (m = 2 to 8; R ¹² = H, CH ₃ ) and their positional isomers, mono (meth) acrylic acid esters of Polyether diols, such as those listed for the monomers II, trimethylolpropane mono- and di (meth) acrylate, pentaerythritol di- and tri (meth) acrylate or reaction products of epoxy compounds with (meth) acrylic acid, as described, for example, in US Pat. No. 357,221 are mentioned. The adducts of (meth) acrylic acid with bisglycidyl ether of diols such as, for example, bisphenol A or butanediol are particularly suitable.

Adducts of (meth) acrylic acid with epoxidized diolefins such as e.g. 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate.

By incorporating the monomers VIII, the polyurethane can, if desired, be cured subsequently thermally or photochemically, optionally in the presence of an initiator.

In general, the proportion of ethylenically unsaturated groups is less than 0.2 mol per 100 g of polyurethane. Overall, the proportion of the structural components is preferably chosen such that the sum of the hydroxyl groups and primary or secondary amino groups reactive towards isocyanate is 0.9 to 1.2, particularly preferably 0.95 to 1.1, based on 1 isocyanate group.

The polyurethanes described, in particular as dispersions, can be prepared by the customary methods, as described, for example, are described in the above-mentioned documents.

Is preferred in an inert, water-miscible solvent, such as acetone, tetrahydrofuran, methyl ethyl ketone or N-methylpyrrolidone from the monomers I and II and optionally III, V, VI, VII and VIII, if VI contains no amino groups, the polyurethane or, if a further reaction with amino-functional monomers IV or VI is intended to produce a polyurethane prepolymer with terminal isocyanate groups.

The reaction temperature is generally between 20 and 160 ° C, preferably between 50 and 100 ° C.

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.

The polyurethane prepolymer obtained can, if appropriate after (further) dilution with solvents of the type mentioned above, preferably with solvents having a boiling point below 100 ° C., be reacted further at a temperature between 20 and 80 ° C. with amino-functional compounds of the monomers VI and optionally IV.

The conversion of potential salt groups, for example carboxyl groups, or tertiary amino groups, which were introduced into the polyurethane via the monomers VI, into the corresponding ions takes place by neutralization with bases or acids or by quaternization of the tertiary amino groups before or during the dispersion of the polyurethane in water. After the dispersion, the organic solvent, if its boiling point is below that of the water, can be distilled off. Any solvents with a higher boiling point that are used can remain in the dispersion.

The content of the polyurethane in the dispersions can in particular be between 5 and 70 percent by weight, preferably between 20 and 50 percent by weight, based on the dispersions.

Customary auxiliaries, e.g. Thickeners, thixotropic agents, oxidation and UV stabilizers or release agents can be added.

Hydrophobic auxiliaries, which can be difficult to distribute homogeneously in the finished dispersion, can also be added to the polyurethane or the prepolymer before the dispersion by the method described in US Pat. No. 4,306,998.

Use of the hydrophilically modified polyisocyanates and polyurethanes

The invention also relates to the use of hydrophilically modified polyisocyanates (A) and of polyurethanes (B) in finishing agents for the anti-crease treatment of textiles containing cellulose. Finishing agents are any liquid formulations which contain the hydrophilically modified polyisocyanates (A) and / or the polyurethanes (B) for application to the textile material in dissolved or dispersed form. The dressing agents according to the invention can be present, for example, as finishing agents in the narrower sense in the manufacture of textiles in the form of an aqueous washing liquor or as liquid textile treatment agents. Suitable solvents are, for example, water, alcohols such as methanol, ethanol and propanol, THF or mixtures thereof. For example, it is possible to treat the textiles with the finishing agent in connection with textile production. Textiles that have not yet been treated or have been insufficiently treated with finishing agents can be treated, for example, in the home area before or after washing, for example when ironing, with a textile treatment agent which contains the highly branched polymers. However, it is also possible to treat the textiles in the main wash cycle or after the main wash cycle in the care or fabric softener cycle of the washing machine with hydrophilically modified polyisocyanates (A) and / or the polyurethanes (B). The present invention also relates to the use of the hydrophilically modified polyisocyanates (A) and / or the polyurethanes (B) in the manufacture of the textiles, in the treatment of the textiles before and after washing, in the main wash cycle, in the fabric rinse cycle and on ironing. Different formulations are required for this.

Textile treatment, detergent and conditioner formulations

In the treatment before or after the textile washing, a textile treatment agent can be used as a finishing agent which, in addition to the hydrophilically modified polyisocyanates (A) and / or polyurethanes (B), contains a surface-active agent in dissolved or dispersed form. In this treatment, the cellulose-containing textiles are sprayed, for example, with the hydrophilically modified polyisocyanates (A) and / or the polyurethanes (B), the amount applied generally being 0.01 to 10% by weight, preferably 0.1 to 7, particularly preferably 0 , 3 to 4 wt.%, Based on the weight of the dry textile goods, may be. The finishing agent can, however, also be applied to the textile material by immersing the textiles in a bath which is generally 0.1 to 10% by weight, preferably 0.3 to 5% by weight, based on the weight of the dry textile material , the hydrophilically modified polyisocyanates (A) and / or the polyurethanes (B) dissolved or dispersed. The textile is either only briefly immersed in the bath or can also remain there for a period of, for example, 1 to 30 minutes.

The cellulose-containing textiles, which have been treated with the finishing agent either by spraying or by immersion, are optionally pressed off and dried. The drying can be done in air or in a dryer or by hot ironing the treated textile. The finishing agent is fixed on the textile by drying. The most favorable conditions for this can easily be determined with the help of searches. The temperature during drying, including ironing, is generally 40 to 150 ° C, preferably 60 to 110 ° C. The iron ironing program is particularly suitable for ironing. The textiles which have been treated with the hydrophilically modified polyisocyanates (A) or polyurethanes (B) in dissolved or dispersed form by the process described above have excellent crease and wrinkle protection which remains after several washes. Ironing the Textiles are often no longer required. The textiles treated in this way also have fiber and color protection.

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 at least one hydrophilically modified polyisocyanate (A) and / or at least one polyurethane (B),

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 colorants, stabilizers, fiber and color protection additives, viscosity modifiers,

Soil release additives, anti-corrosion additives, bactericides, preservatives and spraying aids, and

e) 0 to 99.9% by weight of water,

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

Preferred silicones are amino group-like silicones, which are preferably in microemulsified form, alkoxylated, in particular ethoxylated silicones, polyalkylene oxide polysiloxanes, polyalkylene oxide aniinopolydimethylsiloxanes, 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 formulation is sprayed onto the textile material, the formulation may additionally contain a spraying aid. In some cases, it can also be advantageous to add alcohols such as ethanol, isopropanol, Add 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 quantities. The textile treatment agent can also be applied when the fabric is ironed after washing, generally by spraying. This not only makes ironing considerably easier, the textiles are also equipped with long-lasting crease and wrinkle protection.

The hydrophilically modified polyisocyanates (A) and / or the polyurethanes (B) can also be used for washing the textiles in the main washing cycle of the washing machine.

The invention relates to a solid detergent formulation containing

a) 0.05 to 20% by weight of at least one hydrophilically modified polyisocyanate (A) and / or at least one polyurethane (B),

b) 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant,

c) 0 to 50% by weight of an inorganic builder,

d) 0 to 10% by weight of an organic cobuilder,

e) 0 to 60% by weight of other customary ingredients such as adjusting 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, dissolution improvers and / or disintegrants,

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

Suitable anionic surfactants are in particular:

(Fat) alcohol sulfates of (fatty) alcohols with 8 to 22, preferably 10 to 18 carbon atoms, for example C - to Cn alcohol sulfates, C ₂ - to C ₁₄ alcohol sulfates, C ₁ - 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). Connections this

Art are prepared, for example, by first alkoxylating a C ₈ to C ₂₂ , preferably a C ₁₀ to C ₁₈ alcohol, for example a fatty alcohol, and then sulfating the alkoxylation product. Ethylene oxide is preferably used for the alkoxylation; linear C ₈ - to C o-alkylbenzosulfonates (LAS), preferably linear C ₉ - to C ₁₃ -

Alkylbenzenesulfonates and alkyltoluenesulfonates,

Alkanesulfonates such as C ₈ to C ₂₄ , preferably C ₁₀ to C ₁₈ alkanesulfonates, soaps such as, for example, the Na and K salts of C ₈ to C ₂₄ 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 and ammonium ions such as hydroxy ylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium.

Suitable nonionic surfactants are in particular: alkoxylated 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, per mole of alcohol

Moles of at least one alkylene oxide. 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 ₁ 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 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 partly 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 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 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. agaricinic acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid,

Oxydisuccinic acid, propane tricarboxylic acid, butane tetracarboxylic acid, cyclopentane tetracarboxylic acid, alkyl and alkenyl succinic acids and aminopolycarboxylic acids such as e.g. Nitrilotriacetic acid, ß-alariinediacetic 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 ₂ olefins such as isobutene or long-chain α-olefins, vinyl alkyl ethers with C ₁ -C ₈ alkyl groups, vinyl acetate, vinyl propionate, (Meth) acrylic esters of -Cs alcohols and styrene. It is preferred to use the

Homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid. Polyaspartic acids are also suitable as organic cobuilders. The oligomeric and polymeric carboxylic acids are used in acid form or as the sodium salt.

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

b) 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant,

c) 0 to 20% by weight of an inorganic builder,

d) 0 to 10% by weight of an organic cobuilder,

e) 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, solubility promoters , Hydrotropes, thickeners and / or alkanolamines,

f) 0 to 99.85% by weight of water,

the sum of components a) to f) being 100% by weight. i The abovementioned nonionic and anionic surfactants, builders and cobuilders can be used.

A detailed description of the detergent ingredients mentioned can be found e.g. 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.

The concentration of the hydrophilically modified polyisocyanates or the 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 hydrophilically modified polyisocyanates or polyurethanes in the main wash 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 being washed several times, look less "used" due to their fiber and color protection, ie they have less lint and knots and less color damage or fading. The hydrophilically modified polyisocyanates or the polyurethanes can be used in the so-called soft or conditioner rinse after the main wash cycle. The concentration of the hydrophilically modified polyisocyanates or the 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 at least one hydrophilically modified polyisocyanate (A) and / or at least one polyurethane (B),

b) 0.1 to 40% by weight of a cationic surfactant,

c) 0 to 30% by weight of a nonionic surfactant,

d) 0 to 30% by weight of other conventional ingredients such as silicones, other 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

e) 0 to 99.85% by weight of water,

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

Preferred cationic surfactants are selected from the group of the quaternary diesterammonium salts, the quaternary tetraalkylammonium salts, the quaternary

Diamidoammonium salts, the amidoamine ester and imidazolium salts. Examples are quaternary diesterammonium salts, the two Cπ to C ₂₂ alk (en) ylcarbonyloxy (mono- to have pentamethylene) radicals and two Ci to C ₃ alkyl or hydroxyalkyl radicals on the quaternary N atom and carry, for example, chloride, bromide, methyl sulfate or sulfate as counterion.

Quaternary diesterammonium salts are furthermore, in particular, those which have a Cπ to C ₂ alk (en) ylcarbonyloxytrimethylene radical and which have a Cπ to C ₂₂ alk (en) ylcarbonyloxy radical on the middle C atom of the trimethylene group and three C 1 to C ₃ alkyl or hydroxyalkyl radicals on the quaternary N atom and, for example, chloride, bromide, methyl sulfate or sulfate as counterion.

Quaternary tetraalkylammonium salts are in particular those which have two Q to C ₆ alkyl radicals and two C ₈ to C ₂₄ alk (en) yl radicals on the quaternary N atom and, for example, chloride, bromide, methyl sulfate or sulfate as counterions wear.

Quaternary diamidoammonium salts are in particular those which have two C ₈ - to C ₂₄ -alk (en) ylcarbonylaminoethylene radicals, a substituent selected from hydrogen, methyl, ethyl and polyoxyethylene with up to 5 oxyethylene units and as the fourth radical a methyl group on the quaternary N. -Atom and have as counterion, for example, chloride, bromide, methyl sulfate or sulfate.

Amidoamino esters are, in particular, tertiary amines which, as substituents on the N atom, have a Cπ to C ₂ alk (en) ylcarbonylamino (mono- to trimethylene) radical, a Cπ to C ₂ alk (en) ylcarbonyloxy (mono- to trimethylene) residue and a methyl group.

Imidazolinium salts are in particular those which have a C 1 -C ₁₈ -alk (en) yl radical in the 2-position of the heterocycle and a C ₁₄ -C ₈ -alk (en) ylcarbonyl (oxy or amino) ethylene on the neutral N atom -Rest and carry hydrogen, methyl or ethyl on the N-atom carrying the positive charge, counterions here are, for example, chloride, bromide, methyl sulfate or sulfate.

Claims

claims

1. A method for anti-creasing of cellulose-containing textiles by treating the textiles with a finishing agent and drying the treated textiles, characterized in that the finishing agent (A) one or more hydrophilically modified polyisocyanates and / or (B) one or more polyurethanes in dissolved or dispersed Contains form.

2. Use of hydrophilically modified polyisocyanates (A) and polyurethanes

(B) in textile treatment agents, in solid and liquid detergent formulations and laundry detergents.

3. Use of finishing agents containing at least one hydrophilically modified polyisocyanate (A) and / or at least one polyurethane (B), in which

Manufacture of textiles, in textile treatment, in the main wash cycle, in the wash cycle, and during ironing.

4. Finishing agent for anti-creasing of cellulose-containing textiles, containing at least one hydrophilically modified polyisocyanate (A) and / or

Polyurethane B).

5. Textile treatment agent containing

a) 0.1 to 40 wt .-% of at least one hydrophilically modified polyisocyanate

(A) and / or at least one polyurethane (B),

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 colorants, 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 the components being 100% by weight.

6. Containing solid detergent formulation

b) 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant,

c) 0 to 50% by weight of an inorganic builder,

d) 0 to 10% by weight of an organic cobuilder,

e) 0 to 60% by weight of other conventional ingredients such as adjusting agents, enzymes,

Perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleaching catalysts, cationic surfactants, color transfer inhibitors, graying inhibitors, soil release polyester,

Dyes, bactericides, resolution improvers and / or disintegrants,

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

7. Containing liquid detergent formulation

a) 0.05 to 20% by weight of at least one highly branched polyisocyanate (A) and / or at least one polyurethane (B),

b) 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant,

c) 0 to 20% by weight of an inorganic builder,

d) 0 to 10% by weight of an organic cobuilder, e) 0 to 60% by weight of other conventional ingredients such as soda, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleaching catalysts, cationic surfactants, color enhancement inhibitors, graying inhibitors, soil release polyesters, dyes, bactericides, non-aqueous solvents, solubility , Hydrotropes, thickeners and / or alkanolamines.

f) 0 to 99.85% by weight of water,

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

8. Laundry detergent containing

b) 0.1 to 50% by weight of at least one cationic surfactant,

c) 0 to 25% by weight of a nonionic surfactant,

d) 0 to 30% by weight of other conventional ingredients such as silicones, other 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

e) 0 to 99.85% by weight of water,

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