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

Highly branched polymers for the anti-crease dressing of cellulose containing textiles Download PDF

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Publication number
EP1339910B1
EP1339910B1 EP01989443A EP01989443A EP1339910B1 EP 1339910 B1 EP1339910 B1 EP 1339910B1 EP 01989443 A EP01989443 A EP 01989443A EP 01989443 A EP01989443 A EP 01989443A EP 1339910 B1 EP1339910 B1 EP 1339910B1
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EP
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Prior art keywords
weight
dendrimeric
hyperbranched
highly branched
group
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EP01989443A
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German (de)
French (fr)
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EP1339910A1 (en
Inventor
Jürgen Detering
Peter Neumann
Bernd Bruchmann
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BASF SE
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BASF SE
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3726Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02Natural fibres, other than mineral fibres
    • D06M2101/04Vegetal fibres
    • D06M2101/06Vegetal fibres cellulosic
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/20Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease

Definitions

  • 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.
  • 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.
  • formulations 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.
  • compositions which cause an anti-wrinkle effect in the treated textiles.
  • the compositions containing polyorganosiloxane and and other additives such as. Polyurethane.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • highly branched polyurethanes, highly branched polyesters, highly branched polyethers, highly branched polyesteramides and highly branched polyamines have proven particularly suitable.
  • the hyperbranched polyamines the highly branched polyethylenimines should be mentioned in particular. Very particularly preferred are highly branched polyurethanes.
  • 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.
  • the originally present B groups can also be converted by polymer-analogous reaction with suitable compounds.
  • 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.
  • other functional groups such as -CN or -OR may also be introduced.
  • 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.
  • 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.
  • suitable bases Analogously, basic groups can be converted with suitable acids into the corresponding salts.
  • water-soluble highly branched polymers can be obtained.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • AB x monomers can be synthesized according to the method described in WO 97/02304 using protective group techniques.
  • this technique is illustrated by the preparation of an AB 2 monomer from 2,4-tolylene diisocyanate (TDI) and trimethylolpropane.
  • TDI 2,4-tolylene diisocyanate
  • 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.
  • a molecule having an isocyanate group and 2 OH groups is obtained.
  • the AB x molecules can be synthesized by the method described in DE-A 199 04 444, in which no protective groups are required.
  • 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-diis
  • 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).
  • 2,4-tolylene diisocyanate (2,4-TDI)
  • 2,4'-diphenylmethane diisocyanate (2,4'
  • 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.
  • 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.
  • 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.
  • di-, tri- or tetra-functional compounds whose functional groups have a different reactivity with respect to NCO groups.
  • 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.
  • 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.
  • 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.
  • elevated temperature preferably in the range between 30 and 80 ° C.
  • 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.
  • an AB 2 molecule can be prepared from one mole of glycerol and 2 moles of 2,4-TDI.
  • 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.
  • AB 3 molecules can be obtained by reaction of diisocyanates with compounds having at least 4 isocyanate-reactive groups.
  • reaction of 2,4-tolylene diisocyanate with tris (hydroxymethyl) aminomethane may be mentioned.
  • polyfunctional compounds can be used which can react with the respective A groups.
  • polyfunctional compounds which can react with the respective A groups.
  • 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.
  • 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.
  • the functional groups can also be rendered hydrophobic, hydrophilicized or trans-functionalized as described above.
  • 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.
  • suitable bases Analogously, basic groups can be converted with suitable acids into the corresponding salts.
  • water-soluble highly branched polyurethanes can be obtained.
  • hydrophobicized products 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.
  • suitable reactants are 2-hydroxyacetic acid, 4-hydroxybenzoic acid, 12-hydroxydodecanoic acid, 2-hydroxyethanesulfonic acid, glycine or alanine.
  • 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.
  • monounsaturated or polyunsaturated fatty acids in particular C 8 -C 40 -fatty acids
  • an aliphatic alcohol having at least two OH groups wherein at least one OH group may not be esterified.
  • 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.
  • 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.
  • solvents e.g. Water, alcohols such as methanol, ethanol and propanol, THF or mixtures thereof.
  • 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.
  • a textile treatment agent containing the hyperbranched polymers can, for example, be treated at home before or after washing, for example by ironing, with a textile treatment agent containing the hyperbranched 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the formulation may additionally contain a spray aid.
  • a spray aid 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.
  • 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.
  • a solid detergent formulation according to the invention is usually present in powder or granule form or in extrudate or tablet form.
  • silicones It may be the above-mentioned silicones; nonionic and anionic surfactants, builders and cobuilders.
  • 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 Vietnamese Nygang 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.
  • 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 Vietnamese Hughes Congressgang 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.
  • 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.
  • 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
  • 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
  • chloride, bromide, methyl sulfate or sulfate wear 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.
  • 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).
  • 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.

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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

Die Erfindung betrifft Verfahren zur Antiknitterausrüstung cellulosehaltiger Textilien, Ausrüstungsmittel zur Antiknitterausrüstung, die hochverzweigte Polymere enthalten, die Verwendung der Ausrüstungsmittel und der hochverzweigten Polymere, sowie Textilbehandlungsmittel, feste und flüssige Waschmittelformulierungen und Wäschepflegespülmittel, die hochverzweigte Polymere enthalten.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.

Cellulosehaltige Textilien werden beispielsweise durch Behandlung mit Kondensationsprodukten aus Harnstoff, Glyoxal und Formaldehyd pflegeleicht ausgerüstet. Die Ausrüstung erfolgt dabei während der Herstellung der Textilmaterialien. Bei der Ausrüstung verwendet man häufig weitere Zusätze wie weichmachende Verbindungen. Die so veredelten Textilien besitzen gegenüber den unbehandelten Cellulosetextilien nach dem Waschprozess den Vorteil, dass sie weniger Knitter und Falten aufweisen, leichter zu bügeln und weicher und glatter sind.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.

Aus der WO 92/01773 ist der Einsatz von mikroemulgierten Aminosiloxanen in Weichspülern zur Reduzierung der Knitter- und Faltenbildung während des Waschprozesses (Knitterarmausrüstung) bekannt. Gleichzeitig soll durch die Verwendung der Aminosiloxane das Bügeln erleichtert werden.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.

Aus der WO 98/4772 ist ein Verfahren zur Vorbehandlung von textilen Materialien bekannt, wobei man eine Mischung aus einer Polycarbonsäure und einem kationischen Weichmacher auf die textilen Materialien aufbringt. Man erreicht damit einen Knitterschutz.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.

Aus der EP-A 0 300 525 sind Weichspüler auf Basis von vernetzbaren aminofunktionalisierten Siliconen bekannt, die einen Knitterschutz bzw. einen Bügelleichteffekt für die damit behandelten Textilien bewirken.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.

Aus der WO 99/55953 sind Formulierungen bekannt, die einen Antiknittereffekt bei den behandelten Textilien bewirken. Die Formulierungen bestehen aus Gleitmitteln, Polymeren, die für Dimensions- und Formstabilität der Textilien sorgen, Lithiumsalzen und optional weiteren Inhaltsstoffen wie Weichmachern, ionischen und nichtionischen Tensiden, geruchsbindenden Substanzen und Bakteriziden. Das Aufbringen der Formulierung auf das Textilgut erfolgt vorzugsweise durch Sprühen.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 beschreibt ein Gemisch aus einem Weichmacher und einer Vemetzerkomponente mit kationischen Eigenschaften als Mittel zur Ausstattung von Textilien mit einem Knitter- und Faltenschutz, sowie ein Verfahren zur Antiknitterausrüstung von Textilien.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.

Aus der WO01/25385A sind Weichmacherzusammensetzungen bekannt, die einen Antiknittereffekt bei den behandelten Textilien bewirken. Die Zusammensetzungen enthaltenden Polyorganosiloxanund und weitere Zusätze wie zB. Polyurethan.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.

Aus der US3905929A sind Polyurethan bekannt, die zur Antiknitterausrüstung gebraucht werden können.From US3905929A polyurethane are known that can be used for anti-wrinkle equipment.

Dendrimeren oder hochverzweigten Polyurethanen sind aus DE19904444A bekannt.Dendrimers or highly branched polyurethanes are known from DE19904444A.

Waschmittelzusammensetzungen enthaltenden Tenside, Builder und dendrimer Makromolekule als Farbübertragungsinhibitor sind aus EP0779358A bekannt.Detergent compositions containing surfactants, builders and dendrimer macromolecules as a color transfer inhibitor are known from EP0779358A.

Aufgabe der Erfindung ist es, ein weiteres Verfahren zur Antiknitterausrüstung von cellulosehaltigen Textilien sowie weitere Ausrüstungsmittel zur Antiknitterausrüstung solcher Textilien bereitzustellen.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.

Gelöst wird die Aufgabe durch ein Verfahren zur Antiknitterausrüstung von cellulosehaltigen Textilien durch Behandeln der Textilien mit einem Ausrüstungsmittel und Trocknen der behandelten Textilien, dadurch gekennzeichnet, dass das Ausrüstungsmittel eines oder mehrere hochverzweigte Polymere in gelöster oder dispergierter Form enthält.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.

Gelöst wird die Aufgabe auch durch ein Ausrüstungsmittel zur Antiknitterausrüstung cellulosehaltiger Textilien, das diese hochverzweigten Polymere enthält.The object is also achieved by a finishing agent for anti-wrinkle finishing of cellulosic textiles containing these highly branched polymers.

Hochverzweigte Polymere sind an sich bekannt. Dendrimere, Arborole, Starburst Polymere und hyperverzweigte Polymere sind Bezeichnungen für polymere Strukturen, die sich durch eine verzweigte Struktur und eine hohe Funktionalität auszeichnen.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.

Bei Dendrimeren handelt es sich um molekular und strukturell einheitliche Makromoleküle mit einem hoch symmetrischen Aufbau. Sie werden in vielstufigen Synthesen aufgebaut und sind dementsprechend sehr teuer.Dendrimers are molecularly and structurally uniform macromolecules with a highly symmetric structure. They are built in multi-stage syntheses and are therefore very expensive.

Im Gegensatz dazu sind hyperverzweigte Polymere sowohl molekular als auch strukturell uneinheitlich. Sie weisen Äste unterschiedlicher Länge und Verzweigung auf. Die erfindungsgemäß eingesetzten hochverzweigten Polymere sind bevorzugt solche hyperverzweigten Polymere im engeren Sinn. Es können aber auch strukturell und molekular einheitliche dendrimere Polymere eingesetzt werden. Der Begriff "hochverzweigte Polymere" im Sinne dieser Erfindung umfasst daher hyperverzweigte und dendrimere Polymere.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.

Die erfindungsgemäß eingesetzten hochverzweigten Polymere können insbesondere aus so genannten ABx-Monomeren hergestellt werden. Diese weisen zwei verschiedene funktionelle Gruppen A und B auf, die unter Bildung einer Verknüpfung miteinander reagieren können. Die funktionelle Gruppe A ist dabei nur einmal pro Molekül enthalten und die funktionelle Gruppe B zweifach oder mehrfach. Durch die Reaktion der ABx-Monomere miteinander entstehen unvernetzte Polymere mit regelmäßig angeordneten Verzweigungstellen. Die Polymere weisen an den Kettenenden fast ausschließlich B-Gruppen auf. Nähere Einzelheiten sind beispielsweise in J.M.S. - Rev. Macromol. Chem. Phys., C37(3), 555 - 579 (1997) beschrieben.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).

Funktionelle Gruppen aufweisende hochverzweigte Polymere können in prinzipiell bekannter Art und Weise unter Verwendung von ABx-, bevorzugt AB2-Monomeren synthetisiert werden. Die AB2-Monomere können dabei vollständig in Form von Verzweigungen eingebaut sein, sie können als terminale Gruppen eingebaut sein, also noch zwei freie B-Gruppen aufweisen, oder sie können als lineare Gruppen mit einer freien B-Gruppe eingebaut sein. Die erhaltenen hochverzweigten Polymere weisen je nach dem Polymerisationsgrad eine mehr oder weniger große Anzahl von B-Gruppen, entweder terminal oder als Seitengruppen auf. Weitere Angaben zu hyperverzweigten Polymeren und deren Synthese sind beispielsweise in J.M.S. - Rev. Macromol. Chem. Phys., C37(3), 555 - 579 (1997) und der dort zitierten Literatur zu finden.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.

Die Auswahl von hochverzweigten Polymeren zur Anwendung in dem erfindungsgemäßen Verfahren zur Antiknitterausrüstung ist prinzipiell nicht auf eine bestimmte Polymerklasse beschränkt. In Frage kommen hochverzweigte Polyester, hochverzweigte Polyether, hochverzweigte Polyurethane, hochverzweigte Polyharnstoffurethane, hochverzweigte Polyamine, hochverzweigte Polyamide, hochverzweigte Polysiloxane, hochverzweigte Carbosilane, hochverzweigte Polyetheramide sowie hochverzweigte Polyesteramide. Als besonders geeignet haben sich aber hochverzweigte Polyurethane, hochverzweigte Polyester, hochverzweigte Polyether, hochverzweigte Polyesteramide und hochverzweigte Polyamine erwiesen. Unter den hochverzweigten Polyaminen sind speziell die hochverzweigten Polyethylenimine zu nennen. Ganz besonders bevorzugt sind hochverzweigte Polyurethane.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 Polymere lassen sich beispielsweise wie folgt herstellen:

  • 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

Durch Polymerisation von AB2-Molekülen erhaltene hochverzweigte und hochfunktionelle Polymere können prinzipiell als solche in den erfindungsgemäßen Ausrüstungsmitteln eingesetzt werden, vorausgesetzt, die im Zuge der jeweiligen Ausführungsform der Synthese erhaltenen funktionellen Gruppen sind für die Anwendung der Polymere in gelöster oder dispergierter Form geeignet.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.

Die ursprünglich vorhandenen B-Gruppen können aber auch durch polymeranaloge Umsetzung mit dazu geeigneten Verbindungen umfunktionalisiert werden.However, the originally present B groups can also be converted by polymer-analogous reaction with suitable compounds.

Beispiele für geeignete funktionelle Gruppen, die mittels geeigneter Reaktionspartner eingeführt werden können, umfassen insbesondere saure oder basische, H-Atome aufweisende Gruppen sowie deren Derivate wie -COOH, -COOR, -CONHR, -CONH2, -OH, -SH, -NH2, -NHR, -NR2, -NR3 +, -SO3H, -SO3R -NHCOOR, -NHCONH2, -NHCONHR oder deren Salze. Bei den Resten R handelt es sich im Regelfall um geradkettige oder verzweigte Alkylreste, die auch noch weiter substituiert sein können, beispielsweise um C1 - C8-Alkylreste. Es können aber auch andere funktionelle Gruppen wie beispielsweise -CN oder -OR eingeführt werden.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 einer bevorzugten Ausführungsform weisen die erfindungsgemäß eingesetzten hochverzweigten Polymere eine oder mehrere funktionelle Gruppen, ausgewählt aus der Gruppe bestehend aus. -COOH, -COOR, -CONHR, -CONH2, -OH, -SH, -NH2, -NHR, -NR2, -NR3 +, -SO3H, -SO3R, -NHCOOR, -NHCONH2, -NHCONHR oder deren Salze auf.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.

Zur Umfunktionalisierung eingesetzte Verbindungen können einerseits die gewünschte funktionelle Gruppe sowie eine zweite Gruppe, die mit den B-Gruppen des als Ausgangsmaterial eingesetzten hochverzweigten Polymers unter Bildung einer Bindung zur Reaktion befähigt ist, umfassen. Ein Beispiel ist die Umsetzung einer Isocyanat-Grüppe mit einer Hydroxycarbonsäure.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.

Es können aber auch monofunktionelle Verbindungen eingesetzt werden, mit denen vorhandene Gruppen lediglich modifiziert werden. Beispielsweise können Alkylhalogenide zur Quarternisierung vorhandener Aminogruppen eingesetzt werden.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.

Die Umfunktionalisierung der hyperverzweigten Polymere kann vorteilhaft unmittelbar im Anschluss an die Polymerisationsreaktion oder in einer separaten Reaktion erfolgen.The re-functionalization of the hyperbranched polymers can advantageously be carried out immediately after the polymerization reaction or in a separate reaction.

Funktionelle Gruppen, die über ausreichend acide H-Atome verfügen, können durch Behandlung mit geeigneten Basen in die entsprechenden Salze übergeführt werden. Analog lassen sich basische Gruppen mit geeigneten Säuren in die entsprechenden Salze überführen. Dadurch lassen sich wasserlösliche hochverzweigte Polymere erhalten.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.

Es können auch hochverzweigte Polymere erzeugt werden, die verschiedenartige Funktionalitäten aufweisen. Dies kann beispielsweise durch Umsetzung mit einem Gemisch verschiedener Verbindungen zur Umfunktionalisierung erfolgen, oder auch dadurch, dass man nur einen Teil der ursprünglich vorhandenen funktionellen Gruppen umsetzt.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.

Polymerisationsgrad, Molmasse sowie Art und Anzahl funktioneller Gruppen können vom Fachmann je nach der vorgesehenen Anwendung gewählt werden.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.

Besonders bevorzugte funktionelle Gruppen sind -COOH, -CONH2, -OH, - NH2, -NHR, -NR2, -NR3 + und -SO3H und deren Salze.Particularly preferred functional groups are -COOH, -CONH 2 , -OH, -NH 2 , -NHR, -NR 2 , -NR 3 + and -SO 3 H and their salts.

In einer speziellen Ausführungsform weisen die erfindungsgemäß eingesetzten hochverzweigten Polymere eine oder mehrere funktionelle Gruppen, ausgewählt aus der Gruppe bestehend aus -COOH, -OH, -SO3H und deren Salzen, auf.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 einer weiteren speziellen Ausführungsform weisen die erfindungsgemäß eingesetzten hochverzweigten Polymere eine oder mehrere funktionelle Gruppen, ausgewählt aus der Gruppe bestehend aus -NH2, -NHR, -NR2, -NR3 + und deren Salzen, auf.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.

Die erfindungsgemäß eingesetzten hochverzweigten Polymere weisen im Mittel mindestens 4 funktionelle Gruppen pro Molekül auf. Die Zahl der funktionellen Gruppen ist prinzipiell nicht nach oben beschränkt. Allerdings weisen Produkte mit einer zu hohen Anzahl von funktionellen Gruppen häufig unerwünschte Eigenschaften auf, wie beispielsweise schlechte Löslichkeit oder eine sehr hohe Viskosität. Daher weisen die erfindungsgemäß eingesetzten hochverzweigten Polymere vorzugsweise im Mittel nicht mehr als 200 funktionelle Gruppen auf. Bevorzugt weisen die hochverzweigten Polymere im Mittel 4 bis 150 und besonders bevorzugt 4 bis 100 funktionelle Gruppen auf.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.

Die Molmassen der erfindungsgemäß eingesetzten hochverzweigten Polymere richten sich nach der jeweiligen Polymerklasse und werden vom Fachmann entsprechend ausgewählt. Bewährt haben sich aber Produkte mit einem gewichtsmittleren Molekulargewicht Mw von 1000 bis 20 000 g/mol, bevorzugt 1000 bis 100 000 g/mol.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.

Bevorzugte hochverzweigte Polymere, die in den erfindungsgemäßen Ausrüstungsmitteln eingesetzt werden, sind hochverzweigte Polyurethane.Preferred hyperbranched polymers used in the finishing agents of the present invention are highly branched polyurethanes.

Der Begriff "Polyurethane" im Sinne dieser Erfindung umfasst über das übliche Verständnis hinaus Polymere, die durch Umsetzung von Di- oder Polyisocyanaten mit Verbindungen mit aktivem Wasserstoff erhalten werden können, und die durch Urethanaber auch beispielsweise durch Harnstoff-, Allophanat-, Biuret-, Carbodiimid-, Amid-, Uretonimin-, Uretdion-, Isocyanurat- oder Oxazolidon-Strukturen verknüpft sein können.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.

Zur Synthese der erfindungsgemäß eingesetzten hyperverzweigten Polyurethane werden bevorzugt ABx-Monomere eingesetzt, die sowohl Isocyanat-Gruppen als auch Gruppen, die mit Isocyanat-Gruppen unter Bildung einer Verknüpfung reagieren können, aufweisen. x ist eine natürliche Zahl zwischen 2 und 8, bevorzugt 2 oder 3. Entweder handelt es sich bei A um eine Isocyanat-Gruppe und bei B um mit dieser reaktive Gruppen, oder es liegt der umgekehrte Fall vor.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.

Bei den mit den Isocyanat-Gruppen reaktiven Gruppen handelt es sich bevorzugt um OH-, NH2-, NHR- oder SH-Gruppen.The groups reactive with the isocyanate groups are preferably OH, NH 2 , NHR or SH groups.

Die ABx-Monomere sind in bekannter Art und Weise herstellbar. ABx-Monomere können beispielsweise nach der in WO 97/02304 beschriebenen Methode unter Anwendung von Schutzgruppentechniken synthetisiert werden. Beispielhaft sei diese Technik an der Herstellung eines AB2-Monomers aus 2,4-Toluylendiisocyanat (TDI) und Trimethylolpropan erläutert. Zunächst wird eine der Isocyanat-Gruppen des TDI in bekannter Art und Weise verkappt, beispielsweise durch Umsetzung mit einem Oxim. Die verbleibende freie NCO-Gruppe wird mit Trimethylolpropan umgesetzt, wobei nur eine der drei OH-Gruppen mit der Isocyanat-Gruppe reagiert, während zwei OH-Gruppen über Acetalisierung blockiert sind. Nach Abspalten der Schutzgruppe wird ein Molekül mit einer Isocyanat-Gruppe und 2 OH-Gruppen erhalten.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.

Besonders vorteilhaft können die ABx-Moleküle nach der in der DE-A 199 04 444 beschriebenen Methode synthetisiert werden, bei der keine Schutzgruppen erforderlich sind. Bei dieser Methode werden Di- oder Polyisocyanate eingesetzt und mit Verbindungen, die mindestens zwei mit Isocyanatgruppen reaktive Gruppen aufweisen, umgesetzt. Zumindest einer der Reaktionspartner weist dabei Gruppen mit gegenüber dem anderen Reaktionspartner unterschiedlicher Reaktivität auf. Bevorzugt weisen beide Reaktionspartner Gruppen mit gegenüber dem anderen Reaktionspartner unterschiedlicher Reaktivität auf. Die Reaktionsbedingungen werden so gewählt, dass nur bestimmte reaktive Gruppen miteinander reagieren können.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.

Als Di- und Polyisocyanate kommen die aus dem Stand der Technik bekannten aliphatischen, cycloaliphatischen und aromatischen Isocyanate in Frage. Bevorzugte Di- oder Polyisocyanate sind 4,4'-Diphenylmethandiisocyanat, die Mischungen aus monomeren Diphenylmethandiisocyanaten und oligomeren Diphenylmethandiisocyanaten (Polymer-MDI), Tetramethylendiisocyanat, Hexamethylendiisocyanat, 4,4'-Methylenbis(cyclohexyl)-diisocyanat, Xylylendiisocyanat, Tetramethylxylylendiisocyanat, Dodecyldüsocyanat, Lysinalkylesterdiisocyanat, wobei Alkyl für C1- bis C10-Alkyl steht, 2,2,4- oder 2,4,4-Trimethyl-1,6-hexamethylendiisocyanat, 1,4-Diisocyanatocyclohexan oder 4-Isocyanatomethyl-1,8-octamethylendiisocyanat.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 ,

Besonders bevorzugt sind Di- oder Polyisocyanate mit NCO-Gruppen unterschiedlicher Reaktivität, wie 2,4-Toluylendiisocyanat (2,4-TDI), 2,4'-Diphenylmethandiisocyanat (2,4'-MDI), Trüsocyanatotoluol, Isophorondiisocyanat (IPDI), 2-Butyl-2-ethylpentamethylendiisocyanat, 2-Isocyanatopropylcyclohexylisocyanat, 3(4)-Isocyanatomethyl-1-methylcyclohexylisocyanat, 1,4-Diisocyanato-4-methylpentan, 2,4'-Methylenbis(cyclohexyl)diisocyanat und 4-Methylcyclohexan-1,3-diisocyanat (H-TDI). Weiterhin sind Isocyanate (b) besonders bevorzugt, deren NCO-Gruppen zunächst gleich reaktiv sind, bei denen sich jedoch durch Erstaddition eines Alkohols oder Amins an eine NCO-Gruppe ein Reaktivitätsabfall bei der zweiten NCO-Gruppe induzieren läßt. Beispiele dafür sind Isocyanate, deren NCO-Gruppen über ein delokalisiertes Elektronensystem gekoppelt sind, z. B. 1,3- und 1,4-Phenylendiisocyanat, 1,5-Naphthylendiisocyanat, Diphenyldiisocyanat, Tolidindiisocyanat oder 2,6-Toluylendiisocyanat.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.

Weiterhin können beispielsweise Oligo- oder Polyisocyanate verwendet werden, die sich aus den genannten Di- oder Polyisocyanaten oder deren Mischungen durch Verknüpfung mittels Urethan, Allophanat-, Harnstoff-, Biuret-, Uretdion-, Amid-, Isocyanurat-, Carbodiimid-, Uretonimin-, Oxadiazintrion- oder Iminooxadiazindion-Strukturen herstellen lassen.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.

Als Verbindungen mit mindestens zwei mit Isocyanaten reaktiven Gruppen werden vorzugsweise di-, tri- oder tetrafunktionelle Verbindungen eingesetzt, deren funktionelle Gruppen gegenüber NCO-Gruppen eine unterschiedliche Reaktivität aufweisen. Bevorzugt sind Verbindungen mit mindestens einer primären und mindestens einer sekundären Hydroxylgruppe, mindestens einer Hydroxylgruppe und mindestens einer Mercaptogruppe, besonders bevorzugt mit mindestens einer Hydroxylgruppe und mindestens einer Aminogruppe im Molekül, insbesondere Aminoalkohole, Aminodiole und Aminotriole, da die Reaktivität der Aminogruppe gegenüber der Hydroxylgruppe bei der Umsetzung mit Isocyanat deutlich höher ist.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.

Beispiele für die genannten Verbindungen mit mindestens zwei mit Isocyanaten reaktiven Gruppen sind Propylenglykol, Glycerin, Mercaptoethanol, Ethanolamin, N-Methylethanolamin, Diethanolamin, Ethanolpropanolamin, Dipropanolamin, Diisopropanolamin, 2-Amino-1,3-propandiol, 2-Amino-2-methyl-1,3-propandiol oder Tris(hydroxymethyl)-aminomethan. Weiterhin sind auch Mischungen der genannten Verbindungen einsetzbar.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.

Die Herstellung eines AB2-Moleküls sei beispielhaft für den Fall eines Diisocyanates mit einem Aminodiol erläutert. Hiebei wird zunächst ein Mol eines Diisocyanats mit einem Mol eines Aminodiols bei niedrigen Temperaturen, vorzugsweise im Bereich zwischen - 10 bis 30 °C, umgesetzt. In diesem Temperaturbereich erfolgt eine praktisch vollständige Unterdrückung der Urethanbildungsreaktion und die reaktiveren NCO-Gruppen des Isocyanates reagieren ausschließlich mit der Aminogruppe des Aminodiols. Das gebildete ABx-Molekül weist eine freie NCO-Gruppe sowie zwei freie OH-Gruppen auf und kann zur Synthese eines hochverzweigten Polyurethans eingesetzt werden.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.

Durch Erwärmung und/oder Katalysatorzugabe kann dieses AB2-Molekül intermolekular zu einem hochverzweigten Polyurethan reagieren. Die Synthese des hochverzweigten Polyurethans kann vorteilhaft ohne vorherige Isolierung des ABx-Moleküls in einem weiteren Reaktionsschritt bei erhöhter Temperatur erfolgen, vorzugsweise im Bereich zwischen 30 und 80 °C. Bei Verwendung des geschilderten AB2-Moleküls mit zwei OH-Gruppen und einer NCO-Gruppe entsteht ein hochverzweigtes Polymer, welches pro Molekül eine freie NCO-Gruppe sowie - je nach Polymerisationsgrad - eine mehr oder weniger große Zahl von OH-Gruppen aufweist. Die Reaktion kann bis zu hohen Umsätzen durchgeführt werden, wodurch sehr hochmolekulare Strukturen erhalten werden. Sie kann aber auch beispielsweise durch Zugabe geeigneter monofunktioneller Verbindungen oder durch Zugabe einer der Ausgangsverbindungen zur Herstellung des AB2-Moleküls beim Erreichen des gewünschten Molekulargewichtes abgebrochen werden. Je nach der zum Abbruch verwendeten Ausgangsverbindung entstehen entweder vollständig NCO-terminierte oder vollständig OH-terminierte Moleküle.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.

Alternativ kann beispielsweise auch ein AB2-Molekül aus einem Mol Glycerin und 2 mol 2,4-TDI hergestellt werden. Bei tiefer Temperatur reagieren vorzugsweise die primären Alkoholgruppen sowie die Isocyanat-Gruppe in 4-Stellung und es wird ein Addukt gebildet, welches eine OH-Gruppe und zwei Isocyanat-Gruppen aufweist, welches wie geschildert bei höheren Temperaturen zu einem hochverzweigten Polyurethan umgesetzt werden kann. Es entsteht zunächst' ein hochverzeigtes Polymer, welches eine freie OH-Gruppe sowie - je nach Polymerisationsgrad - eine mehr oder weniger große Zahl von NCO-Gruppen aufweist.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.

Die Herstellung der hochverzweigten Polyurethane kann prinzipiell ohne Lösungsmittel, bevorzugt aber in Lösung erfolgen. Als Lösungsmittel prinzipiell geeignet sind alle bei der Umsetzungstemperatur flüssigen und gegenüber den Monomeren und Polymeren inerten Verbindungen geeignet.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.

Andere Produkte sind durch weitere Synthesevarianten zugänglich. AB3-Moleküle lassen sich beispielsweise durch Reaktion von Diisocyanaten mit Verbindungen mit mindestens 4 gegenüber Isocyanaten reaktiven Gruppen erhalten. Beispielhaft sei die Umsetzung von 2,4-Toluylendiisocyanat mit Tris(hydroxymethyl)aminomethan genannt.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.

Zum Abbruch der Polymerisation können auch polyfunktionelle Verbindungen eingesetzt werden, die mit den jeweiligen A-Gruppen reagieren können. Auf diese Art und Weise können mehrere kleine hochverzweigte Moleküle zu einem großen hochverzweigten Molekül verknüpft werden.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.

Hochverzweigte Polymere mit kettenverlängerten Ästen lassen sich beispielsweise erhalten, indem zur Polymerisationsreaktion neben den ABx-Molekülen zusätzlich im molaren Verhältnis 1:1 ein Diisocyanat und eine Verbindung, die zwei mit Isocyanatgruppen reaktive Gruppen aufweist, eingesetzt werden. Diese zusätzlichen AA- bzw. BB-Verbindungen können auch noch über weitere funktionelle Gruppen verfügen, die aber unter den gewählten Reaktionsbedingungen nicht reaktiv gegenüber den A- oder B-Gruppen sein dürfen. Auf diese Art und Weise können weitere Funktionalitäten in das hyperverzweigte Polymer eingebracht werden.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.

Weitere Synthesevarianten für hochverzweigte Polyurethane finden sich in den Anmeldungen mit den Aktenzeichen DE 100 13 187.5 und DE 100 30 869.4.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.

Die erhaltenen hochverzweigten und hochfunktionellen Polyurethane können bereits als solche in den erfindungsgemäßen Ausrüstungsmitteln eingesetzt werden, vorausgesetzt, die im Zuge der Synthese erhaltenen funktionellen Gruppen sind für die Anwendung der Polyurethane in gelöster oder dispergierter Form geeignet.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.

Die funktionellen Gruppen können aber auch, wie oben beschrieben, hydrophobiert, hydrophiliert oder umfunktionalisiert werden. Auf diese Art und Weise werden für den Einsatz als Lösung oder wässrige Dispersion besonders geeignete hochverzweigte Polyurethane zugänglich. Zur Umfunktionalisierung eignen sich aufgrund ihrer Reaktivität ganz besonders solche hochverzweigten Polyurethane, die Isocyanat-Gruppen aufweisen. Es können auch OH- oder NH2-terminierte Polyurethane mittels geeigneter Reaktionspartner umfunktionalisiert werden.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.

Bevorzugte Gruppen, die in die hochverzweigten Polyurethane eingeführt werden, sind -COOH, -CONH2, -OH, -NH2, -NHR, -NR2, -NR3 +, -SO3H und deren Salze. Speziell bevorzugt sind -NH2, -NHR, -NR2, und -NR3 + gemäß einer Ausführungsform der Erfindung und -COOH, -OH und -SO3H gemäß einer weiteren Ausführungsform der Erfindung.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.

Gruppen, die über ausreichend acide H-Atome verfügen, können durch Behandlung mit geeigneten Basen in die entsprechenden Salze überführt werden. Analog lassen sich basische Gruppen mit geeigneten Säuren in die entsprechenden Salze überführen. Dadurch lassen sich wasserlösliche hochverzweigte Polyurethane erhalten.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.

Durch Umsetzung NCO-terminierter Produkte mit Alkanolen und Alkylaminen, insbesondere Alkanolen und Alkylaminen mit C8-C40-Alkylresten lassen sich hydrophobierte Produkte erhalten.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.

Hydrophilierte, aber nicht ionische Produkte lassen sich durch Reaktion NCO-terminierter Polymere mit Polyetheralkoholen, wie beispielsweise Di-, Tri- oder Tetra- oder Polyethylenglykol erhalten.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.

Säuregruppen lassen sich beispielsweise durch Umsetzung mit Hydroxycarbonsäuren, Hydroxysulfonsäuren oder Aminosäuren einführen. Als Beispiele geeigneter Reaktionspartner seien 2-Hydroxyessigsäure, 4-Hydroxybenzoesäure, 12-Hydroxydodecansäure, 2-Hydroxyethansulfonsäure, Glycin oder Alanin genannt.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.

Durch Umsetzung mit Acrylatgruppen umfassenden Verbindungen wie Acrylatgruppen umfassenden Alkoholen wie 2-Hydroxyethylacrylat oder 2-Hydroxyethylmethacrylat lassen sich hochverzweigte Polyurethane erhalten, die polymerisierbare olefinische Gruppen aufweisen.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.

Oxidativ trocknende hochverzweigte Polyurethane können erhalten werden, indem man zunächst einfach oder mehrfach ungesättigte Fettsäuren, insbesondere C8-C40-Fettsäuren mit einem aliphatischen Alkohol mit mindestens zwei OH-Gruppen umsetzt, wobei mindestens eine OH-Gruppe nicht verestert werden darf. Beispielsweise können Linolsäure, Linolensäure oder Elaeostearinsäure umgesetzt werden. Der erhaltene Fettsäureester, der noch OH-Gruppen aufweist, wird dann mit den NCO-Gruppen umgesetzt.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.

Es können auch hochverzweigte Polyurethane erzeugt werden, die verschiedenartige Funktionalitäten aufweisen. Dies kann beispielsweise durch Umsetzung mit einem Gemisch verschiedener Verbindungen erfolgen, oder auch dadurch, dass man nur einen Teil der ursprünglich vorhandenen funktionellen Gruppen, beispielsweise nur einen Teil der OH- und/oder NCO-Gruppen, umsetzt.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.

Weiterhin kann man auch eine oder mehrere funktionelle Gruppen des hochverzweigten Moleküls mit faseraffinen Reagenzien, zum Beispiel mit Polyaminen, wie Polyethylenimin oder Polyvinylamin, umsetzen. Man erhält dadurch ein hochverzweigtes Polymer, das einen faseraffinen Molekülteil als Ankergruppe für die Faser besitzt.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.

Die Umfunktionalisierung des hochverzweigten Polyurethans kann vorteilhaft unmittelbar im Anschluss an die Polymerisationsreaktion erfolgen, ohne dass das NCO-teminierte Polyurethan vorher isoliert wird. Die Funktionalisierung kann aber auch in einer separaten Reaktion erfolgen.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.

Die erfindungsgemäß eingesetzten hochverzweigten Polyurethane weisen in der Regel im Mittel mindestens 4 und nicht mehr als 200 funktionelle Gruppen auf. Bevorzugt weisen die hochverzweigten Polyurethane 4 bis 150 und besonders bevorzugt 4 bis 100 funktionelle Gruppen auf. Bevorzugt eingesetzte hochverzweigten Polyurethane weisen ein gewichtsmittleres Molekulargewicht MW von 1000 bis 200 000 g/mol, bevorzugt 1000 bis 100 000 g/mol, auf.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.

Gegenstand der Erfindung ist außerdem die Verwendung von hochverzweigten Polymeren, insbesondere von hochverzweigten Polyurethanen, in Ausrüstungsmitteln zur Antiknitterausrüstung von cellulosehaltigen Textilien. Ausrüstungsmittel sind beliebige flüssige Formulierungen, die das hochverzweigte Polymer, insbesondere das hochverzweigte Polyurethan, zur Applikation auf das Textilgut in gelöster oder dispergierter Form enthalten. Die erfindungsgemäßen Ausrüstungsmittel können beispielsweise als Ausrüstungsmittel im engeren Sinne bei der Herstellung der Textilien oder in Form einer wässrigen Waschflotte oder als flüssiges Textilbehandlungsmittel vorliegen. Als Lösemittel eigenen sich z.B. Wasser, Alkohole wie Methanol, Ethanol und Propanol, THF oder deren Mischungen. So ist es beispielsweise möglich, im Zusammenhang mit der Textilherstellung die Textilien mit dem Ausrüstungsmittel zu behandeln. Textilien, die noch nicht oder nur unzureichend mit Ausrüstungsmittel behandelt worden sind, können beispielsweise im Heimbereich vor oder nach dem Waschen, beispielsweise beim Bügeln, mit einem Textilbehandlungsmittel, das die hochverzweigten Polymere enthält, behandelt werden. Es ist aber auch möglich, die Textilien im Hauptwaschgang oder nach dem Hauptwaschgang im Pflege- oder Weichspülgang der Waschmaschine mit hochverzweigten Polymeren zu behandeln.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.

Gegenstand der vorliegenden Erfindung ist auch die Verwendung der hochverzweigten Polymere, insbesondere der hochverzweigten Polyurethane, bei der Herstellung der Textilien, bei der Behandlung der Textilien vor und nach dem Waschen, im Textilwäsche-Hauptwaschgang, im Textilwäsche-Weichspülgang und beim Bügeln. Hierfür benötigt man jeweils unterschiedliche Formulierungen.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.

Bei der Behandlung vor oder nach der Textilwäsche kann ein Textilbehandlungsmittel als Ausrüstungsmittel eingesetzt werden, das außer einem hochverzweigten Polymer in gelöster oder dispergierter Form ein oberflächenaktives Mittel enthält. Bei dieser Behandlung werden die cellulosehaltigen Textilien beispielsweise mit den hochverzweigten Polymeren besprüht, wobei die Auftragsmenge im allgemeinen 0,01 bis 10 Gew.-%, vorzugsweise 0,1 bis 7, besonders bevorzugt 0,3 bis 4 Gew.-%, bezogen auf das Gewicht des trockenen Textilguts, betragen kann. Das Ausrüstungsmittel kann aber auch dadurch auf das Textilgut appliziert werden, indem man die Textilien in ein Bad taucht, das im allgemeinen 0,1 bis 10 Gew.-%, vorzugsweise 0,3 bis 5 Gew.-%, bezogen auf das Gewicht des trockenen Textilguts, eines hochverzweigten Polymers gelöst oder dispergiert enthält. Das Textilgut wird entweder nur kurzzeitig in das Bad getaucht oder kann auch darin für einen Zeitraum von beispielsweise 1 bis 30 Min. verweilen.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.

Die cellulosehaltigen Textilien, die mit dem Ausrüstungsmittel entweder durch Sprühen oder durch Tauchen behandelt worden sind, werden gegebenenfalls abgedrückt und getrocknet. Das Trocknen kann hierbei an der Luft erfolgen oder auch in einem Trockner oder auch dadurch, dass man das behandelte Textilgut heiß bügelt. Durch das Trocknen wird das Ausrüstungsmittel auf dem Textilgut fixiert. Die hierfür jeweils günstigsten Bedingungen können leicht mit Hilfe von Versuchen bestimmt werden. Die Temperatur beim Trocknen, einschließlich des Bügelns, beträgt im allgemeinen 40 bis 150 °C vorzugsweise 60 bis 110 °C. Für das Bügeln eignet sich insbesondere das Baumwollprogramm des Bügeleisens. Die Textilien, die nach dem oben beschriebenen Verfahren mit den hochverzweigten Polymeren in gelöster oder dispergierter Form behandelt worden sind, weisen einen ausgezeichneten Knitter- und Faltenschutz auf, der über mehrere Wäschen bestehen bleibt. Ein Bügeln der Textilien ist häufig nicht mehr erforderlich. Die so behandelten Textilien besitzen zusätzlich einen Faser- und Farbschutz.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.

Gegenstand der Erfindung ist auch ein Textilbehandlungsmittel, enthaltend

  • 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.

Bevorzugte Silicone sind aminogruppenhaltige Silicone, die vorzugsweise in microemulgierter Form vorliegen, alkoxylierte, insbesondere ethoxylierte Silicone, Polyalkylenoxid-Polysiloxane, Polyalkylenoxid-Aminopolydimethylsiloxane, Silicone mit quartären Ammoniumgruppen (Siliconquats) und Silicontenside. Geeignete Weichmacher oder Gleitmittel sind beispielsweise oxidierte Polyethylene oder paraffinhaltige Wachse und Öle. Geeignete wasserlösliche, filmbildende und adhesive Polymere sind beispielsweise (Co)polymere auf Basis von Acrylamid, N-Vinylpyrrolidon, Vinylformamid, N-Vinylimidazol, Vinylamin, N,N'-Dialkylaminoalkyl(meth)acrylaten, N,N'-Dialkylaminoalkyl(meth)acrylamiden, (Meth)acrylsäure, (Meth)acrylsäurealkylester und/oder Vinylsulfonat. Die vorstehend genannten basischen Monomeren können auch in quaternierter Form eingesetzt werden.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.

Falls die Textilvorbehandlungsformulierung auf das Textilgut gesprüht wird, kann die Formulierung zusätzlich ein Sprühhilfsmittel enthalten. In manchen Fällen kann es außerdem von Vorteil sein, der Formulierung Alkohole wie Ethanol, Isopropanol, Ethylenglykol oder Propylenglykol zuzusetzen. Weitere übliche Additive sind Duft- und Farbstoffe, Stabilisatoren, Faser- und Farbschutzadditive, Viskositätsmodifizierer, Soil-Release-Additive, Korrosionsschutzadditive, Bakterizide und Konservierungsmittel in den hierfür üblichen Mengen.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.

Das Texilbehandlungsmittel kann auch beim Bügeln des Textilguts nach der Wäsche im allgemeinen durch Sprühen appliziert werden. Das Bügeln wird dadurch nicht nur erheblich erleichtert, die Textilien werden zusätzlich mit einem langanhaltenden Knitter- und Faltenschutz ausgestattet.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.

Der Einsatz der hochverzweigten Polymere kann auch beim Waschen der Textilien im Hauptwaschgang der Waschmaschine erfolgen.The use of the highly branched polymers can also be done when washing the textiles in the main wash cycle of the washing machine.

Gegenstand der Erfindung ist eine feste Waschmittelformulierung, enthaltend

  • 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.

Geeignete anionische Tenside sind insbesondere:

  • (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 C13-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.

Die genannten anionischen Tenside werden dem Waschmittel vorzugsweise in Form von Salzen zugegeben. Geeignete Kationen in diesen Salzen sind Alkalimetallionen wie Natrium, Kalium und Lithium und Ammoniumionen wie Hydroxyethylammonium, Di(hydroxyethyl)ammonium und Tri(hydroxyethyl)ammonium.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.

Geeignete nichtionische Tenside sind insbesondere:

  • 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.

Geeignete anorganische Builder sind insbesondere:

  • 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 organische Cobuilder sind insbesondere niedermolekulare, oligomere oder polymere Carbonsäuren.

  • 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.

Eine erfindungsgemäße feste Waschmittelformulierung liegt üblicherweise pulver- oder granulatförmig oder in Extrudat- oder Tablettenform vor.A solid detergent formulation according to the invention is usually present in powder or granule form or in extrudate or tablet form.

Gegenstand der Erfindung ist weiterhin eine flüssige Waschmittelformulierung enthaltend

  • 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.

Es können die oben genannten Silicone; nichtionischen und anionischen Tenside, Builder und Cobuilder eingesetzt werden.It may be the above-mentioned silicones; nonionic and anionic surfactants, builders and cobuilders.

Eine detaillierte Beschreibung der genannten Waschmittelinhaltsstoffe findet man z.B. in WO 99/06524 oder WO 99/04313 und in Liquid Detergents, Editor: Kuo-Yann Lai, Surfactant Sci. Ser., Vol. 67, Marcel Decker, New York, 1997, S. 272-304.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.

Die Konzentration der hochverzweigten Polymere in der Waschflotte beträgt beispielsweise 10 bis 5000 ppm und liegt vorzugsweise in dem Bereich von 50 bis 1000 ppm. Die mit den hochverzweigten Polymeren im Hauptwaschgang der Waschmaschine behandelten Textilien knittern nicht nur deutlich weniger als unbehandelte Textilien. Sie sind auch leichter zu bügeln, weicher und glatter, dimensions- und formstabiler und sehen nach mehrmaligem Waschen aufgrund ihres Faser- und Farbschutzes weniger "gebraucht" aus, weisen also weniger Fusseln und Knoten und eine geringere Farbschädigung bzw. -verblassung auf.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.

Der Einsatz der hochverzweigten Polymere kann im sogenannten Weich- oder Pflegespülgang nach dem Hauptwaschgang erfolgen. Die Konzentration der hochverzweigten Polymere in der Waschflotte beträgt beispielsweise 10 bis 5000 ppm und liegt vorzugsweise in dem Bereich von 50 bis 1000 ppm. Für einen Weich- bzw. Pflegespüler typische Inhaltsstoffe können ggf. in der Spülflotte vorhanden sein. Auch die auf diese Weise behandelten Textilien besitzen nach dem Trocknen auf der Leine oder bevorzugt im Wäschetrockner einen sehr guten Knitterschutz, der mit den bereits oben beschriebenen positiven Auswirkungen auf das Bügeln verbunden ist. Der Knitterschutz kann durch ein einmaliges kurzes Bügeln der Textilien nach dem Trocknen noch deutlich verstärkt werden. Die Behandlung im Weich- oder Pflegespülgang wirkt sich zusätzlich günstig auf die Formstabilität der Textilien aus. Weiterhin wird die Bildung von Knoten und Fusseln gehemmt und werden Farbschädigungen unterdrückt.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.

Gegenstand der Erfindung ist auch ein Wäschepflegespülmittel, enthaltend

  • 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.

Bevorzugte kationische Tenside sind ausgewählt aus der Gruppe der quartären Diesterammoniumsalze, der quartären Tetraalkylammoniumsalze, der quartären Diamidoammoniumsalze, der Amidoaminester und Imidazoliumsalze. Diese sind vorzugsweise in einer Menge von 3 bis 30 Gew.-% in den Wäschepflegespülmitteln enthalten. Beispiele sind quartäre Diesterammoniumsalze, die zwei C11- bis C22-Alk(en)ylcarbonyloxy(mono- bis pentamethylen)-Reste und zwei C1- bis C3-Alkyl- oder -Hydroxyalkylreste am quartären N-Atom aufweisen und als Gegenion beispielsweise Chlorid, Bromid, Methylsulfat oder Sulfat tragen.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.

Quartäre Diesterammoniumsalze sind weiterhin insbesondere solche, die einen C11- bis C22-Alk(en)ylcarbonyloxytrimethylen-Rest, der am mittleren C-Atom der Trimethylen-Gruppierung einen C11- bis C22-Alk(en)ylcarbonyloxy-Rest trägt, und drei C1- bis C3-Alkyl- oder -Hydroxyalkylreste am quartären N-Atom aufweisen und als Gegenion beispielsweise Chlorid, Bromid, Methylsulfat oder Sulfat tragen.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.

Quartäre Tetraalkylammoniumsalze sind insbesondere solche, die zwei C1- bis C6-Alkyl-Reste und zwei C8- bis C24-Alk(en)yl-Reste am quartären N-Atom aufweisen und als Gegenion beispielsweise Chlorid, Bromid, Methylsulfat oder Sulfat tragen.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.

Quartäre Diamidoammoniumsalze sind insbesondere solche, die zwei C8- bis C24-Alk(en)ylcarbonylaminoethylen-Reste, einen Substituenten ausgewählt aus Wasserstoff, Methyl, Ethyl und Polyoxyethylen mit bis zu 5 Oxyethylen-Einheiten und als vierten Rest eine Methylgruppe am quartären N-Atom aufweisen und als Gegenion beispielsweise Chlorid, Bromid, Methylsulfat oder Sulfat tragen.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 sind insbesondere tertiäre Amine, die als Substituenten am N-Atom einen C11- bis C22-Alk(en)ylcarbonylamino(mono- bis trimethylen)-Rest, einen C11- bis C22-Alk(en)ylcarbonyloxy(mono- bis trimethylen)-Rest und eine Methylgruppe tragen.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.

Imidazoliniumsalze sind insbesondere solche, die in der 2-Position des Heterocyclus einen C14- bis C18-Alk(en)ylrest, am neutralen N-Atom einen C14- bis C18-Alk(en)ylcarbonyl(oxy oder amino)ethylen-Rest und am die positive Ladung tragenden N-Atom Wasserstoff, Methyl oder Ethyl tragen, Gegenionen sind hierbei beispielsweise Chlorid, Bromid, Methylsulfat oder Sulfat.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.

Die Erfindung wird durch die nachstehenden Beispiele naher erläutert.The invention will be explained in more detail by the following examples.

BeispieleExamples

Die Prozentangaben in den Beispielen bedeuten Gew.-%, sofern sich aus dem Zusammenhang nichts anderes ergibt.The percentages in the examples mean wt .-%, unless otherwise stated in the context.

Folgende Ausrüstungsmittel wurden verwendet:The following equipment was used: Ausrüstungsmittel AEquipment A

1 gew.-%ige alkalische Lösung des hochverzweigten Polyurethans A, das wie folgt hergestellt wurde:

  • 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.

Das feste Endprodukt wies folgende Parameter auf:

  • 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

Ausrüstungsmittel BFinishing equipment B

1 gew.-%ige alkalische Lösung des hochverzweigten Polyurethans B, das wie folgt hergestellt wurde:

  • 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.

Das Reaktionsprodukt wies folgende Parameter auf:

  • 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

Ausrüstungsmittel CEquipment C

1 gew.-%ige alkalische Lösung des hochverzweigten Polyurethans C, das wie folgt hergestellt wurde:

  • 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.

Das feste Endprodukt wies folgende Parameter auf:

  • 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

Ausrüstungsmittel DEquipment D

1 gew.-%ige alkalische Lösung des hochverzweigten Polyurethans D, das wie folgt hergestellt wurde:

  • 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.

Das Reaktionsprodukt wies folgende Parameter auf:

  • 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.

Ausrüstung von GewebeprobenEquipment of tissue samples

Flächengebilde aus Baumwolle (BW) der in Tabelle 1 jeweils angegebenen Größe mit einem Flächengewicht von 160 g/m2 wurden mit den Ausrüstungsmitteln A, B, C und D beidseitig besprüht, so daß die Auftragsmenge 2 %, bezogen auf das jeweilige Gewicht des trockenen Textilguts, betrug und dann in leicht feuchtem Zustand heiß gebügelt.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.

Die so behandelten Gewebeproben wurden zum Vergleich mit unbehandelten Gewebeproben gleicher Größe und in Gegenwart von Ballastgewebe mit einem Flüssigwaschmittel bei 40°C in einer automatischen Haushaltswaschmaschine (Beladung zwischen 1,5 und 3,0 kg) gewaschen und anschließend im Trommeltrockner getrocknet. Zur Anwendung kam ein Standardwasch- bzw. Standardtrocknungsprogramm (Programm Buntwäsche 40°C bzw. Programm Schranktrocken). Nach dem Trocknen erfolgte eine visuelle Benotung der flächigen Gewebeproben in Anlehnung an die AATCC Testmethode 124, wobei die Note 1 bedeutet, daß das Gewebe sehr knittrig ist und viele Falten aufweist, während die Note 5 für knitter- und faltenfreies Gewebe vergeben wurde. Die mit den Ausrüstungsmitteln A, B und C vorbehandelten Gewebeproben erhielten Noten zwischen 2,5 und 3,5. Im Gegensatz dazu erhielten die unbehandelten Gewebeproben jeweils Note 1. Tabelle 1: BW (40 cm x 40 cm) Beladung 1,5 kg BW (40 cm x 40 cm) Beladung 3,0 kg BW (40 cm x 80 cm) Beladung 1,5 kg unbehandelt 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 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.
EP01989443A 2000-11-13 2001-11-08 Highly branched polymers for the anti-crease dressing of cellulose containing textiles Expired - Lifetime EP1339910B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10056183A DE10056183A1 (en) 2000-11-13 2000-11-13 Highly branched polymers for anti-crease finishing of cellulose-containing textiles
DE10056183 2000-11-13
PCT/EP2001/012938 WO2002038851A1 (en) 2000-11-13 2001-11-08 Highly branched polymers for the anti-crease dressing of cellulose containing textiles

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EP1339910A1 EP1339910A1 (en) 2003-09-03
EP1339910B1 true EP1339910B1 (en) 2006-09-20

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EP (1) EP1339910B1 (en)
JP (1) JP2004513260A (en)
CN (1) CN1545584A (en)
AT (1) ATE340284T1 (en)
AU (1) AU2002227908A1 (en)
BR (1) BR0115300A (en)
CA (1) CA2426969A1 (en)
DE (2) DE10056183A1 (en)
ES (1) ES2272562T3 (en)
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WO (1) WO2002038851A1 (en)

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US20040016060A1 (en) 2004-01-29
WO2002038851A1 (en) 2002-05-16
AU2002227908A1 (en) 2002-05-21
EP1339910A1 (en) 2003-09-03
JP2004513260A (en) 2004-04-30
MXPA03004012A (en) 2003-08-19
BR0115300A (en) 2003-10-21
CA2426969A1 (en) 2002-05-16
DE10056183A1 (en) 2002-05-29
DE50111057D1 (en) 2006-11-02
CN1545584A (en) 2004-11-10
ATE340284T1 (en) 2006-10-15
ES2272562T3 (en) 2007-05-01

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