WO2017009160A1 - Avoidance of textile wrinkles - Google Patents

Abstract

The problem addressed by the invention is that of reducing the wrinkling tendency of a cotton textile or other cellulosic textile by a method that can be applied in the home. This is achieved by bringing the textile into contact with a water-based polyurethane dispersion as defined herein and then increasing the temperature of the textile to above the glass transition temperature of the polyurethane. The invention also relates to the polyurethane dispersions, products containing same and the use thereof.

Description

 Avoiding textile wrinkles

The present invention relates to certain water-based polyurethane dispersions, detergents and textile care products containing them, and their use for reducing the tendency to wrinkle and to ease the Bügeins of textiles made of cellulosic material and a feasible method for home ironing and / or wrinkle-reducing Finishing of textiles made of cellulosic material.

Textiles made of cellulose, such as cotton or cellulose regenerated fibers (for example Modal or Lyocel) have from the consumer's point of view positive properties in terms of wearing comfort. However, a major disadvantage of these textiles is the slight creasing after washing and drying. This tendency to wrinkle is due to the swelling of the cellulose fibers and their low elastic restoring forces ("bounce") after deformation.

Therefore, it has long been common practice to iron cotton or cellulosic textiles after washing and drying and thus to bring them into the desired shape. For the consumer, however, it would be advantageous to be able to minimize the formation of wrinkles in the context of textile care, which would facilitate the work of ironing or, ideally, would make ironing completely superfluous.

In the textile production one tries with the help of permanent textile equipment by a cross linking of the cellulose molecules among themselves to reduce their tendency to crease. The crosslinking of the cellulose molecules increases the elasticity of the material. The anti-crease equipment is carried out as part of the textile finishing on the raw material. However, crosslinkers used in the textile industry, such as formaldehyde-urea and formaldehyde-melamine combinations, because of their toxicity or the conditions under which they must be used, are not suitable for use in detergents or household use suitable.

Formaldehyde-free crosslinking processes for cellulose are also known, for example from US 2004/0043915 A1 a crosslinking process which is carried out with the aid of hydroxyl-bearing polymer and polycarboxylic acids, in particular butanetetracarboxylic acid (BTCA). From the article by CMWelch in Textile Research Journal, 1988, 480-486 the use of tetracarboxylic acids for crosslinking cellulose fibers is known. These formaldehyde-free approaches of cellulose crosslinking with the aid of polycarboxylic acids may, from a toxicological point of view, be suitable in principle for home use. Unfortunately, the reactions of the carboxyl groups of polycarboxylic acids with the hydroxyl groups of the cellulose leading to esters both require a large amount on catalysts such as triazoles or hypophosphites or phosphites as well as high temperatures. This is not practical for a consumer product.

In another approach, as described for example by M. Hashem, P. Hauser and B. Smith in Textile Research Journal, 2003, 762-766, ion pair bonds are exploited for the crosslinking of the cellulose. Cotton usually has a content of carboxyl groups of about 10 ^{~ 6} mol / g. To get as many ion pair contacts as possible, the cellulose can be treated with chloro or bromoacetic acid to increase the number of its carboxyl groups. Interaction of the carboxylated cellulose with polycations, such as cationized chitosan, can result in ionic crosslinks that reduce the tendency to crease. Without the carboxylation, the effect is too small and carboxylation of cotton textiles with haloacetic acids is not considered for home use.

From the patent application CN 1793483 A there is known a process for producing modified cotton fibers comprising the steps of oxidizing bleached cotton fibers with periodate, removing the oxidizing agent, washing and drying the cellulose fibers, and crosslinking by reaction with an OH and NH 2 groups containing substance such as collagen, chitosan, silk fibroin or sericin.

Another important aspect of cotton or other cellulosic textiles is their life and the retention of a mint appearance as long as possible. A problem that often occurs and leads to dissatisfaction of consumers, is the so-called pilling, which makes the textiles look worn and their life shortened. Existing approaches to avoiding pilling include the removal of existing pills from the surface of the fabric, for example, by the use of cellulases, which partially or completely hydrolyze microfibers protruding from the surface of the woven yarn, resulting in a smoother Surface remains. However, these approaches do not prevent the pilling as such, but only serve to eliminate the already incurred Pills.

It has now surprisingly been found that the creasing tendency of a cotton or other cellulosic textile (for example of regenerated cellulose fibers) can be reduced by bringing it into contact with certain polyurethane polymers in the form of water-based polyurethane dispersions. It has also been found that the impregnation of the aforementioned textiles with these polyurethane polymers additionally has an anti-pilling effect.

The invention therefore in a first aspect, a water-based polyurethane dispersion containing suitable polyurethane polymers, wherein such a water-based polyurethane dispersion is obtainable by a method comprising (i) reacting a mixture comprising a polyol blend and at least one organic polyisocyanate to produce a polyurethane prepolymer, wherein the polyol blend comprises

(A) at least 1 wt .-%, preferably 2 wt .-% to 70 wt%, more preferably 5 wt .-% to 55 wt .-% of an amorphous polyol having a glass transition temperature T _g of less than 0 ° C, preferably less than -20 ° C, more preferably less than -50 ° C, most preferably less than -100 ° C, and having an average molecular weight M _n of in particular from 200 to 10,000, preferably from 500 to 5,000 g / mol, preferably a hydroxy-functionalized / -terminated polysiloxane, more preferably a dihydroxyalkyl polysiloxane, most preferably a dihydroxyalkyl polydimethylsiloxane;

 (b) 5 wt% to 70 wt%, preferably 10 wt% to 55 wt%, more preferably 10 wt% to 40 wt% of at least one polyol having a melting enthalpy of more than 50 J / g, preferably more than 60 J / g, and more preferably more than 70 J / g;

 (C) 0, 1 wt .-% to 10 wt .-%, in particular 0.5 wt .-% to 5 wt .-%, of at least one polyol, in particular a polyether polyol having at least one ionic or potentially ionic hydrophilic group ; and

 (D) up to 20 wt .-%, in particular 3-10 wt .-%, of at least one nonionic of (a) different polyether polyol, wherein the nonionic polyether polyol is preferably a polyalkylene glycol homo- or copolymer and / or a content of ethylene oxide Has units of less than 50 mol%; and

 (E) up to 10 wt .-%, in particular 0.5 wt .-% to 5 wt .-% of at least one of (a), (b) and (c) different monomeric polyol and / or at least one polyamine;

 (ii) introducing the polyurethane prepolymer into a continuous aqueous phase; and

 (iii) optionally reacting the polyurethane prepolymer with a suitable chain extender.

Another object of the present invention is the use of such a water-based polyurethane dispersion of laundry, laundry aftertreatment or laundry care products.

A further subject matter of the present invention is a particularly liquid laundry, laundry aftertreatment or laundry care composition comprising a polyurethane dispersion as described herein. If the polyurethane dispersion is to be incorporated into particulate agents, it may be particulate form by dropwise coating, for example with polymers such as alginate or pectin, which form spherical films in the presence of polyvalent metal ions in which the dispersion droplet resides. The polyurethane dispersion is preferably present in amounts of from 0.01% to 50%, and more preferably from 1% to 30%, by weight in these laundry, laundry or laundry care compositions. Another object of the invention is the use of the polyurethane dispersions described herein or of agents containing them for minimizing the tendency to crease and / or the pilling of textiles made of cellulosic material. Another object of the invention is the use of such polyurethane dispersions or agents containing them to facilitate the Bügeins of textiles made of cellulosic material.

Finally, the invention also relates to a household process for anti-wrinkle and / or ironing finishing of cellulosic material by contacting it with a polyurethane dispersion as described herein, and subsequently raising the temperature of the fabric above the melt temperature T _m the polymer thereon, for example by using a commercial iron.

The cellulosic materials from which the textiles to be treated are made include cotton, regenerated cellulose fibers such as Modal or Lyocel, and blended fabrics of cotton or regenerated cellulose with other fabrics commonly used in clothing such as polyester and polyamide.

The polyurethane polymers described herein are self-dispersing, that is they spontaneously form dispersions in water without external dispersants. For this purpose, in the polymerization of polyurethanes already stabilizing ionic or nonionic molecules are used, which are incorporated into the polymer chain and later serve to stabilize the polyurethane particles in an aqueous environment. The dispersions can be prepared for example by homogenization of the corresponding polyurethane prepolymer by means of a high shear process in water and optionally subsequent chain extension of the prepolymer to the polyurethane polymer.

Furthermore, the polyurethane polymers described herein are capable of crystallization. Heretofore, it has been difficult to stably disperse crystallization-prone or capable polyurethanes as particles in an aqueous phase. Particularly with polyurethanes based on polyester polyols, it has been very difficult to achieve good long-term stability. Such crystallization of polyurethanes, however, is an important thermo-mechanical property which is essential in the fields of application described herein, as temperature control can rapidly and reversibly control physical interactions between the polymer chains.

The systems described herein can stably disperse crystallization-prone polyurethane particles in an aqueous phase, thereby providing, despite their hydrophobic nature, particles of significantly narrower size distribution and molecular weights than heretofore possible. These properties are based on the knowledge of the inventors that such dispersions can be realized by a special selection of the polyols used to prepare the polyurethanes. In particular, in the methods described herein for preparing stable polyurethane dispersions, certain amounts of ionic and nonionic groups are used which are incorporated into the polyurethane prepolymers during polymerization and impart the desired improved stability to them.

The inventors have also found that the use of only minor amounts of nonionic polyethylene glycol, and instead the use of more hydrophobic polyalkylene glycols, such as, in particular, polypropylene glycol, results in a narrower particle size distribution of the dispersed particles. Furthermore, such polypropylene glycol units are better suited than the corresponding polyethylene glycols to stabilize polyurethane polymers containing groups or units prone to crystallization in aqueous dispersions. Thus, in various embodiments, the polyurethane (pre) polymer contains less than 5 weight percent ethylene oxide units.

To stabilize such polyurethanes containing high melting point polyol units, it is further advantageous to minimize the amount of ionic groups. It is believed, inter alia, that a high proportion of ionic groups or polyethylene glycol units results in a phase separation within the polymer particles between a phase rich in the more hydrophilic portions, such as the ionic groups and the hydrophilic polyether units, and a phase rich in crystallization-prone hydrophobic polyester portions, but which is undesirable because it adversely affects crystallization kinetics and hence particle stability. This can be explained by the fact that such a phase separation reduces the local concentration of non-crystallisable polymer segments. This, in turn, causes the inhibition of crystallization by these non-crystallizable polymer segments, which interfere with nucleation and crystallite growth, to be reduced, i. the probability of formation of crystallites in the polymer particles increases. It is believed that this behavior is also the explanation for the higher stability of homogeneous particles, since the formation of crystallites affects the colloidal stability by disrupting the isotropic stabilization of the crystallite formed at the surface of the particle at the corresponding site ,

The polyurethane (prep) polymers described herein are therefore characterized by containing ionic and certain non-ionic, non-crystallizable polymer segments which are sufficient for stable dispersion in aqueous phases but at the same time inhibiting crystallization in that the nonionic used does not crystallizable polymer segments with the crystallization-prone polyester segments are compatible so that a homogeneous particle can be formed. In various embodiments of the processes described herein, the polyurethane prepolymers are synthesized from a mixture of polyols having the desired properties and suitable polyisocyanates, especially diisocyanates, which link the polyols together. It is obvious to the person skilled in the art that this approach can also be carried out in reverse, that is, a mixture of polyisocyanates having the desired properties can be reacted with corresponding polyols / diols as a linking reagent. In the following, the detailed approach of the invention refers to the former approach, it being understood by those skilled in the art that the following description, with appropriate modifications, is also applicable to a process employing a mixture of polyisocyanates as the starting material.

The polyols used typically have free hydroxyl groups. In particular, they are diols, that is to say (preferably linear) molecules (polymers) which have two terminal hydroxyl groups.

When reference is made to molecular weights in the present application, the statements are based on the number average molecular weight (Mn) unless otherwise specified. The molecular weight M _n can be determined on the basis of an end group analysis (hydroxyl number according to DIN 53240-1: 2013-06 / isocyanate content according to Spiegelberger according to EN ISO 1 1909: 2007-05), or by gel permeation chromatography (GPC) according to DIN 55672-1: 2007-08 be determined with THF as the eluent. Unless otherwise stated, the number average molecular weights reported were determined by end group analysis. In addition, the weight-average molecular weight M _{w can be determined} by GPC as indicated above for M _n .

"At least one" as used herein means 1 or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to an ingredient, the indication refers to the kind of the ingredient and not Thus, "at least one polyol" means at least one type of polyol, that is, a single type of polyol or a mixture of several different polyols can be used. The term "weight information" refers to all compounds of the specified type which are contained in the composition / mixture, that is to say that the composition contains no further compounds of this type beyond the stated amount of the corresponding compounds.

All percentages given in connection with the compositions described herein, unless explicitly stated otherwise, relate to% by weight, in each case based on the mixture in question.

The amorphous polymer segments of the polyurethanes preferably have glass transition temperatures T _g of less than 0 ° C, preferably less than -20 ° C, more preferably less than -50 ° C, most preferably less than -100 ° C. The indication of the glass transition temperatures refers to the glass transition temperature of corresponding high molecular weight, linear polyol homopolymers. Methods suitable for determining the glass transition temperature are known in the art. Particularly suitable is the determination by differential calorimetry (DSC = Differential Scanning Calorimetry) according to IS01 1357 at a heating rate of 20 K / min.

"Amorphous" as used herein refers to polymers having a crystallinity of less than 10%, preferably less than 5%, more preferably less than 2% as determined by DSC according to IS01 1357 at a heating rate of 20K / min. The amorphous polyols further have the low glass transition temperatures given above Below the glass transition temperature, the amorphous polymers are brittle and stiff due to the immobilization of the "frozen" polymer chains. Above the glass transition temperature, the polymer chains become relatively mobile and the polymer softens, the degree of softening depending on the type of polymer, the molecular weight and the temperature. Amorphous polymers show only one glassy state in DSC measurements during transition from the solid to the softened state compared to (semi) crystalline polymers. A melting point measurable for (semi) crystalline polymers is not observed in amorphous polymers in the DSC measurements.

Examples of suitable amorphous polyols (component a) are hydroxyl-terminated polybutadienes, such as are commercially available under the name Krasol®, polytetramethylene ether glycols, such as are commercially available, for example, under the names PolyTHF® and Terathane®, and in particular silicon-containing ones Polyols and here preferably hydroxy-functionalized and / or -terminated polysiloxanes into consideration. Examples of particularly suitable polyols are dihydroxyalkyl polysiloxanes, such as dihydroxyalkyl polydimethylsiloxane. The latter are commercially available, for example, as Tegomer® H-Si 231 1 (Evonik Industries AG). The amorphous polyols of component a) used have, in particular, an average molecular weight M _{n of} from 200 to 10,000, preferably from 500 to 5,000, more preferably from 1,000 to 4,000 and particularly preferably from 2,000 to 3,500 g / mol.

The polyols of component b) are preferably crystalline or semicrystalline. Preference is given to polyester or polycarbonate polyols, in particular polyester polyols. In particular, those polyester polyols are preferred whose melting point T _{m is} greater than 40 ° C but less than 220 ° C. In further embodiments, the melting point T _{m is} > 40 ° C and <160 ° C. The indication of the melting point refers to the melting point of corresponding high molecular weight, linear polyester homopolymers. Methods suitable for determining enthalpy of fusion, melting points and crystallinity are well known and well established in the art. Particularly suitable is the determination by differential calorimetry (DSC = Differential Scanning Calorimetry) according to IS01 1357 at a heating rate of 20 K / min, wherein the determination the enthalpy of fusion to use the results of the second heating run. In particular embodiments of the invention, the polyols of component b) have enthalpies of fusion above 90 J / g, in particular above 15 J / g. If no standard sample of the polyol of known crystallinity is available for determination of crystallinity by means of DSC, it is possible to resort to known alternative methods, for example X-ray diffractometry. "Crystalline" as used herein in this context refers to a crystallinity of at least 90%, preferably at least 95%. Similarly, as used herein, "semicrystalline" means that the corresponding homopolymers have a crystallinity of at least 50%, preferably at least 70% but less than 90%. Semi-crystalline polyols thus include crystalline and non-crystalline, that is amorphous, regions ,

Suitable polyesters can be prepared by known processes, for example condensation reactions, from polyols and polyacids, in particular from diols and diacids. Particularly suitable diols are aliphatic alkanediols, such as ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, and mixtures thereof. In principle, the use of cyclic diols or aromatic diols is conceivable, but preference is given to the use of linear aliphatic diols, such as those mentioned above, in particular 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol and 1, 6- Hexanediol, most preferably from 1, 4-butanediol and 1, 6-hexanediol. The diacids used are above all dicarboxylic acids and here preferably linear aliphatic dicarboxylic acids. Examples of suitable acids include, but are not limited to, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and mixtures thereof. Again, it is in principle possible to use cyclic or aromatic dicarboxylic acids such as phthalic acid, terephthalic acid or isophthalic acid, however, the resulting polyesters have significantly increased melting and glass transition temperatures compared to those produced with aliphatic dicarboxylic acids. Particularly preferably used polyesters can be prepared by a condensation reaction of 1,6-hexanediol and adipic acid or azelaic acid. The polyol components in the polycarbonate polyols correspond to the polyols given above for the polyesters.

Alternatively, suitable polyesters may also be synthesized from cyclic esters, especially lactones, or hydroxycarboxylic acids. A particularly preferred ester used here is ε-caprolactone, the lactone of the ω-hydroxycaproic acid, the polyester from which can be represented by ring-opening polymerization.

The polyester polyols used to form the polyurethane prepolymers usually have an average molecular weight M _n of 200 to 10,000, preferably 500 to 5000, more preferably 1000-4000, and particularly preferably 2000 to 4000 g / mol. The polyols of component b) are used in the polyol mixtures in amounts of 5% by weight to 70% by weight, preferably 10% by weight to 55% by weight, in particular 10% by weight to 40% by weight. each used based on the polyol mixture. In the presence of higher proportions of polyols of component b), the total content of hydrophilic groups may be too low, which may adversely affect the stability.

The polyols of component c) which have at least one ionic or potentially ionic hydrophilic group are preferably compounds having anionic or potentially anionic groups. Examples of such compounds are polyether polyols which have at least one, preferably per molecule, exactly one anionic or potentially anionic hydrophilic group.

Generally, as ionic groups are, but are not limited to, sulfate, sulfonate, phosphate, phosphonate, carboxylate, and ammonium groups, as well as ionic heterocycles, especially nitrogen-containing, 5-6 membered heterocycles. Potentially ionic groups include, but are not limited to, those selected from the group consisting of carboxylic acid and amino groups, as well as uncharged heterocycles, especially nitrogen-containing, 5-6 membered heterocycles. "Potentially ionic" refers herein to Property in an aqueous environment of appropriate pH as an ionic compound Polyols containing such ionic or potentially ionic groups are described, for example, in US 3,756,992, US 3,479,310 and US 4,108,814.

Very particular preference is given to carboxylate and / or sulfonate groups. Sulfonate-containing diols are described for example in DE 2446440 and DE 2437218. Preference according to the invention is given to polyether polyols, in particular those based on propylene glycol, which contain at least one carboxylate or sulfonate group. Suitable examples are dimethylolpropionic acid and an alkoxylated, in particular propoxylated, adduct of an alkenediol, in particular 2-butene-1, 4-diol, and a sulfite, in particular a hydrogen sulfite, such as NaHSCb.

The (potentially) ionic polyols used herein in various embodiments have an average molecular weight M _n in the range of 200 to 1000, preferably 300 to 500 g / mol. Among the particularly preferred (potentially) ionic polyols are dimethylolpropionic acid and alkoxylated, in particular propoxylated, adducts of alkenediols, in particular 2-butene-1, 4-diol, and a sulfite, in particular a hydrogen sulfite, such as NaHSCb, having a molecular weight M _n of about 430th

The (potentially) ionic polyols, in particular anionic polyether polyols, in the polyol mixtures in amounts of 0, 1 wt .-% to 10 wt .-%, in particular from 0.5 wt .-% to 5 wt .-% in each case based on the polyol mixture used. In the presence of lesser amounts, the hydrophilicity may be too low to allow a stable dispersion, at present larger quantities, the adverse effects on stabilization due to phase separations within the particles (microphase separation in the particles) predominate. It is generally advantageous that the (potentially) ionic polyols used, in particular anionic polyols, have a sufficient solubility in the polyols without having to additionally employ solubility promoters. In particular, the use of pyrrolidones such as NMP (N-methylpyrrolidone) or NEP (N-ethylpyrrolidone) and other aprotic solvents, such as without limitation DMSO or DMF, as solubility promoters should, if possible, be avoided by choosing a suitable ionic polyol of sufficient solubility , In a particularly preferred embodiment, therefore, propoxylated or butoxylated ionic polyols are used which carry quasi propylene oxide or butylene oxide repeating units as internal solubility promoters in the molecule.

The (potentially) ionic polyols are preferably used in amounts which are such that the content of ionic groups in the polyurethane prepolymer is a maximum of 20 milliequivalents, preferably a maximum of 10 milliequivalents per 100 g of prepolymer.

The nonionic polyether polyols of component d) used in the polyol mixture are preferably those which are not crystallizing, ie are not capable of crystallization. In various embodiments, they are polylalkylene glycols, with the exception of polyethylene glycol, for example polypropylene glycol, polybutylene glycol, poly (neo) pentylene glycol, or copolymers of the abovementioned or with polyethylene oxide, the content of polyethylene oxide in the corresponding polyol preferably being less than 50% by weight %, in particular less than 45% by weight and more preferably less than 10% by weight. In various embodiments, the HLB value after Griffin (HLB = Hydrophilic-Lipophilic Balance) of these nonionic polyalkylene glycols is <10, preferably <6 and more preferably <3. Particularly preferred is a polypropylene glycol homopolymer or a polypropylene glycol / polyethylene glycol block copolymer, preferably with an ethylene oxide content of 45 mol% or less, more preferably 10% or less. The nonionic polyether polyols in various embodiments have an average molecular weight M _n in the range of 1000 to 4000, preferably 1500 to 2500 g / mol.

The nonionic polyether polyols are used in the polyol mixtures in amounts of up to 20 wt .-%, in particular 3 wt .-% to 10 wt .-% in each case based on the polyol mixture.

The inventors have surprisingly found that the use of such nonionic polyether polyols instead of the hitherto commonly used hydrophilic polyether polyols, which consist predominantly of polyethylene glycol, although larger particle sizes but also provide significantly narrower particle size distributions. In addition, the poor long-term stability of polyethylene englycol-rich polyether polyols which tend to coagulate after a few days or weeks are significantly improved by the use of the polyols described herein. Without wishing to be bound by any particular theory, it is believed that in a conventional dispersion, the polyethylene glycol-rich segments migrate to the interface of the particles (ie towards the water phase), while the crystallizable polyester segments accumulate in the core accordingly. As soon as crystallization begins, the dispersions become unstable. With less polyethylene glycol and / or more polypropylene glycol there is no such phase separation in the particle, the polyester segments in the interior of the particles are "diluted" by polypropylene glycol segments and additionally disturbed in their crystallization, so that the particles remain stably dispersed.

If desired, as component e) further monomeric polyols and / or polyamines may be present in the reaction mixture, in particular diamines, diols or optionally triols. Suitable examples are hydrazine, polyether diamines, alkylenediamines and cycloalkylenediamines, such as ethylenediamine, isophoronediamine and piperazine, and, for example, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1, 6-hexanediol, and mixtures of at least two of these.

In various embodiments of the invention, the polyol mixture comprises:

(a) 5% to 60% by weight of an amorphous hydroxy-functionalized / -terminated polysiloxane, especially a dihydroxyalkyl-polysiloxane, having a glass transition temperature T _g of less than -100 ° C, and an average molecular weight M _n of 500 to 5,000 g / mol;

(B) 10 wt .-% to 70 wt .-%, in particular 10 wt .-% to 40 wt .-% of at least one crystalline or semicrystalline polyester polyol having a melting point T _m of greater than 40 ° C and less than 160 ° C and has a molecular weight M _n in the range of 500 to 5,000 g / mol;

 (c) from 0.5% to 5% by weight of at least one polyol, preferably a polyether polyol, having at least one ionic or potentially ionic hydrophilic group, especially a sulfonated diol; and or

 (D) 3 wt .-% to 10 wt .-% of at least one nonionic polyalkylene glycol homo- or copolymer with a content of ethylene oxide units of less than 50 mol%.

In various embodiments of the methods described herein, the polyurethane prepolymer has an average molecular weight in the range of 1500-25000, especially 2000-15000, more preferably 3000-15000 g / mole. The desired molecular weights are set by using appropriate amounts of polyols and polyisocyanates and determined by means of suitable measuring methods, such as end group analysis (hydroxyl number according to DIN 53240-1: 2013-06 or isocyanate content according to Spielberger according to EN ISO 1 1909: 2007-05). Corresponding calculations and methods are readily known to the person skilled in the art. As already described above, the content of ionic groups in the polyurethane prepolymer is preferably at most 20 milliequivalents, preferably at most 10 milliequivalents per 100 g prepolymer.

The prepolymer, in various embodiments, contains less than 5 weight percent ethylene oxide units, that is, the polyurethane prepolymer synthesized by the methods described herein contains less than 5 weight percent EO units based on total weight.

It is further preferred to use the organic polyisocyanate in molar excess relative to the polyol mixture to obtain an NCO-functionalized polyurethane prepolymer. If the polyisocyanates are used in molar excess, the OH / NCO equivalent ratio is preferably 1: 1, 1 to 1: 4, in particular 1: 1.2 to 1: 1.3.

As stated above, the polyols in the polyol mixture have at least 2 hydroxyl groups, but if desired they may also have 3 or more hydroxyl groups (-OH). Likewise, the organic polyisocyanate is a compound having at least two isocyanate groups (-NCO), in particular a diisocyanate, although under certain circumstances it may be advantageous to use small amounts of isocyanates having a functionality greater than 2. The use of polyols and / or polyisocyanates having more than 2 functional OH or NCO groups can lead to crosslinked systems.

Suitable polyisocyanates include, but are not limited to, aromatic diisocyanates such as diphenylmethane diisocyanate (MDI), polymeric MDI (PMDI) and / or toluene diisocyanate (TDI), and aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI). and / or methylene-4,4-bis (cyclohexyl) diisocyanate (H12MDI), or mixtures thereof. Although both aromatic and aliphatic polyisocyanates can be used, aliphatic polyisocyanates, especially diisocyanates, such as IPDI and HDI, are preferred according to the invention.

To form the prepolymer, the polyols and the polyisocyanates are preferably mixed, whereby the mixture can be heated. This may be particularly necessary if the polyols used are solid at room temperature and must be melted to form the polyol mixture. In preferred embodiments, the polyols are combined and heated with stirring and vacuum to about 70 to 95 ° C, for example about 75 ° C, to melt and optionally dry. The prepolymer synthesis is usually carried out by adding the isocyanates and at elevated temperature, in particular at a temperature which is greater than the melting point T _{m of} the polyester polyols, preferably in the range between 70 and 95 ° C, over a period of about 1 to about 5 hours, preferably about 2-3 hours. The reaction is typically carried out in the presence of a catalyst which is added, for example example of a zinc or titanium-based catalyst. Because of the fields of use described herein, it is preferable to dispense with heavy metal-containing, ie in particular tin-based, catalysts and it is preferable to use zinc-based catalysts, such as zinc (II) neodecanoate or zinc (II) 2-ethylhexanoate. Alternatively, the catalysis can also be carried out as metal-free acidic or basic catalysis.

The reaction is carried out until the free isocyanate content is near the calculated value, as determined by standard titration with dibutylamine. Preferred values for the free isocyanate content are in the range of from 0.2% to 2%, preferably from 0.7% to 1, 8%, by weight relative to the total amount of polyol and polyisocyanate in the mix. Once the desired value is reached, the temperature is reduced, for example to 60 ° C.

"Approximately" as used herein in reference to numerical references refers to ± 10%, preferably ± 5% of the numerical value to which the statement refers. Thus, "about 70 ° C" means 70 ° C ± 7 ° C, preferably 70 ° C ± 3.5 ° C.

As already mentioned above, the isocyanate is preferably used in molar excess, based on the stoichiometric concentration required to completely react all the hydroxyl groups. The excess may be an OH / NCO equivalent ratio of 1: 1.1 to 1: 4. Preferably, the amount of polyisocyanate used is 20% to 150% greater than the stoichiometric concentration required to react all the hydroxyl groups.

The prepolymer formed may be present either as such, but preferably in the form of a solution in a suitable organic solvent, preferably a water-miscible, -NCO group-inert organic solvent, including, but not limited to, acetone, ethyl acetate. Methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK).

When introducing the polyurethane prepolymer into a continuous aqueous phase (step ii), a dispersion or emulsion of the polyurethane prepolymer may be formed in a continuous aqueous phase, usually water or an aqueous solution. To form the emulsion / dispersion, it is possible to use mechanical stirrers or rotor-stator mixers, for example an Ultra-Turrax apparatus, as well as homogenizers or ultrasound machines.

The dispersing or emulsifying step may generally be carried out at elevated temperature, for example in the range of 30-60, for example about 40 ° C. In various embodiments, a preemulsion may first be formed, which is then homogenized in a subsequent step by a suitable method, for example, a high shear method, to form an emulsion.

"Emulsion" as used herein refers to an oil-in-water (O / W) emulsion in which the emulsified phase is in the form of droplets, preferably of approximately spherical shape, in the continuous water phase analogously to the presence of solid particles dispersed (stable) in a continuous water phase. In this case, the droplets / particles have an average size, in approximately spherical shape an average diameter, in the size range of 30 to 500 nm, in particular 50 to 300 nm, particularly preferably 100 to 300 nm. The above-mentioned averaged values refer to the z - Mean ("z-average") from the dynamic light scattering according to ISO 22412: 2008.

Step (ii) of the method described herein therefore comprises the steps in various embodiments:

 (a) emulsifying a solution of the polyurethane prepolymer in a suitable solvent, a continuous aqueous phase, especially water, to form a preemulsion; and

(b) homogenizing the pre-emulsion and optionally removing the solvent, preferably by distillation, to form a stable emulsion.

This step can be modified accordingly when using the prepolymer as such (in cases where no solution of the prepolymer is used). In particular, the prepolymer is then dispersed directly into the continuous phase and then homogenized.

To form the preemulsion, mechanical stirrers or rotor-stator mixers, for example an Ultra-Turrax device, can be used. To form the emulsion, a homogenizer, for example a microfluidizer (as available from Microfluidics), or an ultrasound device are preferably used.

The dispersing step, in particular the homogenization step, can be carried out by means of a high shear process. Suitable high shear methods preferably have shear rates of at least 1,000,000 / s and / or an energy input per time of at least 10 ⁶ J / s ^* m ³ . The shear rate can be calculated by methods known in the art or is known for given equipment. In general, the shear rate is calculated from the ratio of the maximum flow velocity (V _ma x) of a substance, for example a liquid in a capillary, and the radius of the hollow body through which it flows. The energy input per time results from the energy density in J / m ³ per time. If the aqueous polyurethane dispersion in step (ii) does not spontaneously form from the emulsion of the prepolymer, even after prolonged storage (for example, by hydrolysis of terminal isocyanate groups to amine groups and their reaction with other isocyanate groups), the emulsion may be more suitable Chain extender and reacted with the prepolymer to be reacted. Suitable chain extenders are generally compounds which have at least two groups which are reactive with the end groups of the prepolymer, usually -NCO groups. Examples of chain extenders containing at least two terminal NCO-reactive groups include, but are not limited to, diamines such as hydrazine, an alkylenediamine or cycloalkylenediamine, preferably ethylenediamine, isophoronediamine, piperazine, or polyetheramine, and diols such as for example, butanediol or 2-butyl-2-ethyl-1, 3-propanediol. The chain extension reaction can be carried out until complete conversion of the isocyanate groups, that is, the chain extender is added continuously until no more free isocyanate groups are detectable. For the chain extension reaction, the presence of a catalyst and / or an elevated temperature may be required.

The polyurethane dispersions in various embodiments may have solids contents in the range of from 10% to 60%, preferably from about 15% to 50%, more preferably from about 20% to 50% by weight. , in each case based on the polyurethane dispersion.

In the processes according to the invention, after the polymer has been applied by contacting it in the form of a dispersion or an agent containing it to a textile of cellulosic material such as cotton or polyester-cotton blends, then the polymer is added by subsequent temperature elevation melted / liquefied over the melting temperature T _{m of} the polyurethane polymer. Appropriately, the textile is in a desired smooth shape, which, as well as the mentioned temperature increase, for example, by ironing can be achieved. In preferred embodiments of the invention, the textile is ironed following treatment with said polymer with a standard household iron. Upon cooling (below the melting temperature), the polymer solidifies again, giving the textile on which it is based its permanent form.

The measures of the invention considerably reduce the creasing of textiles made of cellulosic material compared to the untreated starting textiles or a treatment with an aminopolysiloxane.

The assessment of the wrinkle-free effect can be done by measuring the crease recovery angle (KEW) according to DIN 53890: 1972. Preferably, the textile of cellulosic material at temperatures in the range of 5 ° C to 100 ° C, in particular from 20 ° C to 60 ° C, brought into contact with said polymer. The application can be carried out, for example, by spraying or dipping the textile in the dispersion or an agent containing it, if necessary diluted ready for use. The application can of course be carried out as part of a textile washing cycle, for example in an automatic household washing machine.

The temperatures which are necessary for the melting / liquefying of the polymer and should therefore be achieved, for example, during ironing, are typically in the range of 50 to 220 ° C, in particular in the range of 50 to 160 ° C.

The method can be carried out, for example, by bringing textiles made of cellulosic material into contact with an aqueous preparation containing said polymer. This can be done as part of a conventional washing process, which can be carried out by means of a household washing machine or by hand. The said polymer in aqueous liquor is preferably used in the rinsing step, ie after the actual washing step, but can also be used in the washing step. Said polymer may be part of detergents or laundry aftertreatment agents commonly used in such washing processes, such as fabric softeners. The concentration of said polymer in aqueous treatment liquor is in particular in the range from 0.1 g / l to 100 g / l, more preferably 0.5 g / l to 50 g / l. However, said polymer can also be part of a laundry care product, which can be present in particular as a liquid spray product, which, after dilution with water or preferably undiluted, applied to a textile of cellulose-containing material, in particular sprayed on, without having to follow a washing process or the application must be preceded by a washing process immediately.

Detergents, laundry aftertreatment or laundry care products which contain the active ingredient to be used according to the invention or are used together or used in the process according to the invention are preferably liquid and may be present, for example, as a single dose (for example in the form of a bag package). Examples of concrete agents in which the polyurethane dispersions can be used are liquid detergents and fabric softeners.

All of the abovementioned agents may contain such conventional excipients of such agents which do not undesirably interact with the polyurethane polymers essential to the invention. Such agent preferably contains synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20% by weight, in particular from 0.1 to 18% by weight, in each case based on the total agent. Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. Preference is given to the derivatives of fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. The sulfate-type surfactants which can be used with particular preference include the abovementioned sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids. The anionic surfactants which can be used also include the salts of sulfosuccinic acid esters, which are also referred to as alkylsulfosuccinates or dialkylsulfosuccinates, and which are monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cs to Cis fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol radical, which in itself is a nonionic surfactant. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Another synthetic anionic surfactant is alkylbenzenesulfonate in question.

A further embodiment of the compositions comprises the presence of nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, in particular in an amount in the range of 2 wt .-% to 25 wt .-%.

Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols be prepared with the corresponding alkylene oxides. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates. Useful are accordingly the alkoxylates, in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof. In addition, suitable alkoxylation products of alkylamines, vicinal diols and carboxylic acid amides, which correspond to the said alcohols with respect to the alkyl part, usable. In addition, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and Fettsäurepolyhydroxyamide into consideration. So-called alkylpolyglycosides which are suitable for incorporation into the compositions according to the invention are compounds of the general formula (G) _n -OR ² , in which R ^{2 is} an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean. The glycoside component (G) _n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, bose, arabinose, xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomerisierungsgrad. The degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1, 5, in particular between 1, 2 and 1, 4. Preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl moiety R ^{2 of} the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can be used to prepare useful glycosides. Accordingly, the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable. Particularly preferred alkyl glycosides contain a coconut oil alkyl radical, ie mixtures with essentially R ² = dodecyl and R ² = tetradecyl.

Nonionic surfactant is preferably present in the described compositions in amounts of from 1% to 30% by weight, especially from 1% to 25% by weight, with amounts in the upper part of this range being more likely to be found in liquid agents and particulate agents preferably contain lower amounts of up to 5% by weight.

Other optional surface-active ingredients are soaps, suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated C 12-18 fatty acid soaps and up to 50% by weight of oleic acid soap. Preferably, soap is contained in amounts of 0.1% to 5% by weight. In particular, in liquid agents which contain an active ingredient according to the invention, however, higher amounts of soap of usually up to 20 wt .-% may be included.

If desired, the compositions may also contain betaines and / or cationic surfactants, which, if present, are preferably used in amounts of from 0.5% by weight to 7% by weight. Among these, esterquats are particularly preferred.

If desired, the compositions may contain peroxygen bleaching agents, in particular in amounts ranging from 5% to 70% by weight, and optionally bleach activators, especially in amounts ranging from 2% to 10% by weight. The bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts. Such bleaching agents are in detergents containing an active ingredient used in the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15% by weight and particularly preferably from 5 wt .-% to 15 wt .-%, respectively on total agent, present, in particular percarbonate is used. The optionally present component of the bleach activators comprises the conventionally used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and Cyanurates, also carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitrile derivatives such as trimethylammoniumacetonitrile salts. In order to avoid interaction with the peroxygen compounds, the bleach activators may have been coated and / or granulated in a known manner with coating substances, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1, with the aid of carboxymethylcellulose. 5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or in particulate form, trialkylammonium acetonitrile is particularly preferred. Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.

In a further embodiment, the composition contains water-soluble and / or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%. The agent preferably contains from 20% to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which may also contain copolymerized small amounts of polymerizable substances without carboxylic acid functionality. The relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, that of the copolymers between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on the free acid , A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 g / mol to

100000 g / mol. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. Terpolymers which contain two carboxylic acids and / or salts thereof as monomers and also vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer may also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt may be a derivative of a C4-Cs dicarboxylic acid, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. Particularly preferred are vinyl alcohol derivatives which are an ester of short chain carboxylic acids, for example, C1-C4 carboxylic acids, with vinyl alcohol. Preferred terpolymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate and also 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, of vinyl alcohol and / or vinyl acetate. Very particular preference is given to terpolymers in which the weight ratio of (meth) acrylic acid and / or (meth) acrylate to maleic acid and / or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2.5: 1. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt may also be a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives is. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, 10% by weight to 30% by weight, preferably from 15% by weight to 25% by weight, of methallylsulfonic acid and / or methallylsulfonate and, as the third monomer, from 15% by weight to 40% by weight, preferably from 20% by weight to 40% by weight. % of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or poly- be saccharide, with mono-, di- or oligosaccharides are preferred, particularly preferred is sucrose. The use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a molecular weight between 1000 g / mol and 200000 g / mol, preferably between 2000 g / mol and 50,000 g / mol and in particular between 3000 g / mol and 10,000 g / mol. They can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.

Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used. Among these, the detergent-grade crystalline aluminosilicates, especially zeolite NaA and optionally NaX, are preferred. Amounts near the stated upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 μm, and preferably consist of at least 80% by weight of particles having a size of less than 10 μm. Their calcium binding capacity, which can be determined according to the specifications of the German patent DE 24 12 837, is in the range of 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali metal silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1, 1 to 1: 12, and may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of from 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those with a molar ratio of Na 2 O: SiO 2 of 1: 1, 9 to 1: 2.8 are preferably added in the course of the production as a solid and not in the form of a solution. As crystalline silicates which may be present alone or in a mixture with amorphous silicates, preference is given to using crystalline sheet silicates of the general formula Na.sub.2SixO.sub.2.sup.x + i.sub.yH.sub.20 in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na 2 Si 2 O 5-yH 2 O) are preferred. Also produced from amorphous alkali metal silicates, practically anhydrous Crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2, 1 can be used in the compositions described herein. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in another preferred embodiment of detergents. Their content of alkali metal silicates is preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali silicate is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance. The weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1. In compositions containing both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2 : 1 and especially 1: 1 to 2: 1.

In addition to the said inorganic builder, other water-soluble or water-insoluble inorganic substances may be contained in the compositions together with it or used in the process according to the invention. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.

In addition, the agents may contain other ingredients customary in detergents or cleaners. These optional constituents include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives. Preferably, in agents containing the polyurethane dispersions described herein, up to 1% by weight, especially 0.01% by weight to

0.5% by weight of optical brighteners, in particular compounds from the class of the substituted 4,4'-bis (2,4,6-triamino-s-triazinyl) stilbene-2,2'-disulfonic acids, up to 5 Wt .-%, in particular

0.1 wt .-% to 2 wt .-% complexing agent for heavy metals, especially Aminoalkylenphos- phosphonic acids and their salts and up to 2 wt .-%, in particular 0, 1 wt .-% to 1 wt .-% foam inhibitors, wherein said parts by weight each refer to total means.

Solvents that can be used in particular for liquid agents are, in addition to water, preferably those nonaqueous solvents which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric buta- nole, glycerol, lower glycols, for example ethylene and propylene glycol, and the derivable from the mentioned classes of compounds ethers.

Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and mixtures thereof. First and foremost, proteases derived from microorganisms, such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®. The lipase which can be used can be obtained, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species. Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano®-Lipase, Toyo-Jozo®-Lipase, Meito®-Lipase and Diosynth®-Lipase. Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm. The usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5. Such cellulases are commercially available under the names Celluzyme®, Carezyme® and Ecostone®. Suitable pectinases are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L ®, Rohapect 10L®, Rohapect B1 L® from AB Enzymes and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.

The customary enzyme stabilizers present, if appropriate, in particular in liquid agents include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid, alkali borates, boric acid-carboxylic acid combinations, boric acid esters, boronic acid derivatives, calcium salts, for example Ca-formic acid combination, magnesium salts, and / or sulfur-containing reducing agents.

Suitable foam inhibitors include long-chain soaps, in particular behenose, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica. For use in particulate agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances.

The known polyester-active soil release polymers include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR-) aOH, also known as polymeric diol H - (0- (CHR -) _a ) bOH may be present. Therein, Ph is an o-, m- or p-phenylene radical which may carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R is hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyesters obtainable from these, both monomer diol units -0- (CHR -) _a O- and also polymeric diol units - (0- (CHR ¹¹ -) _a ) bO-. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polymers is in the range from 250 g / mol to 100,000 g / mol, in particular from 500 g / mol to 50,000 g / mol. The acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable. If desired, instead of the monomer HOOC-Ph-COOH, small proportions, in particular not more than 10 mol% based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups may be present in the soil release-capable polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. Preferred diols HO- (CHR-) _a OH include those in which R is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R is hydrogen and the alkyl radicals have from 1 to 10 , in particular 1 to 3 C-atoms is selected. Among the latter diols, those of the formula HO-CH 2 -CHR -OH in which R has the abovementioned meaning are particularly preferred. Examples of diol components are ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-decanediol, 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range from 1000 g / mol to 6000 g / mol. If desired, the polyesters may also be end-capped, alkyl groups having from 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups. The end groups bonded via ester bonds may be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 C atoms, in particular 5 to 18 C atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, Myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroseloic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignocinic acid, cerotic acid, melissic acid, benzoic acid, which can carry 1 to 5 substituents with a total of up to 25 C atoms, in particular 1 to 12 C atoms, for example tert-butylbenzoic acid. The end groups may also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, the hydrogenation product of which includes hydroxystearic acid and o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 g / mol to 5000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 50:50 to 90: 10, used in combination with an essential ingredient of the invention. The soil release polymers are preferably water-soluble, wherein the term "water-soluble" is to be understood as meaning a solubility of at least 0.01 g, preferably at least 0.1 g of the polymer per liter of water at room temperature and pH 8. Preferably, polymers used are based However, these conditions have a solubility of at least 1 g per liter, in particular at least 10 g per liter.

In one embodiment of the invention, in particular the laundry care products used as aftertreatment agents may contain additional plasticizer components, preferably cationic surfactants. Examples of fabric softening components are quaternary ammonium compounds, cationic polymers and emulsifiers, such as those used in hair care products and also in textile saliva.

Suitable examples are quaternary ammonium compounds of the formulas (II) and (III),

wherein in (II) R and R is an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{2 is} a saturated C ¹ -C ⁴ alkyl or hydroxyalkyl radical, R ^{3 is} either R, R or R ² or is an aromatic radical. X ^" is either a halide, methosulfate, methoxy phat or phosphate ion and mixtures of these. Examples of cationic compounds of the formula (II) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.

Compounds of formula (III) are so-called ester quats. Esterquats are characterized by their good biodegradability and are preferred in the context of the present invention. Here, R ^{4 is} an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds; R ⁵ is H, OH or 0 (CO) R ⁷ , R ⁶ is independently of R ^{5 is} H, OH or 0 (CO) R ⁸ , wherein R ⁷ and R ⁸ are each independently an aliphatic alkyl radical having 12 to 22 carbon atoms having 0, 1, 2 or 3 double bonds, m, n and p may each independently have the value 1, 2 or 3 have. X ^" can be either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof Preferred are compounds which for R ^{5 are} the group O (CO) R ⁷ and for R ⁴ and R ^{7 are} alkyl radicals having from 16 to 18 carbon atoms. particularly preferred are compounds in which R ⁶ is also OH. Examples of compounds of formula (III) are methyl-N- (2-hydroxyethyl) -N, N-di (talgacyl- oxyethyl) ammonium methosulfate , Bis (palmitoyl) ethyl hydroxyethyl methyl ammonium methosulfate or methyl N, N bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate.

In a preferred embodiment, the agents contain the additional plasticizer components in amounts of up to 35% by weight, preferably from 0.1 to 25% by weight, more preferably from 0.5 to 15% by weight and especially from 1 to 10 Wt .-%, each based on the total agent.

In addition to the aforementioned components, the agents may contain pearlescing agents. Pearlescing agents give the textiles an extra shine and are therefore preferably used in mild detergents. Examples of suitable pearlescing agents are: alkylene glycol esters; fatty acid; partial glycerides; Esters of polybasic, optionally hydroxysubstituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms; Ring opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms, fatty acids and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

Furthermore, liquid agents may additionally contain thickeners. To increase consumer acceptance, the use of thickening agents has proven particularly useful in gel-type liquid detergents. Naturally derived polymers which can be used as thickening agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein, cellulose derivatives such as carboxymethyl cellulose hydroxyethyl and -propylcellulose, and polymeric polysaccharide thickeners such as xanthan; In addition, fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes are also suitable. In a preferred embodiment, the textile care agents according to the invention comprise thickeners, preferably in amounts of up to 10% by weight, more preferably up to 5% by weight, in particular from 0.1 to 1% by weight, in each case based on the total composition ,

Furthermore, the agents may additionally contain odor absorbers and / or color transfer inhibitors. In a preferred embodiment, the agents optionally contain from 0.1% to 2% by weight, preferably from 0.2% by weight to 1% by weight, of a color transfer inhibitor which, in a preferred embodiment of the invention, comprises a polymer of vinylpyrrolidone, Vinyl imidazole, vinyl pyridine N oxide or a copolymer of these. Useful are, for example, polyvinylpyrrolidones having molecular weights of from 15,000 to 50,000 as well as polyvinylpyrrolidones having molecular weights of more than 1,000,000, in particular from 1,500,000 to 4,000,000, N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyloxazolidones, copolymers based on vinyl monomers and carboxamides, pyrrolidone-containing polyesters and polyamides, grafted polyamidoamines, polyamine-N-oxide polymers, polyvinyl alcohols and copolymers based on acrylamidoalkenylsulfonic acids. However, it is also possible to use enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which gives off hydrogen peroxide in water. The addition of a mediator compound for the peroxidase, for example an acetosy ringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, it also being possible to additionally use the above-mentioned polymeric dye transfer inhibiting agents. Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10 000 to 60 000, in particular in the range from 25 000 to 50 000, for use in compositions according to the invention. Among the copolymers, those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred.

Preferred deodorizing substances are metal salts of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms and / or a rosin acid with the exception of the alkali metal salts and any desired mixtures thereof. A particularly preferred unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms is ricinoleic acid. A particularly preferred rosin acid is abietic acid. Preferred metals are the transition metals and the lanthanides, in particular the transition metals of Groups VIII-a, Ib and IIb of the Periodic Table and lanthanum, cerium and neodymium, more preferably cobalt, nickel, copper and zinc, most preferably zinc. The cobalt, nickel and copper salts and the zinc salts are similarly effective, but for toxicological reasons, the zinc salts are to be preferred. To be advantageous and therefore particularly preferred as deodorizing substances. are one or more metal salts of ricinoleic acid and / or abietic acid, preferably Zinkricinoleat and / or Zinkabietat, in particular Zinkricinoleat. Cyclodextrins, as well as mixtures of the abovementioned metal salts with cyclodextrin, preferably in a weight ratio of from 1:10 to 10: 1, particularly preferably from 1: 5 to 5: 1 and in particular from 1, also prove to be suitable further deodorizing substances in the sense of the invention. 3 to 3: 1. The term "cyclodextrin" includes all known cyclodextrins, ie both unsubstituted cyclodextrins having 6 to 12 glucose units, in particular alpha-, beta- and gamma-cyclodextrins and also their mixtures and / or their derivatives and / or their mixtures.

Liquid or pasty compositions in the form of common solvents, in particular water, containing solutions are usually prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

In a particularly preferred embodiment, the agents are present, preferably in liquid form, as a portion in a completely or partially water-soluble coating. Portioning makes it easier for the consumer to dose.

The funds can be packed, for example, in foil bags. Pouches made of water-soluble film make it unnecessary for the consumer to tear open the packaging. In this way, a convenient dosing of a single, sized for a wash portion by inserting the bag directly into the washing machine or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or hand basin, possible. The film bag surrounding the washing portion dissolves without residue when it reaches a certain temperature.

There are numerous processes in the prior art for producing water-soluble detergent portions, which are basically also useful in the context of the present invention. The best known methods are the tubular film processes with horizontal and vertical sealing seams. Also suitable for the production of film bags or dimensionally stable detergent portions is the thermoforming process (thermoforming process). However, the water-soluble envelopes do not necessarily consist of a film material, but can also represent dimensionally stable containers that can be obtained for example by means of an injection molding process.

Furthermore, methods for producing water-soluble capsules of polyvinyl alcohol or gelatin are known, which in principle offer the possibility to provide capsules with a high degree of filling. The methods are based on introducing the water-soluble polymer into a shaping cavity. The filling and sealing of the capsules is carried out either synchronously or in successive steps, in the latter case, the filling of the capsules by a small opening occurs. The capsules are filled, for example, by a filling wedge, which is arranged above two drums rotating against each other, which have spherical half-shells on their surface. The drums carry polymer belts that cover the ball half-shell cavities. At the positions where the polymer band of one drum coincides with the polymer tape of the opposite drum, a seal takes place. In parallel, the filling material is injected into the forming capsule, wherein the injection pressure of the filling liquid presses the polymer bands in the Kugelhalbschalenkavitäten. A process for the preparation of water-soluble capsules, in which initially the filling and then the sealing takes place, is based on the so-called Bottle-Pack ^® method. In this case, a tubular preform is guided into a two-part cavity. The cavity is closed, the lower tube portion is sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.

The shell material used for the preparation of the water-soluble portion is preferably a water-soluble polymeric thermoplastic, more preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof , Blends and composites, inorganic salts and mixtures of the materials mentioned, preferably hydroxypropylmethylcellulose and / or polyvinyl alcohol blends. Polyvinyl alcohols are commercially available, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88, Mowiol ^® 8-88 and Clariant L648. The water-soluble thermoplastic used to prepare the portion may additionally optionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above polymers. It is preferred if the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%. It is further preferred that the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol / preferably from 1 1 .000 to 90,000 gmol / more preferably from 12,000 to 80,000 gmol ^-1 and especially from 13,000 to 70,000 gmol ^{. 1} lies. It is further preferred if the thermoplastics are used in amounts of at least 50% by weight, preferably of at least 70% by weight, more preferably of at least 80% by weight and in particular of at least 90% by weight, based in each case on the weight the water-soluble polymeric thermoplastic. Examples

Example 1: Synthesis of polyurethane prepolymers a) Polymer A

12.00 g (6.3 mmol) K-HN-8200 (ethylene oxide / propylene oxide copolymer, 1901 g / mol), 12.00 g (5.6 mmol) Tergitol L-61 (propylene oxide / ethylene oxide copolymer 21 17 g / mol) , 12.00 g (28.2 mmol) of GS-7Q (sulfonated diol, 425 g / mol) and 226.53 g (90.8 mmol) of Tegomer H-Si 231 1 (dihydroxyalkyl polydimethylsiloxane, about 2200 g / mol ) were placed in an 11-round-bottomed flask, melted at 80 ° C bath temperature and dehydrated for 1.5 h in a high vacuum. It was aerated with nitrogen. The 2-phase mixture was homogenized with dried ethyl acetate (303 g). Nitrogen was not transferred. Isophorone diisocyanate (IPDI, 37.47 g, 168.6 mmol, 222.3 g / mol) was added at 57 ° C (OH = 0. 1309 mol, NCO = 0.0377 mol). Addition of the catalyst (Zn catalyst; Borchi Kat 22; 50% in ethyl acetate; 0.156 g (50%) = 0.026% by weight) was carried out at 54 ° C (non-exothermic). After 30 minutes (of which 20 minutes 70 ° C.) the NCO content was 1.44% (FS = 50.8%), after 50 minutes (of which 40 minutes 70 ° C.) the NCO content was 1.00% ( FS = 51, 3%).

The reaction was stopped and the mixture cooled to 40 ° C. One drop of Lumogen green solution and 0.1 g of defoamer (Foamaster® 223) and 10 ml of acetone were added dropwise, and the mixture (565, 17 g) was added to 40 ° C water (940.00 g) and stirred for 10 minutes (Ultra Turrax, IKA T25, level 4 = 190000 rpm). The preemulsion was given 4x at 40 ° C. by the homogenizer (Microfluidics Corp. 1 10Y / 2007094) (PSI 10000) and then determined as solids content and particle size (Malvern Instruments GmbH). The results are shown in Table 1:

Table 1

300 g of the miniemulsion were added dropwise, while stirring, to 5.1 l of aqueous piperazine-hexahydrate solution (20% in water, Mw 194.23 g / mol, 5.3 mmol). The particle size was determined again. The results are shown in Table 2. Table 2

The ethyl acetate was then distilled off on a rotary evaporator (55 ° C.) and filtered and the particle size was determined again. The results are shown in Table 3. This polyurethane dispersion is referred to below as PUD V-1.

Table 3

Alternatively, 1068 g of the miniemulsion were added dropwise with stirring to 15.97 g of aqueous isophoronediamine (IPDA) solution (20% in water, Mw 170.3 g / mol, 18.8 mmol). The particle size was determined again. The results are shown in Table 4.

Table 4

The ethyl acetate was then distilled off on a rotary evaporator (55 ° C.) and filtered and the particle size was determined again. The results are shown in Table 5. This polyurethane dispersion is referred to below as PUD V-2.

Table 5

 z-average (d / nm) volume PDS 1 19

 Particle size (Malvern

 Pdl (M) 0.09

 Instruments GmbH)

 Peak size (d.nm) /% / width good 1 12 100 45

Solid No coagulum 24.42% b) Polymer B

37.83 g Dynacoll 7381 (polyester, 3937 g / mol), 12.00 g (6.3 mmol) K-HN-8200 (ethylene oxide / propylene oxide copolymer, 1901 g / mol), 12.00 g (5.6 mmol ) Tergitol L-61 (propylene oxide / ethylene oxide copolymer 21 17 g / mol), 12.00 g (28.2 mmol) of GS-7Q (sufonated diol, 425 g / mol) and 150.00 g of Tegomer H-Si 231 1 (dihydroxyalkyl polydimethylsiloxane, about 2200 g / mol) were introduced into an 11-necked four-necked round bottom flask, melted at 80 ° C bath temperature and dehydrated for 2 h under high vacuum. It was aerated with nitrogen. At 69 ° C, 12.00 g of 1,4-butanediol (90.12 g / mol) was added. The 2-phase mixture was homogenized with dried ethyl acetate (305 g). Nitrogen was not transferred. At 68 ° C, isophorone diisocyanate (IPDI; 64, 17 g, 222.3 g / mol) was added (OH = 0.2512 mol, NCO = 0.0375 mol). Addition of the catalyst (Zn catalyst; Borchi Kat 22; 50% in ethyl acetate; 0, 16 g (50%) = 0.027% by weight) was carried out at 67 ° C (non-exothermic). It was heated to 70 ° C (then exothermic to 75.6 ° C). After 15 minutes 70 ° C, the NCO content was 1, 58%, after 30 minutes 70 ° C, the NCO content was 1, 07%.

The reaction was stopped and the mixture cooled to 45 ° C. Lumogen Green solution, defoamer and acetone were added dropwise as described above, the mixture was added to 40 ° C warm water and stirred for 10 minutes (Ultra Turrax, IKA T25, level 4 = 190000U / min). The preemulsion was given 4x at 40 ° C. by the homogenizer (Microfluidics Corp. 1 10Y / 2007094) (PSI 10000) and then determined as solids content and particle size (Malvern Instruments GmbH). The results are shown in Table 6:

Table 6

The miniemulsion (455.0 g, FS 19.55%) was added dropwise with stirring to 7.07 g of aqueous isophoronediamine (IPDA) solution (20% strength in water) and stirred at room temperature for 1 h. Thereafter, the polyurethane dispersion was rotary evaporated on a rotary evaporator (55 ° C) and filtered. The particle size was determined again, the results are given in Table 7. This polyurethane dispersion is referred to below as PUD P-1. Table 7

Alternatively, the miniemulsion (455.0g, FS 19.55%) was added dropwise with stirring to 1.93g of aqueous hexamethylenediamine (HDA) solution (20% in water) and stirred at room temperature for 1 day. Thereafter, the polyurethane dispersion was rotary evaporated on a rotary evaporator (55 ° C) and filtered. The particle size was determined again, the results are given in Table 8. This polyurethane dispersion is referred to below as PUD P-2.

Table 8

c) polymer C

36, 17 g Realkyd XTR201 12 (polyester; 21 17 g / mol), 12.00 g (6.3 mmol) K-HN-8200 (ethylene oxide / propylene oxide copolymer, 1901 g / mol), 12.00 g (5, 6 mmoles) Tergitol L-61 (propylene oxide / ethylene oxide copolymer, 21 17 g / mol), 12.00 g (28.2 mmol) of GS-7Q (sulfonated diol, 425 g / mol) and 150.00 g of Tegomer H -Si 231 1 (dihydroxyalkyl polydimethylsiloxane, about 2200 g / mol) were placed in a 11-four-necked round bottom flask, melted at 80 ° C bath temperature and dehydrated for 2 h under high vacuum. It was aerated with nitrogen. At 74 ° C, 12.00 g of 1,4-butanediol (90.12 g / mol) was added. The 2-phase mixture was homogenized with dried ethyl acetate (305 g). Nitrogen was not transferred. At 60 ° C, isophorone diisocyanate (IPDI, 65.83 g, 222.3 g / mol) was added (OH = 0.2564 mol, NCO = 0.0375 mol). Addition of the catalyst (Zn catalyst; Borchi Kat 22; 50% in ethyl acetate; 165.15 g (50%) = 0.0275% by weight) was carried out at 66 ° C (exothermic to 80 ° C). It was further stirred at 70 ° C. After 20 minutes 70 ° C, the NCO content was 1, 67%, after 35 minutes 70 ° C, the NCO content was 1, 25%, after 45 minutes 70 °, the NCO content was 1, 08%.

The reaction was stopped and the mixture cooled to 45 ° C. As described above, Lumogen green solution, defoamer and acetone were added dropwise, and the mixture was added to 40 ° C water and stirred for 10 minutes (Ultra Turrax, IKA T25, step 4 = 190000 rpm). The preemulsion was passed through the homogenizer (Microfluidics Corp. 1 10Y / 2007094) at 40 ° C. for 4 times (PSI 10000) and then the solids content was determined. The solids content was 18.32%.

The miniemulsion (450.5 g, FS 18.32%) was added dropwise with stirring to 6.59 g of aqueous isophoronediamine (IPDA) solution (20% strength in water) and stirred at room temperature for 2 h. Thereafter, the polyurethane dispersion was rotary evaporated on a rotary evaporator (55 ° C) and filtered. The particle size was determined again, the results are given in Table 9. This polyurethane dispersion is referred to below as PUD P-3.

Table 9

Alternatively, the miniemulsion (450.5 g, FS 18.32%) was added dropwise while stirring with 3.95 g of aqueous Neopentyldiamin (NPDA) solution (20% in water) and stirred for 1 day at room temperature. Thereafter, the polyurethane dispersion was rotary evaporated on a rotary evaporator (55 ° C) and filtered. The particle size was determined again, the results are given in Table 10. This polyurethane dispersion is referred to below as PUD P-4.

Table 10

Example 2: Crease tendency

Lappets (12x18 cm) of a cotton fabric (type "Stella Royal" of the manufacturer Brenneth) were prewashed to remove impregnating substances and then ironed.The polyurethane dispersions were diluted to 1% of active substance and used in an amount corresponding to the weight of the lobe that a fluid intake of 100% of Textile weight yielded. The lobes were dried at room temperature for 1 h and then ironed with a household iron (temperature setting two points, about 150 ° C).

The samples were characterized for their Wrinkle Recovery Angles (WRA) according to DIN 53890: 1972. Each sample was prepared and measured 5x and the average value is given in Table 1 1. Higher WRA for better anti-wrinkle effect.

Table 1 1

It can be seen that the coating with the polyurethane dispersions leads to an increase in the recovery angle and thus a reduction in the crease tendency.

Example 3: Anti-pilling

The tested cotton fabric was by the meter knitted fabric, turquoise 100% CO (38x70cm). The samples were prewashed in a beaker at 40 ° C. The PUD P-2 was diluted to 1% of active ingredient and used in an amount corresponding to the weight of the textile sample, resulting in a fluid intake of 100% of the textile weight. The fabric was dried and then ironed on each side for 1 minute (temperature setting 2 points, about 150 ° C).

The determination of the anti-pilling effect was carried out according to the DIN EN ISO 12945-2: 2000 standard with a polyurethane dispersion-treated sample and an untreated, prewashed reference sample. The results are shown in Table 12, wherein the anti-pilling effect was determined visually and wherein 1 is the worst and 5 is the best value. Table 12

It can be seen that the coating with the polyurethane dispersions led to a reduction of the pilling, wherein the effect is already visually readily detectable.

Claims

claims

A water-based polyurethane dispersion obtainable by a process comprising

 (i) reacting a mixture comprising a polyol mixture and at least one organic polyisocyanate to produce a polyurethane prepolymer, the polyol mixture comprising

(A) at least 1 wt .-% of an amorphous polyol having a glass transition temperature T _g of less than 0 ° C and in particular an average molecular weight M _n of 200 g / mol to 10,000 g / mol;

 (b) from 5% to 70% by weight of at least one polyol having a melting enthalpy greater than 50 J / g;

 (c) 0.1 to 10% by weight of at least one polyol, in particular a polyether polyol, which has at least one ionic or potentially ionic hydrophilic group; and

 (d) up to 20% by weight of at least one nonionic polyether polyol other than (a), wherein the nonionic polyether polyol is preferably a polyalkylene glycol homo- or copolymer and / or has a content of ethylene oxide units of less than 50 molar % having; and

 (e) up to 10% by weight of at least one of (a), (b) and (c) different monomeric polyol and / or at least one polyamine;

 (ii) introducing the polyurethane prepolymer into a continuous aqueous phase; and

(iii) optionally reacting the polyurethane prepolymer with a suitable one

 Chain.

2. A water-based polyurethane dispersion according to claim 1, characterized in that the polyol mixture comprises:

(A) 2 wt .-% to 70 wt%, in particular 5 wt .-% to 55 wt .-% of an amorphous hydroxy-functionalized / -terminated polysiloxane, in particular a dihydroxyalkyl polysiloxane, having a glass transition temperature T _g of less than -20 ° C, and an average molecular weight M _n of 500 g / mol to 5,000 g / mol;

(B) 10 wt .-% to 55 wt .-%, in particular 10 wt .-% to 40 wt .-% of at least one polyol having a melting enthalpy of more than 60 J / g, in particular more than 70 J / g has, in particular a crystalline or semi-crystalline polyester polyol having a melting point T _m of greater than 40 ° C and less than 160 ° C and a molecular weight Mn in the range of 500 to 5,000 g / mol;

(c) from 0.5% to 5% by weight of at least one polyol, preferably a polyether polyol, having at least one ionic or potentially ionic hydrophilic group, especially a sulfonated diol; (d) from 3% to 10%, by weight, of at least one nonionic polyalkylene glycol homopolymer or copolymer containing less than 50% by mole of ethylene oxide units; and or

 (e) from 0.5% to 5% by weight of at least one of (a), (b) and (c) different monomeric polyol and / or polyamine, especially selected from hydrazine, polyether diamines, alkylenediamines and cycloalkylenediamines such as ethylenediamine, isophoronediamine and piperazine, and 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and mixtures of at least two of these.

Water-based polyurethane dispersion according to claim 1 or 2, characterized in that the polyisocyanate is an aliphatic polyisocyanate, in particular diisocyanate, and is used in molar excess based on the hydroxyl groups of the polyols.

Use of a water-based polyurethane dispersion according to one of claims 1 to

3 for the production of laundry, laundry aftertreatment or laundry care products.

Washing, laundry aftertreatment or laundry care composition, characterized in that it contains a water-based polyurethane dispersion according to one of claims 1 to 3.

Composition according to claim 5, characterized in that the polyurethane dispersion in amounts of 0.01 wt .-% to 50 wt .-%, in particular from 1 wt .-% to 30 wt .-% in the washing, Wäschenachbehandlungs- or laundry care agent is included.

Use of a water-based polyurethane dispersion according to one of claims 1 to

4 or a composition according to any one of claims 6 or 7 for minimizing the crease tendency and / or the pilling of textiles made of cellulosic material.

Use of a water-based polyurethane dispersion according to one of claims 1 to 4 or of an agent according to one of claims 6 or 7 for facilitating the ironing of textiles made of cellulosic material.

A process for wrinkle-reducing and / or ironing-facilitating finishing of cellulosic-textile fabrics by contacting with a water-based polyurethane dispersion as claimed in any one of claims 1 to 4, and subsequently increasing the temperature of the fabric above the melting temperature T _m of the polymer thereon. Use according to one of claims 8 or 9 or method according to claim 10, characterized in that the textile is ironed after treatment with the polymer with a conventional household iron.