DE10056163A1 - Anticreasing finish, textile treatment, solid or liquid laundry detergent and laundry conditioner formulations for cellulose textiles, contain hydrophilic modified polyisocyanate and/or polyurethane - Google Patents

Abstract

Anticreasing finish for textiles containing cellulose contains hydrophilic modified polyisocyanate(s) (I) and/or polyurethane(s) (II). Independent claims are also included for: (a) a method of providing textiles containing cellulose with an anticreasing finish by treatment with (I) and/or (II) in dissolved or dispersed form and drying; (b) the use of (I) and (II) in textile treatment agents, solid and liquid laundry detergent formulations and laundry conditioners; and (c) compositions comprising (c.1) textile treatment agents, (c.2) solid laundry detergents, (c.3) liquid laundry detergents and (c.4) laundry conditioners containing (I) and/or (II).

Description

The invention relates to methods for the anti-crease finishing of cellulose-containing textiles, Anti-crease finishing agent, the hydrophilically modified polyisocyanate and / or contain polyurethanes, the use of the equipment 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, for example, treated with condensates tion products made from urea, glyoxal and formaldehyde are easy to care for. The Equipment is used during the manufacture of the textile materials. In the Equipment often uses other additives such as plasticizing compounds. The textiles finished in this way are compared to the untreated cellulose textiles the advantage of the washing process that they have fewer creases and wrinkles iron and are softer and smoother.

WO 92/01773 describes the use of microemulsified aminosiloxanes in Fabric softener to reduce the formation of creases and wrinkles during the Washing process (wrinkle arm equipment) known. At the same time, through the use the aminosiloxanes make ironing easier.

WO 98/4772 describes a method for pretreating textile materials known, where a mixture of a polycarboxylic acid and a cationic Applying plasticizer to the textile materials. You get one with it Crease.

EP-A 0 300 525 discloses fabric softeners based on crosslinkable aminofunctionalized silicones known to provide anti-crease or Ironing effect for the textiles treated with it.  

Formulations are known from WO 99/55953 which have 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 non-ionic Surfactants, odor-binding substances and bactericides. Applying the Formulation on the textile material is preferably carried out by spraying.

EP-A 0 978 556 describes a mixture of a plasticizer and one Crosslinker component with cationic properties as a means of equipping Textiles with anti-crease and wrinkle protection, as well as an anti-wrinkle process finishing of textiles.

The object of the invention is to provide a further method for anti-creasing cellulose-containing textiles and other finishing agents for anti-wrinkle finishing to provide such textiles.

The object is achieved by a method for anti-creasing 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

contains in dissolved or dispersed form.

The task is also solved by an anti-crease finishing agent cellulose-containing textiles containing the hydrophilically modified polyisocyanates and / or Polyurethanes included.

Hydrophilically modified polyisocyanates

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

As the basis for the hydrophilically modified polyisocyanates used according to the invention serve conventional diisocyanates and / or customary higher functional polyisocyanates with a  average NCO functionality from 2.0 to 4.5. These components can be used alone or in Mixture.

Examples of conventional 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 (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate) or 2,4- or 2,6-diisocyanato 1-methylcyclohexane and aromatic diisocyanates such as 2,4- or 2,6- Toluene diisocyanate, tetramethylxylylene diisocyanate, p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane, 1,3- or 1,4-phenylene diisocyanate, 1-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 Diphenylether-4,4'-diisocyanate. Mixtures of the diisocyanates mentioned can also be used available. Of these, aliphatic diisocyanates are preferred, in particular Hexamethylene diisocyanate and isophorone diisocyanate.

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

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

• a) polyisocyanates containing isocyanurate groups of aliphatic and / or cycloaliphatic diisocyanates. The are particularly preferred here corresponding isocyanato isocyanurates based on hexamethylene diisocyanate and isophorone diisocyanate. The present isocyanurates are especially simple tris-isocyanatoalkyl- or triisocyanatocycloalkyl- Isocyanurates, which are cyclic trimers of the diisocyanates, or um Mixtures with their higher, more than one isocyanurate ring Homologues. The isocyanato isocyanurates generally have an NCO content  from 10 to 30% by weight, in particular 15 to 25% by weight, and an average NCO Functionality from 2.6 to 4.5.
• b) polyisocyanates containing uretdione groups with aliphatic and / or Cycloaliphatic isocyanate groups, preferably of hexamethylene derived diisocyanate or isophorone diisocyanate. Uretdiones are cyclic dimers of two NCO groups.
• c) Biuret groups containing polyisocyanates with aliphatic bound Isocyanate groups, especially tris (6-isocyanatohexyl) biuret or its Mixtures with its higher homologues. These biuret groups Polyisocyanates generally have an NCO content of 18 to 25 wt .-% and an average NCO functionality of 3 to 4.5.
• d) polyisocyanates containing urethane and / or allophanate groups with aliphatic or cycloaliphatically bound isocyanate groups, as described, for example, by Implementation of excess amounts of hexamethylene diisocyanate or Isophorone diisocyanate with simple polyhydric alcohols such as Trimethylolpropane, glycerol, 1,2-dihydroxypropane or mixtures thereof can be. These have urethane and / or allophanate groups Polyisocyanates generally have an NCO content of 12 to 20 wt .-% and an average NCO functionality of 2.5 to 3.
• e) polyisocyanates containing oxadiazinetrione groups, preferably from Hexamethylene diisocyanate or isophorone diisocyanate derived. Such Polyisocyanates containing oxadiazinetrione groups are made from diisocyanate and Can produce carbon dioxide.
• f) Uretonimine-modified polyisocyanates.

The described diisocyanates and / or more functionalized polyisocyanates for conversion into non-ionic hydrophilic modified polyisocyanates, which are particularly suitable for the use according to the invention are preferred, reacted with NCO-reactive compounds that render hydrophilic Structural elements with non-ionic groups or with polar groups that are not in Ion groups can be transferred. The diisocyanate or  Polyisocyanate in a stoichiometric excess, so that the resulting hydrophilic modified polyisocyanate still has free NCO groups.

Hydroxyl group-terminated polyethers of the general formula I in particular come as such NCO-reactive compounds with hydrophilicizing structural elements

R ⁸ -E- (DO) _n -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 ₂₀ 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 the Containing polyether I incorporated is therefore also a preferred embodiment.

These are particularly preferably on C ₁ - 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.

One can from the described diisocyanates and / or more functionalized Polyisocyanates also first by reaction with a deficit hydroxyl-terminated polyesters, on other hydroxyl-terminated Polyethers or on polyols, e.g. B. ethylene glycol, trimethylolpropane or butanediol, Generate prepolymers and then these prepolymers subsequently or simultaneously  with the polyethers I in deficit to the hydrophilically modified polyisocyanates implement free NCO groups.

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

The enumerated types of non-ionically hydrophilically modified polyisocyanates are in the Writings 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 464 781 and EP- A 516 361 described in more detail.

The described diisocyanates and / or higher functionalized polyisocyanates are for conversion into anionically hydrophilically modified polyisocyanates with NCO-reactive Compounds implemented, the hydrophilic anionic groups, in particular Acid groups such as carboxyl groups, sulfonic acid groups or phosphonic acid groups, contain. The diisocyanate or polyisocyanate is stoichiometric Excess so that the resulting hydrophilically modified polyisocyanate is still free Has NCO groups.

Above all come as such NCO-reactive compounds with anionic groups Hydroxycarboxylic acids such as 2-hydroxyacetic acid, 3-hydroxypropionic acid, 4-hydroxy butyric acid or hydroxylpivalic acid and 2,2-bis- and 2,2,2- Tris (hydroxymethyl) alkanoic acids, e.g. B. 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 partially or to be completely neutralized by a base to be in a water soluble or water-dispersible form. A tertiary base is preferably used here Amine, which is known to be inert to isocyanate.

The described diisocyanates and / or higher functionalized polyisocyanates can also with a mixture of non-ionically hydrophilic modifying and anionic hydrophilically modifying compounds, which are used successively or simultaneously be added, implemented, for example with a deficit from the Polyethers I and the described hydroxycarboxylic acids.  

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

The described diisocyanates and / or higher functionalized polyisocyanates are for conversion into cationically hydrophilic modified polyisocyanates with NCO-reactive Compounds implemented, the chemically incorporated alkylatable or protonatable Functions with the formation of a cationic center included. In particular are such functions tertiary nitrogen atoms, which are known to be isocyanate are inert and can be easily quaternized or protonated. When implementing Diisocyanate or polyisocyanate with these NCO-reactive compounds are the former in excess so that the resulting hydrophilically modified polyisocyanate is still free Has 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 also contains an O atom or a can contain tertiary N atom, in particular a piperidine, morpholine, piperazine, pyrrolidine, oxazoline or dihydrooxazine ring, where the radicals R ² and R ³ 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 ₂ 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-diethyl (iso) propanolamine, 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) piperazine, 2-hydroxyethyl oxazoline, 2-hydroxypropyl oxazoline, 3- Hydroxypropyl oxazoline, 2-hydroxyethyl dihydrooxazine, 2-hydroxypropyl dihydrooxazin or 3-hydroxypropyl-dihydrooxazin.

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

in which R ⁹ to R ^{11 have} the abovementioned meanings and R ¹² denotes C ₁ to C ₅ alkyl or forms a five- or six-membered ring, in particular a piperazine ring, with R ⁹ .

Particularly suitable diamines IIIa are N, N-dimethylethylenediamine, N, N-diethyl- ethylenediamine, N, N-dimethyl-1,3-diamino-2,2-dimethylpropane, N, N-diethyl-1,3- propylenediamine, N- (3-aminopropyl) morpholine, N- (2-aminopropyl) morpholine, N- (3- Aminopropyl) piperidine, N- (2-aminopropyl) piperidine, 4-amino-1- (N, N- diethylamino) pentane, 2-amino-1- (N, N-dimethylamino) propane, 2-amino-1- (N, N- diethylamino) propane or 2-amino-1- (N, N-diethylamino) -2-methylpropane.

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

Furthermore, polyether (poly) oles can also be used as NCO-reactive compounds built-in tertiary nitrogen atoms by propoxylation and / or ethoxylation of starter molecules containing amine nitrogen can be used.  

Such polyether (poly) ole are, for example, the propoxylation and Ethoxylation products of ammonia, ethanolamine, diethanolamine, ethylenediamine or N-methylaniline.

Other usable NCO-reactive compounds are tertiary nitrogen atoms having polyester and polyamide resins, tertiary nitrogen atoms polyols containing urethane groups and tertiary nitrogen atoms Polyhydroxypolyacrylates.

The described diisocyanates and / or higher functionalized polyisocyanates can also with a mixture of non-ionically hydrophilic modifying and cationic hydrophilically modifying compounds, which are used successively or simultaneously be added, implemented, for example with a deficit from the Polyethers I and the amino alcohols II or the diamines IIIa and IIIb. Also Mixtures of non-ionically hydrophilic modifying and anionically hydrophilic modifying connections are possible.

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

Since the hydrophilically modified polyisocyanates (A) mentioned are generally in aqueous Media are used to ensure sufficient dispersibility of the polyisocyanates to care. Preferably act within the group of hydrophilic described modified polyisocyanates certain reaction products from di- or Polyisocyanates and hydroxyl-terminated polyethers (polyether alcohols) such as the compounds I 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 quickly decompose aqueous environment. Nevertheless, the used according to the invention Polyisocyanates in the aqueous liquor have a pot life of several hours, i.e. H. the The present polyisocyanate dispersions are part of the usual processing permanently stable. A dispersion is said to be stable when its components remain dispersed in each other without separating into discrete layers. With the The term "pot life" means the time during which the dispersions can be processed stay before gelling and setting. Aqueous isocyanate dispersions gel and  set because of a reaction between the water and the isocyanate, whereby a polyurea is formed.

Polyurethane

The finishing agent according to the invention can (B) one or more polyurethanes contain.

Polyurethanes are made from polyisocyanates (hereinafter also referred to as monomers I) and polyisocyanate-reactive compounds with at least one Hydroxyl group and optionally compounds with at least one primary or to understand secondary amino group built systems. The polyurethanes have generally no free isocyanate groups.

As polyisocyanates for the production of those contained in the finishing agent Polyurethanes (B) serve the usual diisocyanates and / or the usual higher functional ones Polyisocyanates as described for the hydrophilically modified polyisocyanates (A) are. Here too, aliphatic diisocyanates and aliphatic ones become more functional Polyisocyanates 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 those known per se Reaction products of dihydric alcohols with dihydric carboxylic acids. Instead of the free polycarboxylic acids, the corresponding ones can also be used Polycarboxylic anhydrides or corresponding polycarboxylic esters of lower Alcohols or mixtures thereof can be used to produce the polyester polyols. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic or heterocyclic be and if necessary, e.g. B. 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,  Hexahydrophthalic anhydride, tetrachlorophthalic anhydride, Endomethylene tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, Maleic anhydride, fumaric acid, dimeric fatty acids. Coming as polyhydric alcohols z. B. ethylene glycol, propylene glycol (1,2) and - (1,3), butanediol- (1,4), - (1,3), butenediol- (1,4), butynediol (1,4), pentanediol (1,5), hexanediol (1,6), octanediol (1,8), neopentyl glycol, Cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, Pentanediol- (1,5), also diethylene glycol, triethylene glycol, tetraethylene glycol, Polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and Polybutylene glycols in question.

Lactone-based polyester diols are also suitable, these being homo- or Copolymers of lactones, preferably around terminal hydroxyl groups having addition products of lactones or lactone mixtures, such as. B. s- Caprolactone, β-propiolactone, γ-butyrolactone and / or methyl-ε-caprolactone to suitable difunctional starter molecules, e.g. B. the above as a structural component for the Polyester polyols called low molecular weight, dihydric alcohols. The corresponding polymers of ε-caprolactone are particularly preferred. Even lower ones Polyester diols or polyether diols can be used as starters for the preparation of the lactone Polymers can be used. Instead of the polymers of lactones, the corresponding chemically equivalent polycondensates corresponding to the lactones Hydroxycarboxylic acids are used.

The - optionally also in a mixture with polyester diols - usable polyether diols are in particular by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for. B. in the presence of BF ₃ or by the addition of these compounds, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms, such as alcohols or amines, for. B. water, ethylene glycol, propylene glycol (1,3) or - (1,2), 4,4'-dihydroxy-diphenylpropane, aniline available.

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 Monomers II based on 1 gram equivalent of isocyanate of the polyisocyanate.  

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

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

In particular, those listed above are used to prepare the polyester polyols suitable diols and triols, and higher than trifunctional alcohols such as pentaerythritol or sorbitol into consideration.

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 with a molecular weight of 32 up to 500 g / mol, preferably from 60 to 300 g / mol, which have at least two primary, two contain secondary or a primary and a secondary amino group.

Examples include diamines, such as diaminoethane, diaminopropanes, diaminobutanes, Diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethyl cyclohexane (isophoronediamine, IPDA), 4,4'-diaminodicyclohexylmethane, 1,4-diamino cyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as Diethylenetriamine or 1,8-diamino-4-aminomethyloctane. Those containing amino groups Chain extenders can also be used in a blocked form, e.g. B. in the form of the corresponding Ketimines (see e.g. CA-1 129 128), ketazines (see e.g. US-A-4,269,748) or Amine salts (see US-A-4,292,226) can be used. Also oxazolidines, such as those used in US-A-4 192 937 are capped polyamines which are used for the Production of the polyurethanes for chain extension of the invention Prepolymers can be used. When using such capped Polyamines are generally used with the prepolymers in the absence of Water mixed and then this mixture with the water of dispersion or part of the dispersion water mixed, so that the hydrolytic intermediate corresponding polyamines are released.  

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

In the case of the monomers V which may also be used as chain extenders it is 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 from 0 to 0.4, particularly preferably 0 to 0.2 gram equivalent, based on 1 gram equivalent of isocyanate Polyisocyanate.

As a further structural component, compounds can be used that at least one, preferably two groups that are reactive toward isocyanate groups, ie Hydroxyl, primary or secondary amino groups, and also in contrast to the Monomers described above ionic groups or by a simple Neutralization or quaternization reaction convertible into ionic groups potentially have ionic groups. (Monomers VI). By introducing the Monomers VI make the polyurethanes themselves dispersible, i.e. H. when dispersing in In this case, water does not become a dispersing agent such as protective colloids or Emulsifiers needed.

The introduction of the cationic or anionic groups can also be used of (potential) cationic or (potential) anionic groups Connections with hydrogen atoms reactive towards isocyanate take place. To these groups of compounds include e.g. B. having tertiary nitrogen atoms Polyether with preferably two terminal hydroxyl groups, such as z. B. by Alkoxylation of two hydrogen atoms bonded to amine nitrogen Amines, e.g. As methylamine, aniline, or N, N'-dimethylhydrazine, in a conventional manner are accessible. Such polyethers generally have between 500 and 6000 g / mol lying molecular weight.

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

Preferred (potential) ionic monomers VI are N-Akyldialkanolamine, such as. B. 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 that Na salt of N- (2-aminoethyl) -2-aminoethane carboxylic acid and diamines with at least an additional tertiary amine nitrogen atom, e.g. B. N-methyl-bis- (3-aminopropyl) - amine.

Diamino and dihydroxycarboxylic acids are particularly preferred, especially that Adduct of ethylenediamine with sodium acrylate or dimethylolpropionic acid.

The transfer of those which may have been initially built into the polyaddition product Potential ionic groups happen at least partially in ionic groups usually by neutralizing the potential anionic or cationic Groups or by quaternization of tertiary amine nitrogen atoms.

To neutralize potential anionic groups, e.g. B. carboxyl groups inorganic and / or organic bases used such as alkali metal hydroxides, carbonates or hydrogen carbonates, ammonia or primary, secondary and particularly preferably tertiary Amines such as triethylamine or dimethylaminopropanol.

To transfer the potential cationic groups, e.g. B. the tertiary amine groups in the corresponding cations, e.g. B. ammonium groups are as neutralizing agents inorganic or organic acids, e.g. B. salt, phosphorus, ants, vinegar, Fumaric, maleic, lactic, tartaric or oxalic acid or as a quaternizing agent, e.g. B. Methyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, benzyl chloride, Chloroacetic acid ester or bromoacetamide suitable. Further neutralization or Quaternizing agents are e.g. Example, in US Pat. No. 3,479,310, column 6.

This neutralization or quaternization of the potential ion groups can 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 suitably chosen so that the polyurethane has a content of 0.05 to 2 meq / g Polyurethane, preferably from 0.07 to 1.0 and particularly preferably from 0.1 to 0.7 meq / g Have polyurethane on ionic groups.

If appropriate, monofunctional amine or hydroxyl compounds are also used as Construction components also used (monomers VII). It is preferably about monohydric polyether alcohols with a molecular weight of 500 to 10,000 g / mol, preferably from 800 to 5000 g / mol. Monohydric polyether alcohols are e.g. B. by Alkoxylation of monovalent starter molecules, such as. B. methanol, ethanol or n- Butanol available, with ethylene oxide or mixtures of Ethylene oxide with other alkylene oxides, especially propylene oxide, can be used. in the 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 optionally in the polyurethanes Polyethylene chains present at the end of the polyether chains be, in addition to the ionic groups, the hydrophilic character in the polyurethane influence and ensure or improve dispersibility in water.

The compounds of the type mentioned are preferred if they are used makes, used in such amounts that from 0 to 10, preferably from 0 to 5 wt .-% polyethylene oxide units are introduced into the polyurethane.

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

As monomers VIII, which, in contrast to the above monomers, contain ethylenically unsaturated groups, z. B. esters of acrylic or methacrylic acid with polyols, at least one OH group of the polyol remains 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. B. listed in 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, such as z. B. are mentioned in US-A-357 221. The adducts of (meth) acrylic acid with bisglycidyl ether of diols such as, for. B. bisphenol A or butanediol.

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

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

In general, the proportion of ethylenically unsaturated groups is less than 0.2 mol per 100 g polyurethane.

Overall, the proportion of structural components is preferably chosen so that the Sum of the hydroxyl groups and primary or reactive towards isocyanate secondary amino groups 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 usual methods such as z. B. are described in the documents cited above, respectively.

Preference is given to 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 be a polyurethane prepolymer with still terminal Isocyanate groups produced.

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

To accelerate the reaction of the diisocyanates, the usual catalysts, such as dibutyltin dilaurate, tin (II) octoate or diazabicyclo (2,2,2) octane become.

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

The transfer of potential salt groups, e.g. B. carboxyl groups, or tertiary Amino groups which were introduced into the polyurethane via the monomers VI in the corresponding ions take 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 dispersion, the organic solvent, if its boiling point below that of the water, are distilled off. Possibly also used Solvents with a higher boiling point can remain in the dispersion.

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

The dispersions can be conventional aids, e.g. B. thickeners, thixotropic agents, Oxidation and UV stabilizers or release agents can be added.

Hydrophobic auxiliaries, which under certain circumstances are difficult to produce homogeneously Dispersion to be distributed can also be described in US Pat. No. 4,306,998 Method added to the polyurethane or the prepolymer before the dispersion become.  

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 equipment for Anti-wrinkle finishing of cellulosic textiles. Equipment is any liquid formulations containing the hydrophilically modified polyisocyanates (A) and / or the Polyurethanes (B) for application to the textile in dissolved or dispersed form contain. The equipment according to the invention can, for example, as Equipment in the narrower sense in the manufacture of textiles in the form of a aqueous wash liquor or as a liquid textile treatment agent. As Solvents are suitable for. B. water, alcohols such as methanol, ethanol and propanol, THF or their mixtures. For example, it is possible in connection with the Textile manufacturing to treat the textiles with the finishing agent. Textiles that have not yet been treated or have been treated insufficiently with equipment for example in the home area before or after washing, for example when ironing, treated with a textile treatment agent containing the highly branched polymers become. But it is also possible to wash the textiles in the main wash cycle or after Main wash in the care or fabric softener of the washing machine with hydrophilic to treat modified polyisocyanates (A) and / or the polyurethanes (B).

The present invention also relates to the use of the hydrophilic modified polyisocyanates (A) and / or the polyurethanes (B) in the production of Textiles, in the treatment of textiles before and after washing, in textile laundry Main wash, in the fabric wash and rinse cycle, and when ironing. Needed for this different wording.

Textile treatment, detergent and conditioner formulations

In the treatment before or after the textile washing, a textile treatment agent can be used as Equipment are used, in addition to the hydrophilically modified Polyisocyanates (A) and / or polyurethanes (B) in dissolved or dispersed form contains surfactant. In this treatment, the cellulose-containing ones Textiles, for example, with the hydrophilically modified polyisocyanates (A) and / or sprayed the polyurethanes (B), the application amount generally being 0.01 to 10% by weight, preferably 0.1 to 7, particularly preferably 0.3 to 4% by weight, based on the  Weight of the dry textile goods. The equipment can also by being applied to the textile goods by immersing the textiles in a bath, which generally 0.1 to 10 wt .-%, preferably 0.3 to 5 wt .-%, based on the Weight of the dry textile goods, the hydrophilically modified polyisocyanates (A) and / or the polyurethane (B) contains dissolved or dispersed. The textile is either only briefly immersed in the bath or can also be in it for a period of for example, linger for 1 to 30 minutes.

The cellulosic textiles that are sprayed with the finishing agent either or have been treated by diving may be depressed and dried. Drying can be done in air or in a dryer or by hot ironing the treated textile. By drying the finishing agent is fixed on the textile. The cheapest for this Conditions can easily be determined with the help of experiments. The temperature drying, including ironing, is generally 40 to 150 ° C preferably 60 to 110 ° C. This is particularly suitable for ironing Cotton program of the iron. The textiles made after the above Process with the hydrophilically modified polyisocyanates (A) or polyurethanes (B) in dissolved or dispersed form have an excellent Wrinkle and wrinkle protection that lasts over several washes. Ironing the Textiles are often no longer required. Have the textiles treated in this way additionally fiber and color protection.

The invention also relates to a textile treatment composition containing

• a) 0.1 to 40 wt .-%, preferably 0.5 to 25 wt .-% of at least one hydrophilic modified polyisocyanate (A) and / or 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, fragrance and Dyes, stabilizers, fiber and color protection additives, viscosity modifiers, Soil release additives, anti-corrosion additives, bactericides, preservatives agents 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 are silicones containing amino groups, which are preferably in microemulsified form, alkoxylated, especially 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 containing paraffin and oils. 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 above-mentioned basic monomers can also be used in quaternized form can be used.

If the textile treatment formulation is sprayed onto the textile material, the Formulation additionally contain a spraying aid. In some cases it can also be advantageous to the formulation alcohols such as ethanol, isopropanol, Add ethylene glycol or propylene glycol. Other common additives are fragrance and Dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil Release additives, anti-corrosion additives, bactericides and preservatives in the usual quantities for this.

The textile treatment agent can also be used when ironing the textile after washing generally by spraying. This not only makes ironing considerably easier, the textiles are additionally treated with a long-lasting wrinkle and wrinkle protection.

The use of the hydrophilically modified polyisocyanates (A) and / or polyurethanes (B) can also be done when washing the textiles in the main wash 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 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, Resolution 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, e.g. B. C ₉ to C ₁₁ alcohol sulfates, C ₁₂ to C ₁₄ alcohol sulfates, C _{12 to} 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 firstly using a C ₈ to C ₂₂ , preferably a C ₁₀ to C ₁₈ alcohol, e.g. B. a fatty alcohol, alkoxylated and the alkoxylation product then sulfated. Ethylene oxide is preferably used for the alkoxylation;
• linear C ₈ to C ₂₀ alkyl benzosulfonates (LAS), preferably linear C ₉ to C ₁₃ alkyl benzene sulfonates and alkyl toluenesulfonates,
• - Alkane sulfonates such as C ₈ - to C ₂₄ -, preferably C ₁₀ - to C ₁₈ alkane sulfonates
• - Soaps such as the Na and K salts of C ₈ to C ₂₄ carboxylic acids.

The anionic surfactants mentioned are preferably in the form of Added salts. Suitable cations in these salts are alkali metal ions such as Sodium, potassium and lithium and ammonium ions such as hydroxyethylammonium, 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, 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 with 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 exchange properties such as especially 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 against others Cations such as Li, K, Ca, Mg, or ammonium are exchanged;
• - Crystalline silicates such as, in particular, disilicate or layered silicates, e.g. B. δ-Na ₂ Si ₂ O ₅ or β-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 in the form of their alkali metal, Alkaline earth metal or ammonium salts are used. Na, Li and Mg carbonates or bicarbonates, especially sodium carbonate and / or sodium hydrogencarbonate;
• - Polyphosphates such as B. pentasodium triphosphate;

Suitable organic cobuilders are in particular low molecular weight, oligomeric or polymeric carboxylic acids.

• Suitable low-molecular 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, imidodisuccinic acid, Oxydisuccinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentane tetracarboxylic acid, alkyl and alkenyl succinic acids and aminopolycarboxylic acids such as  z. B. nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, Serine diacetic acid, isoserine diacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, Ethylenediamine disuccinic 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. B. isobutene or long-chain α-olefins, vinyl alkyl ethers with C ₁ -C ₈ alkyl groups, vinyl acetate, vinyl propionate, (meth) acrylic esters of C ₁ -C ₈ 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 used in acid form or as the sodium salt.

A solid detergent formulation according to the invention is usually powdered or granular or in extrudate or tablet form.

The invention further relates to a liquid detergent formulation

• a) 0.05 to 20% by weight of at least one hydrophilically modified polyisocyanate (A) and / or 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 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, not aqueous solvents, solubilizers, 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.  

The above-mentioned nonionic and anionic surfactants, builders and Cobuilder can be used.

A detailed description of the detergent ingredients mentioned can be found e.g. B. in WO 99/06524 or WO 99/04313 and in Liquid Detergents, Editor: Kuo-Yann Lai, Surfactant Sci. 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 that Range from 50 to 1000 ppm. The with the hydrophilically modified polyisocyanates or Polyurethanes in the main wash of the washing machine creased textiles not only significantly less than untreated textiles. They're also easier to iron softer and smoother, more dimensionally and dimensionally stable and look after repeated washing due to their fiber and color protection less "used", so less Lint and knots and less color damage or fading.

The hydrophilically modified polyisocyanates or the polyurethanes can be used in So-called soft or care rinse after the main wash. The Concentration of the hydrophilically modified polyisocyanates or the polyurethanes in the Washing liquor is, for example, 10 to 5000 ppm and is preferably in that Range from 50 to 1000 ppm. Typical ingredients for a fabric softener or conditioner may be present in the washing solution. Even those treated this way Textiles are on a line after drying or preferably in a tumble dryer a very good anti-crease, which with the positive already described above Effects on ironing is related. The anti-crease can be achieved by a one-off brief ironing of the textiles after drying can be significantly increased. The Treatment in a soft or conditioner cycle also has a beneficial effect on the Dimensional stability of the textiles. The formation of knots and lint continues inhibited and color damage 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 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 customary 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 esters and imidazolium salts. Examples are quaternary diesterammonium salts which have two C ₁₁ to C ₂₂ alk (en) ylcarbonyloxy (mono- to pentamethylene) residues and two C ₁ to C ₃ alkyl or hydroxyalkyl residues on the quaternary N atom and as a counter ion for example, wear chloride, bromide, methyl sulfate or sulfate.

Quaternary diesterammonium further include in particular those having a C ₁₁ - a trimethylene moiety to C ₂₂ -alk (en) ylcarbonyloxytrimethylen radical, on the central carbon atom, are a C ₁₁ - transmits to C ₂₂ -alk (en) ylcarbonyloxy radical , and three C ₁ - to C ₃ - alkyl or hydroxyalkyl radicals on the quaternary N atom and, for example, carry chloride, bromide, methyl sulfate or sulfate as counterion.

Quaternary tetraalkylammonium salts are in particular those which have two C ₁ 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 Wear sulfate.

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 have a C ₁₁ to C ₂₂ alk (en) ylcarbonylamino (mono- to trimethylene) radical, a C ₁₁ 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.

Claims (8)

1. A method for anti-creasing cellulosic 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 detergents formulations and laundry detergents. 3. Use of finishing agents containing hydrophilically modified Polyisocyanates (A) and / or polyurethanes (B) in the manufacture of the textiles, in textile treatment, in the main wash cycle, in the textile wash cycle Fabric softener, and when ironing. 4. finishing agent for anti-wrinkle finishing of cellulose-containing textiles, containing hydrophilically modified polyisocyanates (A) and polyurethanes (B). 5. Textile treatment agent containing

• a) 0.1 to 40% by weight of at least one hydrophilically modified polyisocyanate (A) and / or 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

• a) 0.05 to 20% by weight of at least one hydrophilically modified polyisocyanate (A) and / or 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 conventional ingredients such as bulking 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 explosives,

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 polymer as defined in one of claims 1 to 8,
• 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, Solubilizers, 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

• a) 0.05% to 40% by weight of at least one hydrophilically modified polyisocyanate (A) and / or polyurethane (B),
• 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 customary 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.