EP1339910B1 - Highly branched polymers for the anti-crease dressing of cellulose containing textiles - Google Patents

Abstract

A process for wrinkleproofing cellulosic textiles by treating the textiles with a finish and drying the treated textiles, which comprises using a finish comprising one or more highly branched polymers in dissolved or dispersed form.

Description

This invention relates to anticaking equipment for cellulosic textiles, anticaking equipment containing highly branched polymers, the use of finishing agents and hyperbranched polymers, and to fabric treating agents, solid and liquid detergent formulations, and laundry detergents containing highly branched polymers.

Cellulose-containing textiles are easy-care, for example, by treatment with condensation products of urea, glyoxal and formaldehyde. The equipment is carried out during the production of textile materials. The equipment often uses other additives such as softening compounds. The textiles treated in this way have the advantage over the untreated cellulose textiles after the washing process that they have less wrinkles and wrinkles, are easier to iron and are softer and smoother.

WO 92/01773 discloses the use of microemulsified aminosiloxanes in fabric conditioners to reduce wrinkling and wrinkling during the washing process (crease arm equipment). At the same time ironing should be facilitated by the use of aminosiloxanes.

From WO 98/4772 a process for the pretreatment of textile materials is known, wherein applying a mixture of a polycarboxylic acid and a cationic plasticizer on the textile materials. This achieves a crease protection.

EP-A 0 300 525 discloses fabric softeners based on crosslinkable amino-functionalized silicones which bring about crease protection or an easy-iron effect for the textiles treated therewith.

From WO 99/55953 formulations are known which cause an anti-wrinkle effect in the treated textiles. The formulations consist of lubricants, polymers which ensure dimensional and dimensional stability of the textiles, lithium salts and optionally further ingredients such as plasticizers, ionic and nonionic surfactants, odor-binding substances and bactericides. The application of the formulation to the textile material is preferably carried out by spraying.

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

From WO 01/25385A plasticizer compositions are known which cause an anti-wrinkle effect in the treated textiles. The compositions containing polyorganosiloxane and and other additives such as. Polyurethane.

From US3905929A polyurethane are known that can be used for anti-wrinkle equipment.

Dendrimers or highly branched polyurethanes are known from DE19904444A.

Detergent compositions containing surfactants, builders and dendrimer macromolecules as a color transfer inhibitor are known from EP0779358A.

The object of the invention is to provide a further process for anti-wrinkle finishing of cellulosic textiles as well as other finishing agents for anti-wrinkle finishing of such textiles.

The object is achieved by a method for anti-wrinkle finishing of cellulosic textiles by treating the textiles with a finishing agent and drying the treated textiles, characterized in that the finishing agent contains one or more highly branched polymers in dissolved or dispersed form.

The object is also achieved by a finishing agent for anti-wrinkle finishing of cellulosic textiles containing these highly branched polymers.

Highly branched polymers are known per se. Dendrimers, arborols, starburst polymers and hyperbranched polymers are designations for polymeric structures characterized by a branched structure and high functionality.

Dendrimers are molecularly and structurally uniform macromolecules with a highly symmetric structure. They are built in multi-stage syntheses and are therefore very expensive.

In contrast, hyperbranched polymers are both molecularly and structurally nonuniform. They have branches of different length and branching. The highly branched polymers used according to the invention are preferably such hyperbranched polymers in the narrower sense. But it can also be structural and molecularly uniform dendrimeric polymers are used. The term "highly branched polymers" in the context of this invention therefore includes hyperbranched and dendrimeric polymers.

The highly branched polymers used according to the invention can be prepared in particular from so-called AB _x monomers. These have two different functional groups A and B, which can react with each other to form a linkage. The functional group A is contained only once per molecule and the functional group B twice or more times. The reaction of the AB _x monomers together produces uncrosslinked polymers with regularly arranged branching sites. The polymers have almost exclusively B groups at the chain ends. Further details are for example in JMS - Rev. Macromol. Chem. Phys., C37 (3), 555-579 (1997).

Highly branched polymers containing functional groups can be synthesized in a manner known in principle using AB _x , preferably AB _2, monomers. The AB ₂ monomers can be completely incorporated in the form of branches, they can be incorporated as terminal groups, so have two free B groups, or they can be incorporated as linear groups with a free B group. Depending on the degree of polymerization, the highly branched polymers obtained have a more or less large number of B groups, either terminal or as side groups. Further details on hyperbranched polymers and their synthesis are described, for example, in JMS Rev. Macromol. Chem. Phys., C37 (3), 555-579 (1997) and the literature cited therein.

The choice of highly branched polymers for use in the process of the invention for anti-whitening equipment is in principle not limited to a particular class of polymer. Highly branched polyesters, highly branched polyethers, highly branched polyurethanes, highly branched polyureaurethanes, highly branched polyamines, highly branched polyamides, highly branched polysiloxanes, highly branched carbosilanes, highly branched polyetheramides and highly branched polyester amides are possible. However, highly branched polyurethanes, highly branched polyesters, highly branched polyethers, highly branched polyesteramides and highly branched polyamines have proven particularly suitable. Among the hyperbranched polyamines, the highly branched polyethylenimines should be mentioned in particular. Very particularly preferred are highly branched polyurethanes.

• hochverzweigte Polyurethane nach WO 97/02304 oder nach DE 199 04 444
• hochverzweigte Polyester nach SE 468771 oder nach SE 503342
• hochverzweigte Polyether nach DE 199 47 631
• hochverzweigte Polyesteramide nach WO 99/16810
• hochverzweigte Polyamine nach WO 93/14147

Highly branched polymers can be prepared, for example, as follows:

• highly branched polyurethanes according to WO 97/02304 or DE 199 04 444
• highly branched polyester according to SE 468771 or SE 503342
• highly branched polyethers according to DE 199 47 631
• highly branched polyesteramides according to WO 99/16810
• highly branched polyamines according to WO 93/14147

In principle, highly branched and highly functional polymers obtained by polymerization of AB ₂ molecules can be used as such in the finishing agents according to the invention, provided that the functional groups obtained in the respective embodiment of the synthesis are suitable for the use of the polymers in dissolved or dispersed form.

However, the originally present B groups can also be converted by polymer-analogous reaction with suitable compounds.

Examples of suitable functional groups which can be introduced by means of suitable reactants include, in particular, acidic or basic groups which contain H atoms, and derivatives thereof such as -COOH, -COOR, -CONHR, -CONH ₂ , -OH, -SH, -NH ₂ , -NHR, -NR ₂ , -NR ₃ ⁺ , -SO ₃ H, -SO ₃ R -NHCOOR, -NHCONH ₂ , -NHCONHR or salts thereof. The radicals R are as a rule straight-chain or branched alkyl radicals which may also be further substituted, for example C ₁ -C ₈ -alkyl radicals. However, other functional groups such as -CN or -OR may also be introduced.

In a preferred embodiment, the highly branched polymers used according to the invention have one or more functional groups selected from the group consisting of. -COOH, -COOR, -CONHR, -CONH ₂ , -OH, -SH, -NH ₂ , -NHR, -NR ₂ , -NR ₃ ⁺ , -SO ₃ H, -SO ₃ R, -NHCOOR, -NHCONH ₂ , -NHCONHR or salts thereof.

Compounds used for re-functionalization may comprise, on the one hand, the desired functional group and a second group capable of reacting with the B groups of the highly branched polymer used as the starting material to form a bond. An example is the reaction of an isocyanate group with a hydroxycarboxylic acid.

However, it is also possible to use monofunctional compounds with which existing groups are merely modified. For example, alkyl halides can be used to quaternize existing amino groups.

The re-functionalization of the hyperbranched polymers can advantageously be carried out immediately after the polymerization reaction or in a separate reaction.

Functional groups which have sufficiently acidic H atoms can be converted into the corresponding salts by treatment with suitable bases. Analogously, basic groups can be converted with suitable acids into the corresponding salts. As a result, water-soluble highly branched polymers can be obtained.

It is also possible to produce highly branched polymers which have various functionalities. This can be done, for example, by reaction with a mixture of different compounds for re-functionalization, or also by reacting only a part of the originally present functional groups.

The degree of polymerization, molecular weight and the type and number of functional groups can be selected by the skilled person depending on the intended application.

Particularly preferred functional groups are -COOH, -CONH ₂ , -OH, -NH ₂ , -NHR, -NR ₂ , -NR ₃ ⁺ and -SO ₃ H and their salts.

In a specific embodiment, the highly branched polymers used according to the invention have one or more functional groups selected from the group consisting of -COOH, -OH, -SO ₃ H and salts thereof.

In a further specific embodiment, the highly branched polymers used according to the invention have one or more functional groups selected from the group consisting of -NH ₂ , -NHR, -NR ₂ , -NR ₃ ⁺ and their salts.

The highly branched polymers used according to the invention have on average at least 4 functional groups per molecule. The number of functional groups is in principle not limited to the top. However, products with too many functional groups often have undesirable properties, such as poor solubility or very high viscosity. Therefore, the preferably not more than 200 functional groups on average according to the invention used highly branched polymers. The highly branched polymers preferably have on average 4 to 150 and particularly preferably 4 to 100 functional groups.

The molecular weights of the highly branched polymers used according to the invention depend on the particular polymer class and are selected accordingly by the person skilled in the art. However, products having a weight-average molecular weight M _{w of} from 1000 to 20 000 g / mol, preferably from 1000 to 100 000 g / mol, have proven useful.

Preferred hyperbranched polymers used in the finishing agents of the present invention are highly branched polyurethanes.

The term "polyurethanes" in the context of this invention includes, beyond the usual understanding, polymers which can be obtained by reacting di- or polyisocyanates with compounds having active hydrogen, and which by urethane but also, for example, by urea, allophanate, biuret, Carbodiimide, amide, uretonimine, uretdione, isocyanurate or oxazolidone structures may be linked.

For the synthesis of the hyperbranched polyurethanes used according to the invention, preference is given to using AB _x monomers which have both isocyanate groups and groups which can react with isocyanate groups to form a linkage. x is a natural number between 2 and 8, preferably 2 or 3. Either A is an isocyanate group and B is reactive with these groups, or the opposite is the case.

The groups reactive with the isocyanate groups are preferably OH, NH ₂ , NHR or SH groups.

The AB _x monomers can be prepared in a known manner. For example, AB _x monomers can be synthesized according to the method described in WO 97/02304 using protective group techniques. By way of example, this technique is illustrated by the preparation of an AB ₂ monomer from 2,4-tolylene diisocyanate (TDI) and trimethylolpropane. First, one of the isocyanate groups of the TDI is capped in a known manner, for example by reaction with an oxime. The remaining free NCO group is reacted with trimethylolpropane, wherein only one of the three OH groups reacts with the isocyanate group, while two OH groups on Acetalization are blocked. After cleavage of the protecting group, a molecule having an isocyanate group and 2 OH groups is obtained.

Particularly advantageously, the AB _x molecules can be synthesized by the method described in DE-A 199 04 444, in which no protective groups are required. In this method di- or polyisocyanates are used and reacted with compounds having at least two isocyanate-reactive groups. At least one of the reactants in this case has groups with respect to the other reactants of different reactivity. Both reactants preferably have groups with different reactivity than the other reactant. The reaction conditions are chosen so that only certain reactive groups can react with each other.

Suitable diisocyanates and polyisocyanates are the aliphatic, cycloaliphatic and aromatic isocyanates known from the prior art. Preferred di- or polyisocyanates are 4,4'-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates and oligomeric diphenylmethane diisocyanates (polymeric MDI), tetramethylene diisocyanate, hexamethylene diisocyanate, 4,4'-methylenebis (cyclohexyl) diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dodecyl diisocyanate, lysine alkyl ester diisocyanate where alkyl is C ₁ - to C ₁₀ -alkyl, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 1,4-diisocyanatocyclohexane or 4-isocyanatomethyl-1,8-octamethylene diisocyanate ,

Particularly preferred are di- or polyisocyanates with NCO groups of different reactivity, such as 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), triisocyanatotoluene, isophorone diisocyanate (IPDI), 2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 3 (4) isocyanatomethyl-1-methylcyclohexyl isocyanate, 1,4-diisocyanato-4-methylpentane, 2,4'-methylenebis (cyclohexyl) diisocyanate and 4-methylcyclohexane-1, 3-diisocyanate (H-TDI). Furthermore, particular preference is given to isocyanates (b) whose NCO groups are initially identically reactive, but in which a drop in reactivity in the second NCO group can be induced by initial addition of an alcohol or amine to an NCO group. Examples are isocyanates whose NCO groups are coupled via a delocalized electron system, e.g. As 1,3- and 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl diisocyanate, tolidine diisocyanate or 2,6-toluene diisocyanate.

Furthermore, it is possible to use, for example, oligoisocyanates or polyisocyanates which are prepared from the abovementioned diisocyanates or polyisocyanates or mixtures thereof by linking with urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine , Oxadiazinetrione or iminooxadiazinedione structures.

As compounds having at least two isocyanate-reactive groups it is preferred to use di-, tri- or tetra-functional compounds whose functional groups have a different reactivity with respect to NCO groups. Preference is given to compounds having at least one primary and at least one secondary hydroxyl group, at least one hydroxyl group and at least one mercapto group, particularly preferably having at least one hydroxyl group and at least one amino group in the molecule, in particular amino alcohols, amino diols and aminotrioles, since the reactivity of the amino group relative to the hydroxyl group at the reaction with isocyanate is significantly higher.

Examples of the stated compounds having at least two isocyanate-reactive groups are propylene glycol, glycerol, mercaptoethanol, ethanolamine, N-methylethanolamine, diethanolamine, ethanolpropanolamine, dipropanolamine, diisopropanolamine, 2-amino-1,3-propanediol, 2-amino-2-methyl 1,3-propanediol or tris (hydroxymethyl) aminomethane. Furthermore, mixtures of the compounds mentioned can be used.

The preparation of an AB ₂ molecule is exemplified in the case of a diisocyanate with an amino diol. Hiebei first one mole of a diisocyanate is reacted with one mole of an aminodiol at low temperatures, preferably in the range between - 10 to 30 ° C. In this temperature range, a virtually complete suppression of the urethane formation reaction takes place and the more reactive NCO groups of the isocyanate react exclusively with the amino group of the aminodiol. The formed AB _x molecule has a free NCO group and two free OH groups and can be used for the synthesis of a highly branched polyurethane.

By heating and / or catalyst addition, this AB ₂ molecule can intermolecularly react to form a highly branched polyurethane. The synthesis of the highly branched polyurethane can advantageously be carried out without prior isolation of the AB _x molecule in a further reaction step at elevated temperature, preferably in the range between 30 and 80 ° C. When using the described AB ₂ molecule with two OH groups and one NCO group, a highly branched polymer is formed, which pro Molecule has a free NCO group and - depending on the degree of polymerization - a more or less large number of OH groups. The reaction can be carried out to high conversions, resulting in very high molecular structures. However, it can also be terminated, for example, by adding suitable monofunctional compounds or by adding one of the starting compounds for the production of the AB ₂ molecule upon reaching the desired molecular weight. Depending on the starting compound used for termination, either completely NCO-terminated or completely OH-terminated molecules are formed.

Alternatively, for example, an AB ₂ molecule can be prepared from one mole of glycerol and 2 moles of 2,4-TDI. At low temperature, preferably the primary alcohol groups and the isocyanate group react in the 4-position and an adduct is formed which has an OH group and two isocyanate groups, which can be reacted as described at higher temperatures to form a highly branched polyurethane. The result is first 'a highly advanced polymer, which has a free OH group and - depending on the degree of polymerization - a more or less large number of NCO groups.

The preparation of the highly branched polyurethanes can in principle be carried out without a solvent, but preferably in solution. All solvents which are liquid at the reaction temperature and inert to the monomers and polymers are suitable as solvents.

Other products are accessible through further synthetic variants. For example, AB ₃ molecules can be obtained by reaction of diisocyanates with compounds having at least 4 isocyanate-reactive groups. By way of example, the reaction of 2,4-tolylene diisocyanate with tris (hydroxymethyl) aminomethane may be mentioned.

To terminate the polymerization and polyfunctional compounds can be used which can react with the respective A groups. In this way, several small hyperbranched molecules can be linked to form a large hyperbranched molecule.

Highly branched polymers with chain-extended branches can be obtained, for example, by adding a diisocyanate and a compound having two isocyanate-reactive groups in addition to the AB _x molecules in addition to the AB _x molecules in the molar ratio of 1: 1. This additional AA or BB compounds may also have other functional groups, but may not be reactive to the A or B groups under the selected reaction conditions. In this way, additional functionalities can be introduced into the hyperbranched polymer.

Other synthetic variants for highly branched polyurethanes can be found in the applications with the file numbers DE 100 13 187.5 and DE 100 30 869.4.

The resulting highly branched and highly functional polyurethanes can be used as such in the finishing agents according to the invention, provided that the functional groups obtained in the course of the synthesis are suitable for the use of the polyurethanes in dissolved or dispersed form.

However, the functional groups can also be rendered hydrophobic, hydrophilicized or trans-functionalized as described above. In this way, particularly suitable highly branched polyurethanes are available for use as a solution or aqueous dispersion. Due to their reactivity, especially highly branched polyurethanes which have isocyanate groups are particularly suitable for re-functionalization. OH- or NH ₂ -terminated polyurethanes can also be functionalized by means of suitable reaction partners.

Preferred groups introduced into the hyperbranched polyurethanes are -COOH, -CONH ₂ , -OH, -NH ₂ , -NHR, -NR ₂ , -NR ₃ ⁺ , -SO ₃ H and their salts. Especially preferred are -NH ₂ , -NHR, -NR ₂ , and -NR ₃ ⁺ according to one embodiment of the invention and -COOH, -OH and -SO ₃ H according to another embodiment of the invention.

Groups which have sufficiently acidic H atoms can be converted into the corresponding salts by treatment with suitable bases. Analogously, basic groups can be converted with suitable acids into the corresponding salts. As a result, water-soluble highly branched polyurethanes can be obtained.

By reacting NCO-terminated products with alkanols and alkylamines, in particular alkanols and alkylamines with C ₈ -C ₄₀ -alkyl radicals, hydrophobicized products can be obtained.

Hydrophilic but nonionic products can be obtained by reaction of NCO-terminated polymers with polyether alcohols, such as di-, tri- or tetra- or polyethylene glycol.

Acid groups can be introduced, for example, by reaction with hydroxycarboxylic acids, hydroxysulfonic acids or amino acids. Examples of suitable reactants are 2-hydroxyacetic acid, 4-hydroxybenzoic acid, 12-hydroxydodecanoic acid, 2-hydroxyethanesulfonic acid, glycine or alanine.

By reaction with compounds comprising acrylate groups, such as alcohols comprising acrylate groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, it is possible to obtain highly branched polyurethanes which have polymerizable olefinic groups.

Oxidatively drying highly branched polyurethanes can be obtained by first reacting monounsaturated or polyunsaturated fatty acids, in particular C ₈ -C ₄₀ -fatty acids with an aliphatic alcohol having at least two OH groups, wherein at least one OH group may not be esterified. For example, linoleic acid, linolenic acid or elaeostearic acid can be reacted. The resulting fatty acid ester, which still has OH groups, is then reacted with the NCO groups.

It is also possible to produce highly branched polyurethanes which have various functionalities. This can be done for example by reaction with a mixture of different compounds, or by reacting only a portion of the originally present functional groups, for example, only a portion of the OH and / or NCO groups.

Furthermore, it is also possible to react one or more functional groups of the highly branched molecule with fiber-affine reagents, for example with polyamines, such as polyethyleneimine or polyvinylamine. This gives a highly branched polymer which has a fiber-affine moiety as an anchor group for the fiber.

The re-functionalization of the highly branched polyurethane can be advantageously carried out immediately after the polymerization reaction, without the NCO-terminated polyurethane is previously isolated. The functionalization can also be done in a separate reaction.

The highly branched polyurethanes used according to the invention generally have on average at least 4 and not more than 200 functional groups. The highly branched polyurethanes preferably have 4 to 150 and more preferably 4 to 100 functional groups. Preferred highly branched polyurethanes have a weight-average molecular weight M _{W of} from 1000 to 200 000 g / mol, preferably from 1000 to 100 000 g / mol.

The invention also relates to the use of highly branched polymers, in particular highly branched polyurethanes, in finishing agents for the anticaking of cellulose-containing textiles. Finishing agents are any liquid formulations containing the highly branched polymer, especially the highly branched polyurethane, for application to the fabric in dissolved or dispersed form. The finishing agents according to the invention can be present, for example, as finishing agents in the strict sense in the manufacture of the textiles or in the form of an aqueous wash liquor or as a liquid textile treatment agent. As solvents, e.g. Water, alcohols such as methanol, ethanol and propanol, THF or mixtures thereof. Thus, it is possible, for example, to treat the textiles with the finishing agent in the context of textile production. Textiles which have not or only insufficiently been treated with finishing agents can, for example, be treated at home before or after washing, for example by ironing, with a textile treatment agent containing the hyperbranched polymers. However, it is also possible to treat the textiles in the main wash cycle or after the main wash cycle in the care or fabric conditioning cycle of the washing machine with highly branched polymers.

The present invention also relates to the use of the highly branched polymers, in particular the highly branched polyurethanes, in the manufacture of textiles, in the treatment of textiles before and after washing, in the main wash textile wash, in the fabric wash and in the ironing. For this one needs in each case different formulations.

In the treatment before or after the textile washing, a textile treatment agent may be used as a finishing agent containing, in addition to a highly branched polymer in dissolved or dispersed form, a surface-active agent. In this treatment, the cellulosic textiles are sprayed, for example, with the highly branched polymers, the order amount generally 0.01 to 10 wt .-%, preferably 0.1 to 7, particularly preferably 0.3 to 4 wt .-%, based on the weight of the dry textile goods, can be. However, the finishing agent can also be applied to the fabric by immersing the fabrics in a bath, which is generally 0.1 to 10 wt .-%, preferably 0.3 to 5 wt .-%, based on the weight of the dry Textilguts, a highly branched polymer dissolved or dispersed contains. The textile material is either immersed in the bath only for a short time or may also stay in it for a period of, for example, 1 to 30 minutes.

The cellulosic fabrics which have been treated with the finishing agent either by spraying or by dipping are optionally squeezed and dried. The drying can be carried out in air or in a dryer or even by hot ironing the treated textile. By drying the finishing agent is fixed on the fabric. The most favorable conditions for each can be easily determined by means of experiments. The temperature of drying, including ironing, is generally 40 to 150 ° C, preferably 60 to 110 ° C. For ironing is especially the cotton program of the iron. The textiles which have been treated with the hyperbranched polymers in dissolved or dispersed form according to the process described above, have excellent crease and wrinkle protection, which remains over several washes. Ironing the textiles is often no longer necessary. The treated textiles also have a fiber and color protection.

• a) 0,1 bis 40 Gew.-%, bevorzugt 0,5 bis 25 Gew.-% mindestens eines hochverzweigten Polymeren, insbesondere mindestens eines hochverzweigten Polyurethans,
• b) 0 bis 30 Gew.-% eines oder mehrerer Silicone,
• c) 0 bis 30 Gew.-% eines oder mehrerer kationischer und/oder nichtionischer Tenside,
• d) 0 bis 60 Gew.-% weitere Inhaltsstoffe wie weitere Netzmittel, Weichmacher, Gleitmittel, wasserlösliche, filmbildende und adhesive Polymere, Duft- und Farbstoffe, Stabilisatoren, Faser- und Farbschutzadditive, Viskositätsmodifizierer, Soil-Release-Additive, Korrosionsschutzadditive, Bakterizide, Konservierungsmittel und Sprühhilfsmittel, und
• e) 0 bis 99,9 Gew.-% Wasser,

wobei die Summe der Komponenten a) bis e) 100 Gew.-% ergibt.The invention also provides a textile treatment composition containing

• a) from 0.1 to 40% by weight, preferably from 0.5 to 25% by weight, of at least one highly branched polymer, in particular at least one highly branched polyurethane,
• b) 0 to 30% by weight of one or more silicones,
• c) 0 to 30% by weight of one or more cationic and / or nonionic surfactants,
• d) 0 to 60 wt .-% of other ingredients such as other wetting agents, plasticizers, lubricants, water-soluble, film-forming and adhesive polymers, fragrances and dyes, stabilizers, fiber and color protective additives, viscosity modifiers, soil release additives, anti-corrosion additives, bactericides, Preservatives and spray aids, and
• e) 0 to 99.9% by weight of water,

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

Preferred silicones are amino-containing silicones which are preferably present in microemulsified form, alkoxylated, in particular ethoxylated silicones, polyalkylene oxide polysiloxanes, polyalkylene oxide aminopolydimethylsiloxanes, silicones with quaternary ammonium groups (silicon quats) and silicone surfactants. Suitable plasticizers or lubricants are, for example, oxidized polyethylenes or paraffin-containing waxes and oils. Suitable water-soluble, film-forming and adhesive polymers are, for example, (co) polymers based on acrylamide, N-vinylpyrrolidone, vinylformamide, N-vinylimidazole, vinylamine, N, N'-dialkylaminoalkyl (meth) acrylates, N, N'-dialkylaminoalkyl (meth) acrylamides, (meth) acrylic acid, (meth) acrylic acid alkyl ester and / or vinyl sulfonate. The abovementioned basic monomers can also be used in quaternized form.

If the textile pretreatment formulation is sprayed onto the fabric, the formulation may additionally contain a spray aid. In some cases, it may also be advantageous to add to the formulation alcohols such as ethanol, isopropanol, ethylene glycol or propylene glycol. Further customary additives are fragrances and dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion protection additives, bactericides and preservatives in the quantities customary for this purpose.

The textile treatment agent can also be applied by spraying, in general, when the textile is ironed after washing. The ironing is thus not only considerably easier, the textiles are also equipped with a long-lasting crease and wrinkle protection.

The use of the highly branched polymers can also be done when washing the textiles in the main wash cycle of the washing machine.

• a) 0,05 bis 20 Gew.-% mindestens eines hochverzweigten Polymeren, insbesondere mindestens eines hochverzweigten Polyurethans,
• b) 0 bis 20 Gew.-% Silicone,
• c) 0,1 bis 40 Gew.-% mindestens eines nichtionischen und/oder anionischen Tensids,
• d) 0 bis 50 Gew.-% eines oder mehrerer anorganischer Builder,
• e) 0 bis 10 Gew.-% eines oder mehrerer organischer Cobuilder,
• f) 0 bis 60 Gew.-% weiterer üblicher Inhaltsstoffe wie Stellmittel, Enzyme, Parfum, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, kationische Tenside, Farbübertragungsinhibitoren, Vergrauungsinhibitoren, Soil-Release-Polyester, Farbstoffe, Bakterizide, Auflösungsverbesserer und/oder Sprengmittel,

wobei die Summe der Komponenten a) bis f) 100 Gew.-% ergibt.The invention relates to a solid detergent formulation containing

• a) 0.05 to 20% by weight of at least one highly branched polymer, in particular at least one highly branched polyurethane,
• b) 0 to 20% by weight of silicones,
• c) from 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant,
• d) 0 to 50% by weight of one or more inorganic builders,
• e) 0 to 10% by weight of one or more organic cobuilders,
• f) 0 to 60 wt .-% of other conventional ingredients such as extenders, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleach catalysts, cationic surfactants, dye transfer inhibitors, grayness inhibitors, soil release polyester, dyes, bactericides, dissolution enhancers and / or disintegrants,

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

• (Fett)alkoholsulfate von (Fett)alkoholen mit 8 bis 22, vorzugsweise 10 bis 18 Kohlenstoffatomen, z.B. C₉- bis C₁₁-Alkoholsulfate, C₁₂- bis C₁₄-Alkoholsulfate, C₁₂-C₁₈-Alkoholsulfate, Laurylsulfat, Cetylsulfat, Myristylsulfat, Palmitylsulfat, Stearylsulfat und Talgfettalkoholsulfat;
• sulfatierte alkoxylierte Cg- bis C₂₂-Alkohole (Alkylethersulfate). Verbindungen dieser Art werden beispielsweise dadurch hergestellt, dass man zunächst einen C₈- bis C₂₂-, vorzugsweise einen C₁₀- bis C₁₈-Alkohol, z.B. einen Fettalkohol, alkoxyliert und das Alkoxylierungsprodukt anschließend sulfatiert. Für die Alkoxylierung verwendet man vorzugsweise Ethylenoxid;
• lineare C₈- bis C₂₀-Alkylbenzosulfonate (LAS), vorzugsweise lineare C₉- bis C_13-Alkylbenzolsulfonate und -Alkyltoluolsulfonate;
• Alkansulfonate wie C₈- bis C₂₄-, vorzugsweise C₁₀- bis C₁₈-Alkansulfonate;
• Seifen wie beispielsweise die Na- und K-Salze von C₈- bis C₂₄-Carbonsäuren.

Suitable anionic surfactants are in particular:

• (Fat) alcohol sulfates of (fatty) alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for example C ₉ - to C ₁₁ -alcohol sulfates, C ₁₂ - to C ₁₄ -alcohol sulfates, C ₁₂ -C ₁₈ -alcohol sulfates, lauryl sulfate, cetyl sulfate , Myristylsulfate, palmitylsulfate, stearylsulfate and tallow fatty alcohol sulfate;
• sulfated alkoxylated Cg to C ₂₂ alcohols (alkyl ether sulfates). Compounds of this type are prepared, for example, by first alkoxylating a C ₈ - to C ₂₂ -, preferably a C ₁₀ - to C ₁₈ -alcohol, for example a fatty alcohol, and then sulfating the alkoxylation product. For the alkoxylation is preferably used ethylene oxide;
• linear C ₈ - to C ₂₀ -alkylbenzosulfonates (LAS), preferably linear C ₉ - to C ₁₃ -alkylbenzenesulfonates and -alkyltoluenesulfonates;
• Alkanesulfonates such as C ₈ - to C ₂₄ -, preferably C ₁₀ - to C ₁₈ -alkanesulfonates;
• Soaps such as the Na and K salts of C ₈ to C ₂₄ carboxylic acids.

The anionic surfactants mentioned are preferably added to the detergent in the form of salts. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium ions such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium.

• alkoxylierte C₈- bis C₂₂-Alkohole wie Fettalkoholalkoxylate oder Oxoalkoholalkoxylate. Diese können mit Ethylenoxid, Propylenoxid und/oder Butylenoxid alkoxyliert sein. Als Tenside einsetzbar sind hierbei sämtliche alkoxylierten Alkohole, die mindestens zwei Moleküle eines der vorstehend genannten Alkylenoxide addiert enthalten. Hierbei kommen Blockpolymerisate von Ethylenoxid, Propylenoxid und/oder Butylenoxid in Betracht oder Anlagerungsprodukte, die die genannten Alkylenoxide in statistischer Verteilung enthalten. Die nichtionischen Tenside enthalten pro Mol Alkohol im allgemeinen 2 bis 50, vorzugsweise 3 bis 20 Mol mindestens eines Alkylenoxids. Vorzugsweise enthalten diese als Alkylenoxid Ethylenoxid. Die Alkohole haben vorzugsweise 10 bis 18 Kohlenstoffatome. Je nach Art des bei der Herstellung verwendeten Alkoxylierungskatalysators weisen die Alkoxylate eine breite oder enge Alkylenoxid-Homologenverteilung auf;
• Alkylphenolalkoxylate wie Alkylphenolethoxylate mit C₆- bis C₁₄-Alkylketten und 5 bis 30 Alkylenoxideinheiten;
• Alkylpolyglucoside mit 8 bis 22, vorzugsweise 10 bis 18 Kohlenstoffatomen in der Alkylkette und im allgemeinen 1 bis 20, vorzugsweise 1,1 bis 5 Glucosideinheiten;
• N-Alkylglucamide, Fettsäureamidalkoxylate, Fettsäurealkanolamidalkoxylate sowie Blockcopolymere aus Ethylenoxid, Propylenoxid und/oder Butylenoxid.

Suitable nonionic surfactants are in particular:

• alkoxylated C ₈ - to C ₂₂ -alcohols, such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. These may be alkoxylated with ethylene oxide, propylene oxide and / or butylene oxide. Suitable surfactants here are all alkoxylated alcohols which contain at least two molecules of one of the abovementioned alkylene oxides added. In this case, block polymers of ethylene oxide, propylene oxide and / or butylene oxide or adducts which contain said alkylene oxides in random distribution. The nonionic surfactants generally contain from 2 to 50, preferably from 3 to 20, moles of at least one alkylene oxide per mole of alcohol. Preferably, these contain ethylene oxide as the alkylene oxide. The alcohols preferably have 10 to 18 carbon atoms. Depending on the type of alkoxylation catalyst used in the preparation, the alkoxylates have a broad or narrow alkylene oxide homolog distribution;
• Alkylphenol alkoxylates such as alkylphenol ethoxylates having C ₆ to C ₁₄ alkyl chains and 5 to 30 alkylene oxide units;
• Alkyl polyglucosides having 8 to 22, preferably 10 to 18, carbon atoms in the alkyl chain and generally 1 to 20, preferably 1.1 to 5, glucoside units;
• N-alkylglucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.

• kristalline oder amorphe Alumosilicate mit ionenaustauschenden Eigenschaften wie insbesondere Zeolithe. Als Zeolithe geeignet sind insbesondere Zeolithe A, X, B, P, MAP und HS in ihrer Na-Form oder in Formen, in denen Na teilweise gegen andere Kationen wie Li, K, Ca, Mg oder Ammonium ausgetauscht ist;
• kristalline Silicate wie insbesondere Disilicate oder Schichtsilicate, z.B. δ-Na₂Si₂O₅ oder β-Na₂Si₂O₅. Die Silicate können in Form ihrer Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze eingesetzt werden, vorzugsweise als Na-, Li- oder Mg-Silicate;
• amorphe Silicate wie beispielsweise Natriummetasilicat oder amorphes Disilicat;
• Carbonate und Hydrogencarbonate. Diese können in Form ihrer Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze eingesetzt werden. Bevorzugt sind Na-, Li- und Mg-Carbonate bzw. Hydrogencarbonate, insbesondere Natriumcarbonat und/oder Natriumhydrogencarbonat;
• Polyphosphate wie z.B. Pentanatriumtriphosphat.

Suitable inorganic builders are in particular:

• crystalline or amorphous aluminosilicates with ion-exchanging properties, in particular zeolites. Particularly suitable as zeolites are zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially exchanged with other cations such as Li, K, Ca, Mg or ammonium;
• crystalline silicates such as in particular disilicates or layered silicates, for example δ-Na ₂ Si ₂ O ₅ or β-Na ₂ Si ₂ O ₅ . The silicates may be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li or Mg silicates;
• amorphous silicates such as sodium metasilicate or amorphous disilicate;
• Carbonates and bicarbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate;
• Polyphosphates such as pentasodium triphosphate.

• Geeignete niedermolekulare Carbonsäuren sind beispielsweise Citronensäure, hydrophob modifizierte Citronensäure wie z. B. Agaricinsäure, Äpfelsäure, Weinsäure, Gluconsäure, Glutarsäure, Bernsteinsäure, Imidodibemsteinsäure, Oxydibernsteinsäure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäure, Alkyl- und Alkenylbemsteinsäuren und Aminopolycarbonsäuren wie z.B. Nitrilotriessigsäure, β-Alanindiessigsäure, Ethylendiamintetraessigsäure, Serindiessigsäure, Isoserindiessigsäure, N-(2-Hydroxyethyl)iminodiessigsäure, Ethylendiamindibernsteinsäure und Methyl- und Ethylglycindiessigsäure;
• Geeignete oligomere oder polymere Carbonsäuren sind beispielsweise Homopolymere der Acrylsäure, Oligomaleinsäuren, Copolymere der Maleinsäure mit Acrylsäure, Methacrylsäure, C₂-C₂₂-Olefine wie z.B. Isobuten oder langkettige α-Olefine, Vinylalkylether mit C₁-C₈-Alkylgruppen, Vinylacetat, Vinylpropionat, (Meth)acrylester von C₁-C₈-Alkoholen und Styrol. Bevorzugt verwendet man die Homopolymeren der Acrylsäure sowie Copolymere von Acrylsäure mit Maleinsäure. Weiterhin eignen sich Polyasparaginsäuren als organische Cobuilder. Die oligomeren und polymeren Carbonsäuren werden in Säureform oder als Natriumsalz eingesetzt.
• Geeignete Bleichmittel sind beispielsweise Addukte von Wasserstoffperoxid an anorganische Salze wie z. B. Natriumperborat-Monohydrat, Natriumperborat-Tetrahydrat und Natriumcarbonat-Perhydrat und Percarbonsäuren wie z. B. Phthalimidopercapronsäure.
• Als Bleichaktivatoren eignen sich beispielsweise N,N,N',N'-Tetraacetylethylendiamin, (TAED), Natrium-p-nonanoyloxybenzolsulfonat und N-Methylmorpholiniumacetonitrilmethylsulfat.
• Vorzugsweise in Waschmitteln eingesetzte Enzyme sind Proteasen, Lipasen, Amylasen, Cellulasen, Oxidasen und Peroxidasen.
• Geeignete Farbübertragungsinhibitoren sind beispielsweise Homo- und Copolymere des 1-Vinylpyrrolidons, des 1-Vinylimidazols oder des 4-Vinylpyridin-N-oxids und mit Chloressigsäure umgesetzte Homo- und Copolymere des 4-Vinylpyridins.

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

• Suitable low molecular weight carboxylic acids are, for example, citric acid, hydrophobically modified citric acid such. B. agaricic, malic, tartaric, gluconic, glutaric, succinic, imidodisuccinic, oxydisuccinic, propanetricarboxylic, butanetetracarboxylic, cyclopentanetetracarboxylic, alkyl- and alkenylsuccinic and aminopolycarboxylic acids such as nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic, isoserinediacetic, N- (2-hydroxyethyl ) iminodiacetic acid, ethylenediamine disuccinic acid and methyl and ethylglycinediacetic acid;
• Suitable oligomeric or polymeric carboxylic acids are, for example, homopolymers of acrylic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid, methacrylic acid, C ₂ -C ₂₂ -olefins such as isobutene or long-chain α-olefins, vinyl alkyl ethers having C ₁ -C ₈ -alkyl groups, vinyl acetate, vinyl propionate , (Meth) acrylic esters of C ₁ -C ₈ -alcohols and styrene. Preference is given to using the homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid. Furthermore, polyaspartic acids are suitable as organic cobuilders. The oligomeric and polymeric carboxylic acids are used in acid form or as the sodium salt.
• Suitable bleaching agents are, for example, adducts of hydrogen peroxide with inorganic salts such. As sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate perhydrate and percarboxylic acids such. B. phthalimidopercaproic acid.
• Suitable bleach activators are, for example, N, N, N ', N'-tetraacetylethylenediamine (TAED), sodium p-nonanoyloxybenzenesulfonate and N-methylmorpholinium acetonitrile methylsulfate.
• Enzymes preferably used in detergents are proteases, lipases, amylases, cellulases, oxidases and peroxidases.
• Suitable color transfer inhibitors are, for example, homo- and copolymers of 1-vinylpyrrolidone, of 1-vinylimidazole or of 4-vinylpyridine N-oxides and reacted with chloroacetic acid homo- and copolymers of 4-vinylpyridine.

A solid detergent formulation according to the invention is usually present in powder or granule form or in extrudate or tablet form.

• a) 0,05 bis 20 Gew.-% mindestens eines hochverzweigten Polymeren, insbesondere mindestens eines hochverzweigten Polyurethans,
• b) 0 bis 20 Gew.-% eines oder mehrerer Silicone,
• c) 0,1 bis 40 Gew.-% mindestens eines nichtionischen und/oder anionischen Tensids,
• d) 0 bis 20 Gew.-% eines oder mehrerer anorganischer Builder,
• e) 0 bis 10 Gew.-% eines oder mehrerer organischer Cobuilder,
• f) 0 bis 60 Gew.-% anderer üblicher Inhaltsstoffe wie Soda, Enzyme, Parfum, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, kationische Tenside, Farbübertragungsinhibitoren, Vergrauungsinhibitoren, Soil-Release-Polyester, Farbstoffe, Bakterizide, nicht wässrige Lösemittel, Löslichkeitsvermittler, Hydrotrope, Verdicker und/oder Alkanolamine,
• g) 0 bis 99,85 Gew.-% Wasser,

wobei die Summe der Komponenten a) bis g) 100 Gew.-% ergibt.The invention further relates to a liquid detergent formulation containing

• a) 0.05 to 20% by weight of at least one highly branched polymer, in particular at least one highly branched polyurethane,
• b) 0 to 20% by weight of one or more silicones,
• c) from 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant,
• d) 0 to 20% by weight of one or more inorganic builders,
• e) 0 to 10% by weight of one or more organic cobuilders,
• f) 0 to 60% by weight of other conventional ingredients such as soda, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleach catalysts, cationic surfactants, dye transfer inhibitors, grayness inhibitors, soil release polyesters, dyes, bactericides, nonaqueous solvents, Solubilizers, hydrotropes, thickeners and / or alkanolamines,
• g) 0 to 99.85% by weight of water,

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

It may be the above-mentioned silicones; nonionic and anionic surfactants, builders and cobuilders.

A detailed description of the abovementioned detergent ingredients can be found, for example, in WO 99/06524 or WO 99/04313 and in Liquid Detergents, Editor: Kuo-Yann Lai, Surfactant Sci. Ser., Vol. 67, Marcel Decker, New York, 1997, pp. 272-304.

The concentration of highly branched polymers in the wash liquor is, for example, 10 to 5000 ppm and is preferably in the range of 50 to 1000 ppm. The textiles treated with the hyperbranched polymers in the main wash cycle of the washing machine not only wrinkle significantly less than untreated textiles. They are also easier to iron, softer and smoother, more dimensionally stable, and look less "used" after repeated washing due to their fiber and color protection, so have less lint and knots and less color damage or fading.

The use of highly branched polymers can be carried out in the so-called soft or Pflegespülgang after the main wash. The concentration of highly branched polymers in the wash liquor is, for example, 10 to 5000 ppm and is preferably in the range of 50 to 1000 ppm. Ingredients which may be typical for a softener or conditioner may possibly be present in the rinse liquor. Also, the textiles treated in this way have after drying on a leash or preferably in the tumble dryer a very good crease protection, which is associated with the already described above positive effects on ironing. The crease protection can be significantly enhanced by a one-time short ironing of the textiles after drying. The treatment in the soft or Pflegespülgang also has a favorable effect on the dimensional stability of the textiles. Furthermore, the formation of knots and lint is inhibited and color damage is suppressed.

• a) 0,05 bis 40 Gew.-% mindestens eines hochverzweigten Polymeren, insbesondere mindestens eines hochverzweigten Polyurethans,
• b) 0 bis 20 Gew.-% eines oder mehrerer Silicone,
• c) 0,1 bis 40 Gew.-% mindestens eines kationischen Tensids,
• d) 0 bis 30 Gew.-% eines oder mehrerer nichtionischer Tenside und
• e) 0 bis 30 Gew.-% andere übliche Inhaltsstoffe wie Silicone, andere Gleitmittel, Benetzungsmittel, filmbildende Polymere, Duft- und Farbstoffe, Stabilisatoren, Faser- und Farbschutzadditive, Viskositätsmodifizierer, Soil-Release-Additive, Korrosionsschutzadditive, Bakterizide und Konservierungsmittel, und
• f) 0 bis 99,85 Gew.-% Wasser,

wobei die Summe der Komponenten a) bis f) 100 Gew.-% ergibt.The invention also provides a laundry conditioner comprising

• a) from 0.05 to 40% by weight of at least one highly branched polymer, in particular at least one highly branched polyurethane,
• b) 0 to 20% by weight of one or more silicones,
• c) 0.1 to 40% by weight of at least one cationic surfactant,
• d) 0 to 30 wt .-% of one or more nonionic surfactants and
• e) 0 to 30 wt .-% of other conventional ingredients such as silicones, other lubricants, wetting agents, film-forming polymers, fragrances and dyes, stabilizers, fiber and color protective additives, viscosity modifiers, soil release additives, anti-corrosion additives, bactericides and preservatives, and
• f) 0 to 99.85% by weight of water,

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

Preferred cationic surfactants are selected from the group of the quaternary diester ammonium salts, the tetraalkyl quaternary ammonium salts, the diamido ammonium quaternary salts, the amidoamine esters and imidazolium salts. These are preferably contained in an amount of 3 to 30 wt .-% in the laundry detergent. Examples are diester ammonium quaternary salts which have two C ₁₁ - to C ₂₂ -alk (en) ylcarbonyloxy (mono- to pentamethylene) radicals and two C ₁ - to C ₃ -alkyl or -hydroxyalkyl radicals on the quaternary nitrogen atom and as counterion For example, chloride, bromide, methyl sulfate or sulfate wear.

Quaternary diester ammonium salts are furthermore especially those which carry a C ₁₁ -C ₂₂ -alk (y) ylcarbonyloxytrimethylene radical which carries a C ₁₁ -C ₂₂ -alk (en) ylcarbonyloxy radical at the central C atom of the trimethylene grouping , and three C ₁ - to C ₃ alkyl or hydroxyalkyl radicals on the quaternary nitrogen atom and carry as counterion, for example, chloride, bromide, methyl sulfate or sulfate.

Quaternary tetraalkylammonium salts are in particular those which have two C ₁ - to C ₆ -alkyl radicals and two C ₈ - to C ₂₄ -alk (en) yl radicals on the quaternary nitrogen atom and, as counterion, for example, chloride, bromide, methylsulfate or Wear sulfate.

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

Amidoaminoester are in particular tertiary amines having as substituents on the nitrogen atom, a C ₁₁ - to C ₂₂ -Alk (en) ylcarbonylamino (mono- to trimethylene) radical, a C ₁₁ - to C ₂₂ -alk (en) ylcarbonyloxy (mono - to trimethylene) radical and carry a methyl group.

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

The invention will be explained in more detail by the following examples.

Examples

The percentages in the examples mean wt .-%, unless otherwise stated in the context.

The following equipment was used: Equipment A

• 168 g Hexamethylendiisocyanat (HDI), gelöst in 386 g Dimethylacetamid (DMAc), wurden unter Stickstoffbedeckung bei Raumtemperatur vorgelegt. Anschließend wurde unter intensivem Rühren innerhalb von 1 min 134 g Dimethylolpropionsäure, gelöst in 313 g DMAc, zugegeben. Nach Zudosierung von 0,2 g Dibutylzinndilaurat wurde die Reaktionsmischung auf 70°C erwärmt und die Abnahme des NCO-Gehaltes titrimetrisch verfolgt. Bei Erreichen eines NCO-Gehaltes von 1,5 Gew.-% wies das Reaktionsprodukt eine mittlere Funktionalität bezüglich NCO von 1, bezüglich COOH von 3 und bezüglich OH von 1 auf.
  Diesem Polyadditionsprodukt wurden nun 22 g Trimethylolpropan (TMP), gelöst in 50 g DMAc, zugesetzt und 3 h bei 70°C nachgerührt. Während dieser Zeit sank der NCO-Gehalt der Mischung auf 0 %. Das Produkt wurde anschließend am Rotationsverdampfer bei 80°C im Vakuum von Lösungsmittel befreit.

1% strength by weight alkaline solution of highly branched polyurethane A, which was prepared as follows:

• 168 g of hexamethylene diisocyanate (HDI) dissolved in 386 g of dimethylacetamide (DMAc) were initially charged under nitrogen at room temperature. 134 g of dimethylolpropionic acid, dissolved in 313 g of DMAc, were then added with intensive stirring over the course of 1 minute. After addition of 0.2 g of dibutyltin dilaurate, the reaction mixture was heated to 70 ° C and the decrease in the NCO content was monitored by titration. Upon reaching an NCO content of 1.5% by weight, the reaction product had an average functionality with respect to NCO of 1, with respect to COOH of 3 and with respect to OH of 1.
  22 g of trimethylolpropane (TMP), dissolved in 50 g of DMAc, were then added to this polyaddition product and the mixture was stirred at 70.degree. C. for 3 hours. During this time, the NCO content of the mixture dropped to 0%. The product was then freed from solvent on a rotary evaporator at 80 ° C in vacuo.

• Mittlere Funktionalität bezüglich OH ca. 5 und bezüglich COOH ca. 9
• Mittlere Molmasse: 6018 g/mol

The solid end product had the following parameters:

• Mean functionality regarding OH about 5 and regarding COOH about 9
• Average molecular weight: 6018 g / mol

Finishing equipment B

• 336 g Hexamethylendiisocyanat (HDI), gelöst in 336 g Dimethylacetamid (DMAc), wurden unter Stickstoffbedeckung vorgelegt und auf 0°C abgekühlt. Anschließend wurde unter intensivem Rühren innerhalb von 20 min 105 g Diethanolamin zugegeben und 30 min bei 0°C nachgerührt. Anschließend wurden 134 g Dimethylolpropionsäure, gelöst in 239 g DMAc, zugegeben. Nach Zudosierung von 0,5 g Dibutylzinndilaurat wurde die Reaktionsmischung auf 60°C erwärmt und die Abnahme des NCO-Gehaltes titrimetrisch verfolgt. Bei Erreichen eines NCO-Gehaltes von 1,2 Gew.-% wurde ein Überschuß an Methanol zur Umsetzung noch vorhandener NCO-Gruppen zugegeben. Das Produkt wurde anschließend am Rotationsverdampfer bei 80°C im Vakuum von Lösungsmittel befreit.

1% strength by weight alkaline solution of highly branched polyurethane B, which was prepared as follows:

• 336 g of hexamethylene diisocyanate (HDI), dissolved in 336 g of dimethylacetamide (DMAc), were placed under nitrogen blanketing and cooled to 0 ° C. Subsequently, 105 g of diethanolamine was added with vigorous stirring within 20 min and stirred at 0 ° C for 30 min. Then, 134 g of dimethylolpropionic acid dissolved in 239 g of DMAc was added. After addition of 0.5 g of dibutyltin dilaurate, the reaction mixture was heated to 60 ° C. and the decrease in the NCO content was monitored titrimetrically. Upon reaching an NCO content of 1.2 wt .-%, an excess of methanol was added to the reaction of still existing NCO groups. The product was then freed from solvent on a rotary evaporator at 80 ° C in vacuo.

• Mittlere Funktionalität bezüglich COOH ca. 3 und bezüglich OH ca. 4
• Mittlere Molmasse: 1757 g/mol

The reaction product had the following parameters:

• Average functionality with respect to COOH approx. 3 and with respect to OH approx. 4
• Average molecular weight: 1757 g / mol

Equipment C

• 222 g Isophorondiisocyanat (IPDI) wurden unter Stickstoffbedeckung vorgelegt. Anschließend wurde innerhalb 1 min eine Mischung aus 67 g TMP und 67 g Dimethylolpropionsäure, gelöst in 356 g DMAc, unter intensivem Rühren zugegeben. Nach Zudosierung von 0,4 g Dibutylzinndilaurat wurde die Reaktionsmischung auf 60°C erwärmt, bei dieser Temperatur gerührt und die Abnahme des NCO-Gehaltes titrimetrisch verfolgt. Bei Erreichen eines NCO-Gehaltes von 1,0 Gew.-% wies das Reaktionsprodukt eine mittlere Funktionalität bezüglich NCO von 1, bezüglich COOH von 3 und bezüglich OH von 4 auf.
  Diesem Polyadditionsprodukt wurden nun 32 g Polytetrahydrofuran mit einer mittleren Molmasse von 250 g/mol zugesetzt und es wurde 3 h bei 60°C nachgerührt. Während dieser Zeit sank der NCO-Gehalt der Mischung auf 0 %. Das Produkt wurde anschließend am Rotationsverdampfer bei 80°C im Vakuum von Lösungsmittel befreit.

1% strength by weight alkaline solution of highly branched polyurethane C, which was prepared as follows:

• 222 g of isophorone diisocyanate (IPDI) were initially charged under nitrogen blanketing. Subsequently, within 1 min, a mixture of 67 g of TMP and 67 g of dimethylolpropionic acid dissolved in 356 g of DMAc was added with vigorous stirring. After addition of 0.4 g of dibutyltin dilaurate, the reaction mixture was heated to 60 ° C, stirred at this temperature and the decrease in the NCO content was monitored by titration. Upon reaching an NCO content of 1.0% by weight, the reaction product had an average functionality with respect to NCO of 1, with respect to COOH of 3 and with respect to OH of 4.
  32 g of polytetrahydrofuran having an average molar mass of 250 g / mol were then added to this polyaddition product and the mixture was stirred at 60.degree. C. for 3 h. While During this time, the NCO content of the mixture dropped to 0%. The product was then freed from solvent on a rotary evaporator at 80 ° C in vacuo.

• Mittere Funktionalität bezüglich OH ca. 20 und bezüglich COOH ca. 15
• Mittleres Molekulargewicht: 22610 g/mol

The solid end product had the following parameters:

• Mean functionality regarding OH about 20 and about COOH about 15
• Average molecular weight: 22610 g / mol

Equipment D

• 168 g Hexamethylendiisocyanat (HDI), gelöst in 168 g Dimethylacetamid (DMAc), wurden unter Stickstoffbedeckung vorgelegt und auf 0°C abgekühlt. Anschließend wurde unter intensivem Rühren innerhalb von 20 min 52,5 g Diethanolamin, gelöst in 52,5 g DMAc, zugegeben und 30 min bei 0°C nachgerührt. Anschließend wurden 59,9 g N-Methyldiethanolamin, gelöst in 59,5 g DMAc, zugegeben. Nach Zudosierung von 0,2 g Dibutylzinndilaurat wurde die Reaktionsmischung auf 40°C erwärmt und die Abnahme des NCO-Gehaltes titrimetrisch verfolgt. Bei Erreichen eines NCO-Gehaltes von 1,2 Gew.-% wurde ein Überschuß an Methanol zur Umsetzung noch vorhandener NCO-Gruppen zugegeben. Das Produkt wurde anschließend am Rotationsverdampfer bei 80°C im Vakuum von Lösungsmittel befreit.

1% strength by weight alkaline solution of highly branched polyurethane D, which was prepared as follows:

• 168 g of hexamethylene diisocyanate (HDI), dissolved in 168 g of dimethylacetamide (DMAc), were placed under nitrogen blanketing and cooled to 0 ° C. 52.5 g of diethanolamine, dissolved in 52.5 g of DMAc, were subsequently added with vigorous stirring over a period of 20 minutes and the mixture was stirred at 0 ° C. for 30 minutes. Subsequently, 59.9 g of N-methyldiethanolamine dissolved in 59.5 g of DMAc was added. After addition of 0.2 g of dibutyltin dilaurate, the reaction mixture was heated to 40 ° C. and the decrease in the NCO content was monitored titrimetrically. Upon reaching an NCO content of 1.2 wt .-%, an excess of methanol was added to the reaction of still existing NCO groups. The product was then freed from solvent on a rotary evaporator at 80 ° C in vacuo.

• Mittlere Funktionalität bezüglich NR₂ ca. 3 und bezüglich OH ca. 4
• Mittlere Molmasse: 1782 g/mol.

The reaction product had the following parameters:

• Mean functionality with respect to NR ₂ about 3 and with respect to OH about 4
• Average molecular weight: 1782 g / mol.

Equipment of tissue samples

Cotton fabrics (BW) of the size specified in Table 1 with a basis weight of 160 g / m ² were sprayed on both sides with the finishing agents A, B, C and D, so that the application amount 2%, based on the respective weight of the dry Textilguts, amounted and then hot-ironed in slightly damp condition.

The tissue samples thus treated were washed for comparison with untreated tissue samples of the same size and in the presence of ballast tissue with a liquid detergent at 40 ° C in an automatic household washing machine (load between 1.5 and 3.0 kg) and then dried in a tumble dryer. A standard washing or standard drying program was used (program color wash 40 ° C or program cupboard dry). After drying, the tissue samples were scored visually according to the AATCC test method 124, where the grade 1 indicates that the tissue is very creased and has many wrinkles, while the grade 5 was awarded for wrinkle-free and wrinkle-free tissue. The tissue samples pretreated with finishing agents A, B and C received grades between 2.5 and 3.5. In contrast, the untreated tissue samples each received grade 1. Table 1: BW (40 cm x 40 cm) load 1.5 kg BW (40 cm x 40 cm) load 3.0 kg BW (40 cm x 80 cm) load 1.5 kg untreated 1 1 1 A 3.5 3 3 B 3 2.5 3 C 2.5 2.5 2.5 D 3 2.5 3

Claims (15)

1. A process for wrinkleproofing cellulosic textiles by treating the textiles with a finish and drying the treated textiles, which comprises using a finish comprising one or more dendrimeric or hyperbranched polymers in dissolved or dispersed form.
2. The process according to claim 1 wherein the dendrimeric or hyperbranched polymers are dendrimeric or hyperbranched polyurethanes.
3. The process according to either of claims 1 and 2 wherein the dendrimeric or hyperbranched polymers contain one or more functional groups selected from the group consisting of -COOH, -COOR, -CONHR, -CONH₂, -OH, -SH, -NH₂, -NHR, -NR₂, -NR₃ ⁺, -SO₃H, -SO₃R, -NHCOOR, -NHCONH₂, -NHCONHR and salts thereof.
4. The process according to claim 3 wherein the functional groups are selected from the group consisting of -COOH, CONH₂, -OH, -NH₂, -NHR, -NR₂, -NR₃ ⁺, -SO₃H and salts thereof.
5. The process according to claim 4 wherein the functional groups are selected from the group consisting of -COOH, -OH, -SO₃H and salts thereof.
6. The process according to claim 4 wherein the functional groups are selected from the group consisting of -NH₂, -NHR, -NR₂, -NR₃ ⁺ and salts thereof.
7. The process according to any of claims 1 to 6 wherein the dendrimeric or hyperbranched polymers contain on average at least 4 functional groups.
8. The process according to claim 7 wherein the dendrimeric or hyperbranched polymers contain on average from 4 to 100 functional groups.
9. The use of dendrimeric or hyperbranched polymers selected from the group consisting of dendrimeric or hyperbranched polyesters, polyethers, polyurethanes, polyureaurethanes, polyamides, polysiloxanes, carbosilanes, polyetheramides and polyesteramides in textile treatments, solid and liquid laundry detergents and laundry refreshers.
10. The use of finishes comprising dendrimeric or hyperbranched polymers selected from the group consisting of dendrimeric or hyperbranched polyesters, polyethers, polyurethanes, polyureaurethanes, polyamides, polysiloxanes, carbosilanes, polyetheramides and polyesteramides in the manufacture of textiles, textile treatment, main laundry cycle, final laundry rinse cycle and ironing.
11. The use of dendrimeric or hyperbranched polymers as defined in any of claims 1 to 8 for wrinkleproofing cellulosic textiles.
12. A textile treatment comprising

    a) from 0.1-40% by weight of at least one dendrimeric or hyperbranched polymer selected from the group consisting of dendrimeric or hyperbranched polyesters, polyethers, polyurethanes, polyureaurethanes, polyamides, polysiloxanes, carbosilanes, polyetheramides and polyesteramides,

    b) from 0 to 30% by weight of one or more silicones,

    c) from 0 to 30% by weight of one or more cationic and/or nonionic surfactants,

    d) from 0 to 60% by weight of further ingredients such as further wetting agents, softeners, lubricants, water-soluble, film-forming and adhesive polymers, scents, dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion control additives, bactericides, preservatives and spraying assistants, and

    e) from 0 to 99.9% by weight of water,

    components a) to e) adding up to 100% by weight.
13. A solid laundry detergent comprising

    a) from 0.05 to 20% by weight of at least one dendrimeric or hyperbranched polymer selected from the group consisting of dendrimeric or hyperbranched polyesters, polyethers, polyurethanes, polyureaurethanes, polyamides, polysiloxanes, carbosilanes, polyetheramides and polyesteramides,

    b) from 0 to 20% by weight of one or more silicones,

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

    d) from 0 to 50% by weight of one or more inorganic builders,

    e) from 0 to 10% by weight of one or more organic cobuilders,

    f) from 0 to 60% by weight of other customary ingredients such as standardizers, enzymes, perfume, complexing agents, corrosion inhibitors, bleaches, bleach activators, cationic surfactants, bleach catalysts, dye transfer inhibitors, antiredeposition agents, soil release polyesters, dyes, bactericides, dissolution improvers and/or disintegrants,

    components a) to f) adding up to 100% by weight.
14. A liquid laundry detergent comprising

    a) from 0.05 to 20% by weight of at least one dendrimeric or hyperbranched polymer selected from the group consisting of dendrimeric or hyperbranched polyesters, polyethers, polyurethanes, polyureaurethanes, polyamides, polysiloxanes, carbosilanes, polyetheramides and polyesteramides,

    b) from 0 to 20% by weight of one or more silicones,

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

    d) from 0 to 20% by weight of one or more inorganic builders,

    e) from 0 to 10% by weight of one or more organic cobuilders,

    f) from 0 to 60% by weight of other customary ingredients such as sodium carbonate, enzymes, perfume, complexing agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, cationic surfactants, dye transfer inhibitors, antiredeposition agents, soil release polyesters, dyes, bactericides, nonaqueous solvents, solubilizers, hydrotropes, thickeners and/or alkanolamines,

    g) from 0 to 99.85% by weight of water,

    components a) to g) adding up to 100% by weight.
15. A laundry refresher comprising

    a) from 0.05 to 40% by weight of at least one dendrimeric or hyperbranched branched polymer selected from the group consisting of dendrimeric or hyperbranched polyesters, polyethers, polyurethanes, polyureaurethanes, polyamides, polysiloxanes, carbosilanes, polyetheramides and polyesteramides,

    b) from 0 to 20% by weight of one or more silicones,

    c) from 0.1 to 40% by weight of at least one cationic surfactant,

    d) from 0 to 30% by weight of one or more

    e) from 0 to 30% by weight of other customary ingredients such as silicones, other lubricants, wetting agents, film-forming polymers, scents, dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion control additives, bactericides and preservatives, and

    f) from 0 to 99.85% by weight of water,

    components a) to f) adding up to 100% by weight.