BR112019016441B1 - COPOLYMERS, PROCESS FOR PREPARING COPOLYMERS, COMPOSITIONS, AQUEOUS EMULSION, USE OF AQUEOUS COMPOSITIONS OR EMULSIONS, REPELLENT IMPREGNATION METHOD AND REPELLENT TEXTILE FABRIC - Google Patents

Abstract

The invention relates to copolymers comprising or consisting of, preferably consisting of, three components: component a) having at least one biuret or isocyanurate substructure, component b) selected from polysiloxanes and polyhydrocarbons, preferably polysiloxanes, component c ) comprising a hydrocarbon that is different from component b) and has at least 6 carbon atoms and not more than 3 heteroatoms selected from the group of N, O, S, wherein component b) is joined to 2 components a ) different or identical through at least two positions; and for the preparation and use thereof for finishing fabrics.

Description

[001] The invention refers to formulations based on water and/or organic solvents and their use as a finish on cloths.

[002] It is known that for finishing fabrics, water-based or solvent-based formulations composed of silicone oils, paraffins, fluorocarbon polymers (fluorocarbon is abbreviated to FC hereinafter) and other additives are used, which they impart particular hydrophobic effects to the finished cloth, so as to cope with stresses from rain, splashing water or moisture from other sources during the use of the cloth.

[003] Whereas the creation of water repellent effects with paraffin and silicone-based products merely causes hydrophobization of textile fibers, FC polymers also cause dirt and oil repellency. FC finishes are useful for a large number of items. They are used both in the clothing and household textile products sector and in the technical textile products sector. Typically, FC finishing products are based on polyurethanes or polyacrylates that contain perfluoroalkyl groups of different chain lengths. Aqueous products are generally applied through the exhaust process and filling process through spraying, foaming or filling, often in combination with other additives. These additives can be, for example, thermal curing resins based on methylol compounds that cause dimensional stability, washability and rigidity. For example, documents No. U.S. 6127507 and No. WO 2010/025398 disclose fluoroalkyl-containing polymers of this type.

[004] Substances known as extenders are also used. Typically, these are fatty acid-modified melanin resins, mixtures of wax and zirconium salts, or blocked polyisocyanates. The latter are often used in order to enhance the water and oil repellent effects of the FC finish and to increase wash permanence.

[005] A disadvantage is that, even after a few washes, both hydrophobicity and oleophobicity are largely reduced due to the loss of orientation of the active FC radicals in the polymer molecules, unless reorientation can occur through heat treatment. This means that cloths that have been treated in this way require heat treatment after washing in order to revitalize the desired effects. For example, ironing or at least drying in the laundry dryer at temperatures > 80 °C are a prerequisite for satisfactory repellency properties. A significant disadvantage is its long lifespan in nature and organisms. Therefore, CF polymers or their degradation products such as perfluorooctanoic acid accumulate in organisms, and are difficult to secrete from the human body. Studies have suggested liver-damaging, reprotoxic and carcinogenic properties. Among the most important sources of emissions are consequently carpets and textile products that have become dirt and water repellent, and fire extinguishing foam.

[006] As well as satisfactory initial hydrophobicity, stability of the finish to repeated washing is another important aspect. Therefore, there were already early developments that were intended to improve stability unsuitable for washing operations. For example, document No. DE 1017133 B describes hydrophobizing agents that must be produced by mixing a condensation product formed from hexamethyl ether of hexamethylolmelamine, stearic acid, stearic acid diglyceride and triethanolamine with paraffin. The products thus obtained in the form of flakes or lumps, before use, are converted to an applicable emulsion form of aqueous liquors by melting with hot water or steam and with the addition of acetic acid. However, a disadvantage of cloths and fiber materials finished in this way has been found to be the relatively large quantity applied, the chemical character of the formulation and especially the crosslinking of the fatty acid modified methioltriazine compound with itself and the functional groups of Native-based substrates were associated with a distinct increase in hand character hardness.

[007] Additionally, document No. U.S.5589563 discloses linear block copolymers prepared from diisocyanates by addition with exclusively difunctional compounds.

[008] Document No. WO 2016/049278 discloses non-fluorinated urethanes as coating materials, whose isocyanate-based structure derives from sugar alcohols.

[009] Methods for impregnating textile products using crosslinkable organopolysiloxanes have been proposed for a long time. Crosslinking can be carried out by condensation of Si-H- and Si-OH functional organopolysiloxanes with the aid of a catalyst as described in document No. U.S. 4098701. Similarly, crosslinking is possible by adding Si-H- organopolysiloxanes functional on olefinic radicals linked with SiC (US 4154714 and DE 3332997 A1). Due to the reactive nature of organopolysiloxanes of this type, the production of storage-stable formulations is difficult. Often, the components cannot be mixed until directly before use, which makes them laborious to work with in practice.

[010] Document No. WO 2000/029663 A2 describes formulations for permanent fiber finishing that comprise reaction products of polyisocyanurate functional components with silicone-free and/or silicone-containing softeners and, according to the examples, preferably include a hydrophilizing radical.

[011] Document No. DE 19744612 A1 describes emulsions of organosilicon compounds for the hydrophobization of construction materials with mineral and construction coatings, and also wood. Aqueous emulsions contain alkoxysiloxanes modified with long-chain hydrocarbon chains. However, no application to textile products is revealed. Additionally, U.S. 8318867 B2 describes copolymers based on a hard/soft concept with polyurethanes as the hard segment, polybutadienes and polycarbonates as soft segments, and polyfluoroalkyl compounds as surface active substance for finishing and adding plastics and to increase its thermal stability. With these systems, very satisfactory water-repellent effects can be achieved, but relatively high usage quantities are required. The effect of this is that the breathability of the finished textile product is reduced. Similar to the case of textile products treated with formulations containing CF, washing must be followed by a heat treatment, for example in a laundry dryer or by ironing, in order to restore the original level of effect.

[012] A representative that has a water-repellent effect that is known in nature is the lotus plant. The water falls in drops and in doing so takes all the dirt particles on the surface with it. What is responsible for this is a complex micro- and nanoscopic surface architecture that minimizes the adhesion of dirt particles. The disadvantage is that a slight decrease in the surface tension of the liquid (for example by adding milk) has the effect that the liquid can no longer be washed. The cause of self-cleaning is based on a hydrophobic twin structure of the surface. This twin structure is formed by a characteristic shaped epidermis and waxes present in it. These overlapping waxes are hydrophobic and form the second part of the twin structure. In this way, it is no longer possible for water to reach the interstices on the leaf surface, with the result that the contact area between water and the surface is reduced.

[013] Oil and water repellent systems are known in the insect world (Interface Science No. 14, pages 270 to 280, 2009) in Collembola, also called springtail. The breastplate cannot be moistened even by acetone and ethanol. This superhydrophobic armor is the result of its exclusive structure based on proteins and waxes.

[014] It was an objective of the present invention to provide structures containing silicone with marked microstructure that obtain ideal hydrophobic and oleophobic effects on cloths with low amounts of use.

[015] Surprisingly, copolymers containing not only polysiloxanes, but also additional components (synonymous with the term "substructures") such as polyisocyanates and larger organic hydrocarbyl radicals, as described in the claims, have both hydrophobic and oleophobic properties.

[016] The present invention provides copolymers comprising the following constituents or consisting of the following constituents, preferably consisting of the following features: component a) having at least one biuret or isocyanurate substructure, component b) selected from polysiloxanes and poly -hydrocarbons, preferably from among polysiloxanes, component c) which comprises a hydrocarbon that is different from component b) and has at least 6 carbon atoms and no more than 3 heteroatoms selected from the group of N, O, S, in which component b) is joined to 2 different or identical components a) through at least two positions.

[017] The present invention additionally provides a process for preparing the copolymers according to the invention.

[018] The present invention additionally provides compositions comprising the copolymers according to the invention or the process products according to the invention.

[019] The present invention additionally provides aqueous emulsions comprising the copolymers according to the invention or the process products according to the invention.

[020] The present invention additionally provides for the use of the copolymers according to the invention, the process products according to the invention and the compositions according to the invention for finishing fabrics.

[021] The present invention additionally provides a process for impregnating liquid and dirt repellent of textile fabrics using the copolymers according to the invention.

[022] The invention additionally provides repellent textile cloths comprising the copolymers according to the invention with retention or enhancement of tactile properties.

[023] The copolymers according to the invention have environmental advantages over FC polymers: • reduced environmental pollution • more environmentally compatible polymers that do not damage the environment even in the long term • no use of persistent compounds.

[024] An additional advantage of the copolymers of the invention is their extremely satisfactory mechanical stability in cloths.

[025] An additional advantage of the invention is that textile products finished with the copolymers according to the invention have unaltered breathability.

[026] An additional advantage of the invention is that the textile products finished with the copolymers according to the invention, even after multiple washings, have a high level of effect without any additional heat treatment.

[027] An additional advantage of the invention is that the coating of textile products with the copolymers according to the invention has an improvement in tactile properties and causes pleasant wearing comfort.

[028] An additional advantage of the copolymers according to the invention is their versatile applicability to cellulose and lignin-based fibers.

[029] An additional advantage is the reduction of washing water pollution compared to the previous technique both in production and in use.

[030] The copolymers according to the invention, the process according to the invention for preparing the copolymers, and the aqueous compositions and emulsions according to the invention and the inventive use thereof are described by way of example hereinafter, without no intention that the invention be restricted to these illustrative embodiments. When ranges, general formulas, or classes of compounds are specified below, they are intended to encompass not only the corresponding ranges or groups of compounds that are explicitly mentioned, but also all subranges and subgroups of compounds that can be derived by leaving individual values (ranges). ) or compounds. In which documents are cited for the purposes of the present description, the entire contents of which are intended to be part of the disclosure of the present invention. Where Content Figures (ppm or %) are given below, unless otherwise indicated, they are Figures in % by weight or ppm by weight (wppm). In the case of compositions, Figures of Content, unless otherwise noted, are based on the overall composition. The averages cited below in this document are numerical averages unless otherwise stated. Molar masses used are weight-average molar masses Mw unless expressly stated otherwise. Viscosity values cited in the context of this invention are, unless otherwise stated, dynamic viscosities that can be determined using methods familiar to those skilled in the art. Where measured values are cited below in this document, these measured values were determined at a pressure of 101.325 Pa and a temperature of 23 °C unless otherwise stated.

[031] The various fragments in formulas (I) and (VII) are in static distribution. Statistical distributions are of block construction, with any desired number of blocks and any desired sequence, or being subjected to a random distribution; they may also have an alternative construction, or otherwise form a gradient over the chain; more particularly, they can also form any mixed forms, in which groups with different distributions can optionally follow each other. The nature of specific modalities may result in restrictions on statistical distributions. In all regions not affected by the restriction, there is no change to the static distribution.

[032] The indices shown in formulas (I) and (VII) cited here, and the ranges of values for the declared indices, should be understood as the average values of the possible static distribution of the structures and/or mixtures thereof that are actually gifts. This also applies to structural formulas exactly reproduced by themselves as such.

[033] Anywhere molecules/molecule fragments have one or more stereocenters or can be differentiated into isomers due to symmetries or can be differentiated into isomers due to other effects, for example, restricted rotation, all possible isomers are included by the present invention.

[034] In connection with this invention, the word fragment “poly” covers not only exclusively compounds with at least 3 repeating units of one or more monomers in the molecule, but especially also those compositions of compounds that have a molecular weight distribution and at the same time they have an average molecular weight of at least 200 g/mol. This definition takes into account the fact that it is common in the field of industry in question to refer to such compounds as polymers even if they do not appear to conform to a definition of polymer according to the OECD or REACH guidelines.

[035] The indices cited in this document and the value ranges for the indicated indices can be understood as average values for the possible static distribution of actual existing structures and/or mixtures thereof. This applies equally to structural formulas which, as such, are reproduced exactly by themselves, such are for formula (I) and formula (VII), for example.

[036] Preferably, the copolymer consists of components a), b) and component c), wherein one or more selected from components a), b) and c) may be present in each case.

[037] More preferably, the copolymer according to the invention is free of isocyanate groups.

[038] More preferably, the copolymer is free of halogen atoms, more preferably, free of fluorine atoms.

[039] More preferably, the copolymer is free of polyether structures, more preferably, free of oxyalkylene fragments linked together.

[040] More preferably, the copolymer has components a) and c) in a ratio of the number of c) divided by the number of a) of 1 to 3, more preferably, of 1.3 to 2.7, particularly, preferably, from 1.6 to 2.4 and, with special preference, from 1.8 to 2.2.

[041] Preferably, component a) in each case has two or more biuret or isocyanurate substructures, more preferably, from more than 1 to 4, even more preferably, from 1.2 to 3, with particular preference, from 1.3 to 2.5, and, with special preference, from 1.4 to 2 biuret or isocyanurate substructures.

[042] More preferably, the copolymer according to the invention has components a) and c) in a ratio of the number of c) divided by the number of a) of 1 to 3, more preferably, of 1.3 to 2.7 , with particular preference, from 1.6 to 2.4 and, with special preference, from 1.8 to 2.2; and has, in component a), two or more biuret or isocyanurate substructures in each case, more preferably, from more than 1 to 4, even more preferably, from 1.2 to 3, with particular preference, from 1 .3 to 2.5 and, with special preference, from 1.4 to 2 biuret or isocyanurate substructures.

[043] More preferably, component a) is independently identical or different biuret substructures of Formula (III) and isocyanurate substructures of Formula (IV) on what

[044] L is divalent radicals of tolyl (2,4-; 2,6-), ethylphenyl, 1,5-naphthyl, α,w- tetramethylene, α,w-hexamethylene, α,w-dodecamethylene, α,w -2-methylpentamethylene, α,w-2,2,4-trimethylhexamethylene, cyclohexyl (1,4-), 1-methylcyclohexyl (1,3-; 1,4-; 2,6-), 2,2,6 -trimethylcyclohexyl, isophorone (3,3,5-trimethylcyclohexyl), 4,4'-dicyclohexylmethyl, 4,4'-dicyclohexylpropane-(2,2), 4,4'-diphenylmethane, preferably hexamethylene, 4,4'- diphenylmethane and isophorone.

[045] For example, divalent L radicals derive from diisocyanates selected from toluene 2,4-/2,6-diisocyanate (TDI), diphenylmethane 4,4'-diisocyanate (MDI), naphthyl 1,5-diisocyanate (NDI ), dicyclohexylmethane 4,4'-diisocyanate, 3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate = IPDI), butane 1,4-diisocyanate, hexane 1,6-diisocyanate (HDI), 2- methylpentane 1,5-diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate (TMDI), dodecane 1,12-diisocyanate, cyclohexane 1,4-diisocyanate, 3,3'-dimethyldicyclohexylmethane 4,4' - diisocyanate, dicyclohexylpropane-(2,2)-4,4'-diisocyanate, 3-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane (MCI), 2-methylcyclohexane 1,3-diisocyanate.

[046] Rx is independently the binding site for component b) and component c), and indicates a urethane group or urea group in the case of binding to component b), and indicates a urethane group, a urea group or a thiourea group in the case of bonding to component c), wherein these urethane, urea and thiourea groups are bonded via the nitrogen atom to formula (III) and formula (IV), or Rx indicates a bond to an additional biuret or isocyanurate substructure, preferably with connection of biuret substructures to biuret substructures and preferably of isocyanurate substructures to isocyanurate substructures.

[047] The connection between component a) and component b) can be represented by formula (V):

[048] The connection between components a) and c) can be represented by formula (VI): wherein R8 is hydrogen or a substituted or unsubstituted C1-C30-alkyl, preferably substituted or unsubstituted C1-C30-alkyl which may also be interrupted by heteroatoms, C3-C30-cyclic alkyl, C6-C30-substituted aryl or unsubstituted, with R8 being preferably a C1-C5-alkyl.

[049] If appropriate, the N-H groups in formulas (V) and (VI) can react with additional isocyanate groups to generate additional allophanates and biuret structures.

[050] More preferably, component a) has both exclusively biuret substructures and exclusively isocyanurate substructures, with component a) particularly and preferably having exclusively isocyanurate substructures.

[051] More preferably, component b) is linked exclusively to component a). More preferably, component a) and component b) are linked together by means of urethane or urea groups.

[052] More preferably, component c) is linked exclusively to component a). Even more preferably, component a) and component c) are linked together by means of urethane, urea and/or thiourea groups.

[053] Component b) is selected from the group consisting of polysiloxanes and polyhydrocarbons. It is especially preferred that component b) is selected from the group consisting of polysiloxanes.

[054] Preferably, the polyhydrocarbon of component b) is a linear or branched, saturated or unsaturated hydrocarbon.

[055] More preferably, the polyhydrocarbon of component b) has one or more double bonds and/or triple bonds that can be isolated, conjugated or accumulated.

[056] With special preference, the polyhydrocarbon of component b) has 20 to 400 carbon atoms, more preferably 40 to 200, with special preference 60 to 120, carbon atoms.

[057] More preferably, component b) is selected from the group comprising polysiloxanes and polybutadienes, preferably polysiloxanes.

[058] Preferably, the polysiloxane is a compound of Formula (I) M1a1M2a2M3a3D1b1D2b2D3b3TcQd (I) with M1 = [R13SiO1/2], M2 = [R2R12SiO1/2], M3 = [R3R12SiO1/2], D1 = [R12SiO2/2 ], D2 = [R1R2SiO2/2], D3 = [R1R3SiO2/2], T = [R1SiO3/2], Q = [SiO4/2], where a1 = 0 to 20, preferably 1 to 10, especially 2 to 5; a2 = 0 to 10, preferably 0 to 5, especially 0; a3 = 0 to 20, preferably 1 to 10, especially 2 to 5; b1 = 1 to 1,000, preferably 5 to 500, especially 10 to 200; b2 = 0 to 10, preferably 0 to 5, especially 0; b3 = 0 to 20, preferably more than 0 to 10, especially 1 to 5; c = 0 to 10, preferably more than 0 to 5, especially 1 to 5; d = 0 to 50, preferably 0 to 10, especially 0 to 2; provided that at least one of the indices a3 and b3 is greater than 1, the total sum of a3 and b3 preferably being at least 2; R1 = independently, identical or different linear or branched, saturated or unsaturated hydrocarbyl radicals having 1 to 30 carbon atoms or aromatic hydrocarbyl radicals having 6 to 30 carbon atoms, Preferably, alkyl radicals having 1 to 14 atoms carbon or monocyclic aromatics, more preferably methyl, ethyl, propyl or phenyl, especially methyl; R2 = independently identical or different linear or branched, saturated or unsaturated, optionally substituted hydrocarbyl radicals, wherein preferred hydrocarbons have 2 to 30 carbon atoms, more preferably 2 to 16 carbon atoms, wherein substituents may be selected among methoxy, ethoxy, propoxy, butoxy, pentoxy and glycidyloxy, with R2 being, preferably, an alkylene radical substituted by glycidyloxy having 2 to 6 carbon atoms, with R2 being, with special preference, a glycidyloxypropyl radical; R3 = a divalent hydrocarbon having 2 to 8 carbon atoms, preferably 2 to 6, with special preference 2 to 3, whose second bond is the binding site to component a) preferably through a urethane or urea group. Preferably, the polybutadiene is a compound of Formula (VII) wherein x = 0.3 to 0.8, preferably 0.4 to 0.7, with special preference, 0.5 to 0.6, y = 0.01 to 0.35, preferably 0.1 to 0.3 , z = 0.1 to 0.5, preferably 0.15 to 0.3, the total sum of x, y and z is 1, α = 5 to 100, preferably 10 to 50, with special preference, 15 to 30, R9 is the site of attachment to component a) preferably through a urethane or urea group.

[059] More preferably, component c) is a hydrocarbon that has exactly one binding site for component a). The hydrocarbon has, in addition to carbon and hydrogen, no more than 3 heteroatoms, more preferably no more than 2 heteroatoms, with particular preference no more than one heteroatom, and with special preference no heteroatoms. If component c) has heteroatoms, they are selected from the group of N, O, S.

[060] Component c) may also consist of a mixture of hydrocarbons.

[061] Preferably, the hydrocarbon has 6 to 30 carbon atoms, preferably 12 to 26, more preferably, 14 to 20.

[062] More preferably, the hydrocarbon has an uninterrupted chain of at least 6 carbon atoms, preferably 6 to 21 carbon atoms.

[063] Similarly, more preferably, the hydrocarbon has one or more double bonds and/or triple bonds that can be isolated, conjugated or accumulated.

[064] More preferably, the hydrocarbon has aromatic rings, preferably one or more benzene rings, with one of the aromatic rings, particularly and preferably, the binding site for component a).

[065] With more particular preference, the copolymers of the invention have, as component a), independently identical or different biuret substructures of Formula (III) and isocyanurate substructures of Formula (IV) wherein L is divalent radicals of tolyl, ethylphenyl, 1,5-naphthyl, α,w-hexamethylene, isophorone, 2,2,6-trimethylcyclohexyl, 4,4'-dicyclohexylmethyl, 4,4'-diphenylmethane, preferably hexamethylene and isophorone, Rx is independently the binding site for component b) and component c), and indicates a urethane group or urea group in the case of binding to component b), and indicates a urethane group, a urea group or a thiourea group in the case of bonding to component c), wherein these urethane, urea and thiourea groups are bonded via the nitrogen atom to formula (III) and formula (IV), or Rx indicates a bond to an additional biuret or isocyanurate substructure, preferably with connection of biuret substructures to biuret substructures and preferably of isocyanurate substructures to isocyanurate substructures; and have, as component b), preferably a polysiloxane of Formula (I) M1a1M2a2M3a3D1b1D2b2D3b3TcQd (I) with M1 = [R13SiO1/2], M2 = [R2R12SiO1/2], M3 = [R3R12SiO1/2], D1 = [R12SiO2/ 2], D2 = [R1R2SiO2/2], D3 = [R1R3SiO2/2], T = [R1SiO3/2], Q = [SiO4/2], where a1 = 0 to 20, preferably 1 to 10, especially 2 to 5; a2 = 0 to 10, preferably 0 to 5, especially 0; a3 = 0 to 20, preferably 1 to 10, especially 2 to 5; b1 = 1 to 1,000, preferably 5 to 500, especially 10 to 200; b2 = 0 to 10, preferably 0 to 5, especially 0; b3 = 0 to 20, preferably more than 0 to 10, especially 1 to 5; c = 0 to 10, preferably more than 0 to 5, especially 1 to 5; d = 0 to 50, preferably 0 to 10, especially 0 to 2; provided that at least one of the indices a3 and b3 is greater than 1, preferably greater than 2; R1 = independently, identical or different linear or branched, saturated or unsaturated hydrocarbyl radicals having 1 to 30 carbon atoms or aromatic hydrocarbyl radicals having 6 to 30 carbon atoms, Preferably, alkyl radicals having 1 to 14 atoms carbon or monocyclic aromatics, more preferably methyl, ethyl, propyl or phenyl, especially methyl; R2 = independently identical or different linear or branched, saturated or unsaturated, optionally substituted hydrocarbyl radicals, wherein preferred hydrocarbons have 2 to 30 carbon atoms, more preferably 2 to 16 carbon atoms, wherein substituents may be selected among methoxy, ethoxy, propoxy, butoxy, pentoxy, glycidyloxy, with R2 being, preferably, an alkylene radical substituted by glycidyloxy having 2 to 6 carbon atoms, with R2 being, with special preference, a glycidyloxypropyl radical; R3 = a divalent hydrocarbon having 2 to 8 carbon atoms, preferably 2 to 6, with special preference, 2 to 3, the second bond of which is the binding site to component a) preferably through a urethane or urea group; and have, as component c), hydrocarbons that have exactly one binding site to component a), the hydrocarbons preferably having, in addition to carbon and hydrogen, no more than 3 heteroatoms, more preferably no more than 2 heteroatoms , with particular preference no more than one heteroatom and, with particular preference, no heteroatoms; if component c) has heteroatoms, these are preferably selected from the group of N, O, S.

[066] With special preference, the copolymers according to the invention have in component a), as divalent radical L in formula (III) or (IV), hexamethylene, 4,4'-diphenylmethane and isophorone; in component b), a siloxane of Formula (I) with the indices a3 = 2 to 5 a1 = 0 to 1 a2 = 0 b2 and b3 = 0 d = 0 R1 = methyl or phenyl in component c), a hydrocarbon that is free of heteroatoms and has aromatic rings, preferably one or more benzene rings, with one of the aromatic rings having, particularly and preferably, the binding site for component a).

[067] The copolymers according to the invention can be prepared according to prior art processes, but preferably by the process according to the invention, in which, in the first step, an intermediate having components a) and components c) is prepared and, in the second step, the intermediates are converted into the copolymer according to the invention.

[068] The process according to the invention for the preparation of the copolymers according to the invention can preferably be carried out in such a way that it comprises two process steps, i.e. 1. preparation of an intermediate comprising component a) and component c), and 2. reaction of the intermediate (from the 1st process step) with polymers having amine and/or hydroxyl groups, preferably polysiloxanes, to generate the copolymers according to the invention (2nd process step). This corresponds to a preferred embodiment of the invention.

[069] Both process steps of the aforementioned preferred embodiment of the invention (preparation of an intermediate that has component a) and component c), and reaction of the intermediate with polymers that have amine and/or hydroxyl groups to generate the copolymers of the invention (2a process step)), can be carried out in the process according to the invention either as a one-pot reaction, as successive, separately conducted steps, or under measurement control, but preferably under measurement control. The reaction can be carried out in a batch, semi-batch or continuous process. The one-pot reaction is especially preferred for process step 2.

[070] Preferably, in the 1st stage of the process according to the invention, polyisocyanates containing biuret and/or isocyanurate are reacted with reactive diluents.

[071] Preferably, in the first step, isocyanate groups are converted into urethane and/or urea groups; the products formed here correspond to the intermediates according to the invention.

[072] More preferably, in the first step, half to three-quarters of the isocyanate groups are converted.

[073] In the 2nd step of the process according to the invention, the intermediates are reacted with polymers that bear amine and/or hydroxyl groups, preferably polysiloxanes, to generate the copolymers according to the invention.

[074] Preferably, the process products, after the 2nd step, are checked for the absence of isocyanate groups as described in the examples. If the test is negative, that is, if isocyanate groups are still present, the batch is discarded.

[075] The process according to the invention can be carried out in the presence or absence of a solvent. Suitable inert organic solvents used are preferably anhydrous aliphatic and alicyclic hydrocarbons, e.g. hexane, heptane, cyclohexane, and ethers, e.g. diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diisopropyl ether, esters, e.g. ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, amyl acetate, ketones, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof same.

[076] The reactants may be present here in any desired concentration in a solvent, for example 5% to 99% by weight, preferably 20% to 90% by weight, with special preference 40% to 90% by weight.

[077] In a preferred embodiment, the process according to the invention can be conducted at a temperature of 10 °C to 150 °C, preferably 25 °C to 100 °C, more preferably, 40 °C to 90 °C. °C.

[078] In a preferred embodiment, the process according to the invention can preferably be conducted at a pressure of 50 to 2,000 kpa (0.5 to 20 bar), preferably 100 to 500 kpa (1 to 5 bar), preferably special at standard pressure.

[079] The reaction according to the invention can be carried out both in daylight and with the exclusion of light, preferably in daylight.

[080] The reaction according to the invention can be carried out either under inert conditions (nitrogen, argon) or under an oxygen and/or air atmosphere, preferably under a nitrogen atmosphere.

[081] The polyisocyanates containing biuret- and/or isocyanurate used in the 1st stage of the process are preferably trimers, tetramers, pentamers, hexamers and heptamers of bifunctional isocyanates, in which the isocyanates are aromatic or aliphatic, preferably aliphatic. Bifunctional isocyanates may be selected from the group comprising toluene 2,4-/2,6-diisocyanate (TDI), diphenylmethane 4,4'-diisocyanate (MDI), naphthyl 1,5-diisocyanate (NDI), 4, 4'-dicyclohexylmethane diisocyanate, 3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate = IPDI), 1,4-butane diisocyanate, 1,6-hexane diisocyanate (HDI), 1,5 -2-methylpentane diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate (TMDI), dodecane 1,12-diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-3,3-diisocyanate '-dimethyldicyclohexylmethane, dicyclohexylpropane-(2,2)-4,4'-diisocyanate, 3-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane (MCI), 1,3-2-methylcyclohexane diisocyanate, preferably 3-isocyanatomethyl isocyanate - 3,3,5-trimethylcyclohexyl (isophorone diisocyanate = IPDI), 1,6-hexane diisocyanate (HDI), with particular preference, 1,6-hexane diisocyanate (HDI).

[082] Some of these isocyanates have stereocenters. In particular, reference is made to isophorone isomers. All conceivable isomers are expressly incorporated within the scope of this invention. Thus, for example, isophorone diisocyanate can be differentiated into a cis isomer and a trans isomer. Particular preference is given to an isophorone diisocyanate of a cis/trans mixture of 5:1 to 1:5, preferably 3:1 to 1:3, more preferably 1:1. A particularly preferred commercial product consists of a 3:1 cis/trans mixture. The use of commercial isophorone diisocyanate is preferred. Isophorone Diisocyanate is obtainable under other names which are included as synonyms within the scope of this invention: 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 5-isocyanate-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane, CA RN: 4098-71-9. Several trade names are common; they often contain the name of the precursor molecule isophorone, although other trade names are also common: for example Desmodur®I (BAYER), Isocur IPDI 22-200 (ISO-ELEKTRA), VESTANAT® IPDI (EVONIK INDUSTRIES), which are similarly incorporated within the scope of the present invention. Common specifications for isophorone diisocyanate are: total chloride content <400 mg/kg, hydrolysable chloride <200 mg/kg, purity >99.5% by weight, refractive index n25D 1.483 (DIN 51 423, part 2), NCO 37.5 to 37.8% by weight (EN ISO 11 909 / ASTM D 2572), commercial product is described as colorless to light yellow

[083] Polyisocyanates containing biuret and/or isocyanurate used preferably in the 1st stage of the process can be used individually or as mixtures. They may be identical or different polyisocyanates. If, for example, different polyisocyanates are used, component b) can be joined to two different components a). If, for example, only one polyisocyanurate is used, component b) is joined to 2 identical components a). Preferably, component b) is joined to 2 identical components a).

[084] Reactive diluents in the context of the invention are preferably primary and/or secondary monoamines, monoalcohols and/or monothiols, whose hydrocarbons each have 6 to 30 carbons, and which, preferably, have, separated from carbon and hydrogen, no more than 3 heteroatoms, with more preference, not more than 2 heteroatoms, with particular preference, not more than one heteroatom, and with special preference, no heteroatoms. If the hydrocarbon has heteroatoms, these are preferably selected from the group of N, O, S. The terms "monoamines", "monoalcohols" and "monothiols" are known to those skilled in the art as compounds that have exclusively only one of the functional groups listed; these compounds are thus explicitly defined as having only one of the listed functional groups.

[085] Preferably, the hydrocarbon has 6 to 30 carbon atoms, preferably 12 to 26, more preferably, 14 to 20.

[086] More preferably, the hydrocarbon has an uninterrupted chain of at least 6 carbon atoms, preferably 6 to 21 carbon atoms.

[087] Similarly, more preferably, the hydrocarbon has one or more double bonds and/or triple bonds that can be isolated, conjugated or accumulated.

[088] More preferably, the hydrocarbon has aromatic rings, preferably one or more benzene rings, with one of the aromatic rings having, particularly and preferably, the binding site for component a).

[089] For the reaction of polyisocyanates that contain biuret and/or isocyanurate with reactive diluents to form intermediates that have component a) and component c), and also intermediates with polymers that have amine and/or hydroxyl groups to generating the copolymers of the invention, it is preferable to accelerate the reaction by catalysis. Catalysts used are the tin, bismuth and titanium catalysts known to those skilled in urethane chemistry, such as dibutyltin laurate, dioctyltin diketonate, dibutyltin dilaurate, dioctyltin dilaurate, available for example under the trade name TIB KAT® 216 (Goldschmidt TIB / TIB Chemicals), dibutyltin diacetylacetonate, dibutyltin diacetate, dibutyltin dioctoate, or dioctyltin diacetylacetonate, Borchi® catalysts, bismuth oxides, bismuth carboxylate, available for example under the trade name TIB KAT® 722 (Goldschmidt TIB / TIB Chemicals), bismuth methanesulfonate, bismuth nitrate, bismuth chloride, triphenylabismuth, bismuth sulfide, and also preparations comprising these catalysts, and titanates, e.g. titanium(IV) isopropoxide, iron(III) compounds ), for example iron(III) acetylacetonate, and aluminum compounds such as aluminum triisopropoxide, aluminum trisec-butoxyoxide and other alkoxides and also aluminum acetylacetonate.

[090] Furthermore, zinc salts, such as zinc octoate, zinc acetylacetonate and zinc 2-ethylcaproate, or tetraalkylammonium compounds, such as N,N,N-trimethyl-N-2-hydroxypropylammonium hydroxide, are also suitable. , N,N,N-trimethyl-N-2-hydroxypropylammonium 2-ethylexanoate, or choline 2-ethylexanoate. Preference is given to the use of zinc octoate (zinc-2-ethylexanoate), dioctyltin dilaurate, bismuth oxides, bismuth carboxylate, bismuth catalyst preparations and/or the tetraalkylammonium compounds, and particular preference is given to the use of zinc octoate. zinc, dioctyltin dilaurate and/or bismuth carboxylate, and also preparations with bismuth catalysts.

[091] The catalyst is preferably used in concentrations of 5 to 5,000 ppm. The amount in which the catalyst is used can considerably influence the composition of the final product. For different catalysts, it may be advisable to select different usage concentrations. For example, organotin catalysts can be used preferably in concentrations of 5 to 150 ppm, and bismuth carboxylates, preferably in concentrations of 300 to 2000 ppm. Concentration figures are based on the respective total sum of co-agents present, neglecting additional non-reactive constituents, e.g. solvents.

[092] As an additional component step for preparing the polymer of the invention, a subsequent distillation/purification of the conversion products may be advantageous. Distillation/purification can be carried out with the aid of a rotational evaporator, for example, preferably, at a temperature of 20 °C to 250 °C, preferably 40 °C to 180 °C and with particular preference, 50 °C to 150 °C. °C. The pressure here is preferably 0.00001 to 7.5 Mpa (0.0001 to 0.75 bar), preferably more than 0.0001 to 0.02 Mpa (0.001 to 0.2 bar), and, with particular preference, 0.001 to 0.01 Mpa (0.01 to 0.1 bar). Distillation/purification may in particular be advantageous for removing solvents.

[093] The products of the process according to the invention may have structures that lack component b). Preferably, the products of the process include those products that have only component a) and component c) to an extent of no more than 15% by weight, preferably to an extent of 0.01 percent to 10 percent by weight. .

[094] Compositions according to the invention also comprise, as well as the copolymers according to the invention or the process products according to the invention, additives that can be selected from the list comprising intensifiers, emulsifiers, solvents, perfume, perfume carriers, colorants, viscosity regulators, non-foaming agents, preservatives, active antimicrobial ingredients, germicides, fungicides, antioxidants, organic solvents, non-siloxane-containing polymers and other non-inventive siloxane-containing polymers, e.g. silicone oils , surfactants, auxiliaries, bleaches, bleach activators, enzymes, fluorescers, foam inhibitors, anti-deposition agents, optical brighteners, aging inhibitors, anti-shrinkage agents, anti-wrinkle agents, dye transfer inhibitors, corrosion inhibitors, antistatics, bitter substances, ironing aids, repellency imparting and impregnating agents, anti-swelling and anti-slip agents, neutral filling salts and UV absorbers. It is possible here that substances from one class also exhibit efficacy in another class.

[095] Aqueous emulsions according to the invention also comprise, as well as the copolymers according to the invention or the process products according to the invention, additives that can be selected from the list in the preceding paragraph.

[096] Preferred compositions according to the invention or aqueous emulsions according to the invention are especially concentrates, compound/emulsion concentrates and/or aqueous formulations, aqueous emulsions and/or solutions thereof, or a formulation or emulsion in organic compounds such as polyethers, polyols, alcohols.

[097] More particularly, the compositions according to the invention may contain between 0.001% and 25% by weight, more preferably 0.01% to 15% by weight, based on the total mass of the fabric softener, of one or more different additives or auxiliaries.

[098] Additionally, particularly preferred compositions according to the invention are concentrates containing the copolymers according to the invention or the process products according to the invention in concentrations of about 90% to 99.99% by weight, based in the total mass of concentrate, to which only small proportions of solvents were added. Concentrates are preferably non-aqueous solutions.

[099] Additional particularly preferred compositions according to the invention are emulsion compounds or concentrates containing the copolymers according to the invention or the process products according to the invention in concentrations of 40% to 90% by weight, preferably, 50% to 80% by weight, based on overall composition. Additional constituents of these compositions are water and/or solvents selected from the group of glycols, unbranched and/or branched alcohols and/or alkyl ethers having 1 to 6 carbon atoms and optionally one or more non-ionic emulsifiers, e.g. , an alcohol ethoxylate that has 3 to 25 ethylene oxide units. Composition and emulsion compounds are generally water-soluble or self-emulsifiable.

[0100] Particularly preferred aqueous emulsions according to the invention are fabric softeners for treating textile fabrics.

[0101] Especially preferred compositions according to the invention are cloth softeners for the temporary or permanent finishing of textile products.

[0102] Cloths in the context of this invention are solids or composites of fibers, such as wood, cotton, polyester, polyamide, synthetic fibers, paper and cardboard, viscose, cellulose and/or lignin-based fibers.

[0103] The cloths are preferably selected from the group comprising woven cloths, textile woven cloths, loop-formed meshes, loop-drawn meshes, non-woven fabrics, fabrics (paper fibers) and/or fibers from natural raw materials and/or or synthetics, leather, hair, fur and wood.

[0104] The compositions according to the invention may optionally comprise additional textile product softeners. There are one or more cationic textile softening compounds that have one or more long-chain alkyl groups in a molecule. Widely used cationic textile softening compounds include, for example, methyl-N-(2-hydroxyethyl)-N,N-di(tallowacyloxyethyl)ammonium or N,N-dimethyl-N,N-di(tallowacyloxyethyl)ammonium compounds )ammonium. Suitable additional ammonium compounds are disclosed by document No. U.S. 2010/0184634 in paragraphs [0027] to [0068], the explicit content of the disclosure in this regard is incorporated into this disclosure by reference.

[0105] By diluting with water, it is possible, for example, to produce fabric softeners according to the invention from concentrates, emulsion concentrates and formulations according to the invention.

[0106] The aqueous emulsions according to the invention as softeners for textile cloths contain the copolymers according to the invention or the process products according to the invention in proportions of 0.1% to 10% by weight, preferably 0. .3% to 5% by weight, in particular 0.5% to 3% by weight, based on the general formulation.

[0107] Emulsifiers used are typically fatty alcohol ethoxylates that have ethoxylation levels between 3 and 12, specifically, in a ratio of copolymer to fatty alcohol ethoxylate of 5:1 to 1:1. High boiling glycols such as dipropylene glycol or butyl diglycol are also employed.

[0108] Preferably, emulsifiers are present in the compositions according to the invention and the aqueous emulsions according to the invention to an extent of 0.1% to 5% by weight, more preferably to an extent of 0.5% to 2% by weight.

[0109] As perfume, it is possible to use all fragrances of fragrance mixtures that are known to be suitable for aqueous fabric softeners from the prior art, preferably in the form of a perfume oil. Examples of fragrances or essences are disclosed, inter alia, in document no DE 197 51 151 A1, page 4 lines 11 to 17. More particularly, the compositions according to the invention may contain between 0.01% and 10%, more preferably , 0.1% to 5% by weight, of one or more fragrances or fragrance mixtures.

[0110] Dyes used can be any dyes known to be suitable for aqueous fabric softeners from the prior art, with preference being given to water-soluble dyes. Examples of suitable commercial water-soluble dyes are SANDOLAN® Walkblau NBL 150 (manufacturers: Clariant) and Sicovit® Azorubin 85 E122 (manufacturers: BASF). More particularly, the compositions according to the invention may contain between 0.001% and 0.1% by weight, more preferably 0.002% to 0.05% by weight, of one or more dyes or dye mixtures.

[0111] As a viscosity regulator to reduce viscosity, the aqueous cloth softener may comprise an alkali metal or alkaline earth metal salt, preferably calcium chloride, in an amount of 0.05% to 2% by weight.

[0112] As a viscosity regulator to increase viscosity, the aqueous cloth softener may comprise a thickening agent known to be suitable from the prior art, with preference being given to polyurethane agents known from document No. WO 2007/125005 . Examples of suitable thickening agents are TEGO® Visco Plus 3030 (manufacturers: Evonik Tego Chemie), Acusol® 880 and 882 (manufacturers: Rohm & Haas), Rheovis® CDE (manufacturers: BASF), Rohagit® KF 720 F (manufacturers: Evonik Rohm GmbH) and Polygel® K100 from Neochem GmbH.

[0113] Non-foaming agents used can be any non-foaming agents known to be suitable for aqueous fabric softeners from the prior art. Examples of suitable commercial defoaming agents are Dow Corning® DB-110A and TEGO® Antifoam® 7001 XP. Preferably, the compositions according to the invention contain between 0.0001% and 0.05%, more preferably 0.001% to 0.01% by weight, of one or more different non-foaming agents.

[0114] As a preservative, the aqueous fabric softener may comprise active bactericidal and/or fungicidal ingredients known to be suitable from the prior art, with preference being given to water-soluble active ingredients. Examples of suitable commercial bactericides are methylparaben, 2-bromo-2-nitropropane-1,3-diol, 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one. The aqueous fabric softener may similarly comprise an oxidation inhibitor as a preservative. Examples of suitable commercial oxidation inhibitors are ascorbic acid, 2,6-di-tert-butyl-4-methylphenol (BHT), butylhydroxyanisole (BHA), tocopherol and propyl gallate. Preferably, the compositions according to the invention contain between 0.0001% and 0.5%, more preferably 0.001% to 0.2% by weight, of one or more different preservatives. More particularly, the compositions according to the invention may contain between 0.001% and 0.1%, more preferably 0.001% to 0.01% by weight, of one or more different oxidation inhibitors.

[0115] As an organic solvent, the fabric softener can comprise short-chain alcohols, glycols and glycol monoethers, with preference given to ethanol, 2-propanol, propane-1,2-diol and dipropylene glycol. More particularly, the compositions according to the invention may contain between 0.1% and 10%, more preferably 0.2% to 5% by weight, of one or more different organic solvents.

[0116] The fabric softener may comprise one or more polymers that do not contain siloxane. Examples of these are carboxymethyl cellulose, polyethylene glycol, polyvinyl alcohol, poly(meth)acrylates, polyethyleneimines or polysaccharides. More particularly, the compositions according to the invention may contain between 0.01% and 25% by weight, more preferably 0.1% to 10% by weight, of one or more different polymers that do not contain siloxane.

[0117] Enhancers in the context of the invention are compounds that cause an additional improvement in water repellency in treated cloths. The enhancers have the ability to react in a cross-linking manner with both the free hydroxyl or amino functions of the copolymers according to the invention and with the textile fabrics. Preferred enhancers have carbodiimide functions, with particular preference being given to polycarbodiimides.

[0118] Preferred compositions according to the invention and aqueous emulsions according to the invention comprise at least one polycarbodiimide as an enhancer.

[0119] With special preference, the compositions according to the invention and aqueous emulsions according to the invention, the copolymers according to the invention or the process products according to the invention comprise a polycarbodiimide as an enhancer, at least one emulsifier , preservatives, optionally at least one solvent selected from ethyl acetate, butyl acetate, propylene glycol and TPM.

[0120] The invention further provides for the use of the copolymers according to the invention and the process products according to the invention for finishing fabrics.

[0121] Preference is given to use for finishing textile fabrics, with more preference in textile product care compositions, especially in textile product softening compositions (cloth softeners).

[0122] Similarly, it is preferred to use the copolymers according to the invention or the process products according to the invention as coating compositions for wood.

[0123] Preferably, the copolymers according to the invention and the process products according to the invention are used as fabric softeners.

[0124] Preferred cloths are selected from the group comprising woven textile cloths, wood, leather, hair and fur, with preference being given to woven textile cloths, loop-formed meshes, loop-drawn fabrics, non-woven fabrics, fabric (paper fibers ) and/or fibers made from natural and/or synthetic raw materials.

[0125] The present invention additionally provides a process for impregnating liquid and dirt repellent of textile fabrics using the copolymers according to the invention.

[0126] Within the scope of the present invention, repellency means that textile cloths become repellent against liquids and dirt, preferably water and aqueous solutions and/or oils and fats. Liquids, in particular, are at least partially repelled by the finish.

[0127] Repellency is preferably guaranteed by ensuring the respective contact angle (DIN EN ISO 14419) and/or through determination by a spray test in accordance with AATCC M22-2014, as shown in the examples. An improvement in the contact angle is manifested by an increase in the contact angle or by slower immersion of the droplet into the material, i.e. an increase in the contact angle after a contact time, preferably 60 seconds after application of the droplet. . In the sprinkler test, an increase in value means an improvement. Evaluations are carried out in comparison to an analogous treatment without an active ingredient.

[0128] A preferred process for impregnating liquid and dirt repellent of textile fabrics is the use of compositions according to the invention, preferably aqueous emulsions, more preferably aqueous emulsions using intensifiers, with special preference of aqueous emulsions using a polycarbodiimide as an intensifier.

[0129] The invention additionally provides repellent textile cloths comprising the copolymers according to the invention, preferably in combination with an enhancer, more preferably with a polycarbodiimide as an enhancer, with retention of or improvement in tactile properties.

[0130] Tactile properties are based on the hand, with the hand preferably being determined with the aid of a TSA as described in the examples. With special preference, the hand is determined with a piece of textile cloth that has been cut to size, after previous conditioning (4 hours) at 25 °C and 50% relative air humidity, inserting and stapling it into the TSA (Tissue Soft Analyzer, from Emtec Electronic GmbH). The testing instrument then determines individual values for the softness, smoothness and stiffness of the textile cloth and uses these to guarantee the overall impression, the feel in the hand (HF). This HF value was guaranteed using an algorithm specially designed for textile products by EMTEC. An increasing HF value means greater softness. Evaluations are carried out in comparison to an analogous treatment without an active ingredient.

[0131] Work examples:

GENERAL METHODS AND MATERIALS

[0132] Determination of isocyanate content (proportion by mass of isocyanate groups) to EN ISO 11909:2007: The initial weight is guided by the isocyanate content. If the approximate isocyanate content is unknown, it must be guaranteed in a preliminary experiment with an initial weight of 3.5 g of polymer. Weigh the sample to approximately 1 mg in a 500 ml Erlenmeyer flask and dissolve it in 25 ml of toluene, if necessary with slight heating. After cooling to room temperature, add 20 ml of the appropriate dibutylamine solution with a pipette. Seal the bottle and leave it to rest for 15 minutes, with occasional shaking. Dilute with 150 ml of ethanol and, after adding a few drops of bromophenol blue solution, titrate with the appropriate hydrochloric acid until the color changes to yellow. If separation occurs during the titration, add additional ethanol.

GPC:

[0133] GPC measurements to determine polydispersity and weight-average molar masses Mw were performed under the following measurement conditions: SDV 1,000/10,000 A column combination (length 55 cm), temperature 35 °C, THF as mobile phase , flow rate 0.35 ml/min, sample concentration 10 g/l, RI detector, polymers according to the invention evaluated with polystyrene standard (162-2 520 000 g/mol).

MATERIALS:

[0134] Unidyne TG-580: a fluoroalkyl acrylate as an aqueous emulsion, content of 30% by weight; Vestanat® HT 2500/LV (brand of Evonik, Germany) an aliphatic polyocyanurate based on hexamethylene diisocyanate with an NCO value of 22.8%; it contains isocyanurate structures and has an NCO functionality between 3 and 4; Vestanat® T 1890/100: an aliphatic polyocyanurate based on isophorone diisocyanate with an NCO value of 17.2%; it contains isocyanurate structures and has an NCO functionality between 3 and 4; Vestanat® HB 2640 LV: an aliphatic polyocyanurate based on hexamethylene diisocyanate with an NCO value of 22.8%; it contains biuret and has an NCO functionality between 3 and 4; Novares® LS 500: (brand of RÜTGERS Novares, Germany) a reaction product of styrene with phenol that has an average of 1.5 units of styrene per phenol; the product has an OHN of 242.7; TIB Kat 716 (from TIB Chemicals AG); isostearyl alcohol with an OHN of 203.5 Falc; stearyl alcohol (97% by weight), from ABCR; myristyl alcohol (>96%), Kao Chemicals; cetyl alcohol (>98%), Evonik; lauryl alcohol (98% by weight), from Aldrich; Polyvest® EP HT: (brand name of Evonik) a hydroxy-terminated polybutadiene that has an OHN of 47 mg KOH/g; α,w-dihydroxypolydimethylsiloxane, OHN 51, 30 siloxane units; α,w-dihydroxypolydimethylsiloxane, OHN 14, 80 siloxane units; tris-terminal trihydroxypolydimethylsiloxane, OHN 35, formula (I) M3D57T1Q0; terminal aminopolydimethylsiloxane with a nitrogen content of 3.1% by weight, 10 siloxane units; PM 3705 is a 3M polycarbodiimide, 25% by weight propylene glycol/water (8%/67%); Synperonic PE/F 108: an ethoxylated polypropylene oxide having a molar mass of about 14,000 g/mol; Acticide MBS, 5% aqueous by weight preservative, mixture of two isothiazolinone biocides, from Thor; n-Butyl acetate (98% by weight) from Brenntag; ethyl acetate (99.5%) from Sigma-Aldrich; Dowanol TPM: a tripropylene glycol monomethyl ether, from DOW;

TISSUE:

[0135] Textile Products: cotton, woven cloth: base weight 205 g/m2, thickness: 400 μm; polyester: basis weight 170 g/m2, thickness: 200 μm; polyamide: basis weight 65 g/m2, thickness: 50 μm, all samples from WFK-Testgewebe GmbH (Christenfeld 10 41379 Brüggen); Wood: natural beech, 5.0 x 5.0 cm test plates, from Rocholl GmbH.

EXAMPLE 1, SYNTHESIS EXAMPLES, A) ISOCYANURATES: EXAMPLE 1A.1:

[0136] A heatable glass flask with mechanical stirrer, thermometer and gas inlet was initially charged with 552.63 g of Vestanat HT 2500 LV and heated to 50 °C. 463 g of Novares LS 500 and 423.41 g of n-butyl acetate and 1000 ppm of TIB Kat 716 were added dropwise within 90 min. (This amount of catalyst, in all examples, is based on the sum total of the isocyanate compounds and the respective component c)). The reaction temperature was maintained at 50 °C for 3 hours. Then, the NCO value was determined using a sample taken.

[0137] As expected, 2/3 of the NCO groups were converted. The temperature was increased to 70°C, 1111 g of a hydroxysiloxane with OHN, 51 mg of KOH/g and 100 ppm of TIB Kat LA 716 were added within 5 minutes, the temperature was increased to 80°C and the mixture was stirred for another 2 hours. After cooling to room temperature, complete conversion of the remaining NCO groups was verified using a final sample.

[0138] GPC: Mw: 38.832 g/mol; Mn: 20.373 g/mol; Mw/Mn: 1.91.

EXAMPLE 1A.2:

[0139] In an analogous experimental setup and with the same experimental procedure as in 1a.1, 22.1 g of Vestanat HT 2500 LV were reacted with 18.5 g of Novares LS 500 in 40.3 g of n-butyl acetate with 1,000 ppm of TIB Kat 716. 2/3 of the NCO groups were converted. The temperature was increased to 70°C, 161.9 g of a hydroxysiloxane with OHN, 14 mg KOH/g and 100 ppm of TIB Kat LA 716 were added within 3 minutes, the temperature was increased to 80°C and the mixture was stirred for another 2 hours. Conversion check as in 1a.1.

[0140] GPC: Mw: 30.919 g/mol; Mn: 5.308 g/mol; Mw/Mn: 5.82.

EXAMPLE 1A.3:

[0141] In an analogous experimental setup and with the same experimental procedure as in 1a.1, 66.3 g of Vestanat HT 2500 LV were reacted with 66.1 g of isostearyl alcohol in 53 g of n-butyl acetate with 1,000 ppm of TIB Kat 716. 2/3 of the NCO groups were converted. The temperature was increased to 70 °C, 133.32 g of a hydroxysiloxane with OHN, 51 mg of KOH/g and 100 ppm of TIB Kat LA 716 were added within 3 minutes, the temperature was increased to 80 °C and the mixture was stirred for another 2 hours. Conversion check as in 1a.1.

[0142] GPC: Mw: 27.081 g/mol; Mn: 9.237 g/mol; Mw/Mn: 2.93.

EXAMPLE 1A.4:

[0143] In an analogous experimental setup and with the same experimental procedure as in 1a.1, 77.36 g of Vestanat HT 2500 LV were reacted with 64.9 g of Novares LS 500 in 47.74 g of n-butyl acetate with 1,000 ppm of TIB Kat 716. 2/3 of the NCO groups were converted. The temperature was increased to 70°C, 168.7 g of a Polyvest® EP HT with OHN 47 mg KOH/g and 30 g of n-butyl acetate and 100 ppm of TIB Kat LA 716 were added within 3 minutes, at temperature was increased to 80 °C and the mixture was stirred for another 2 hours. Conversion check as in 1a.1.

[0144] GPC: Mw: 84,560 g/mol; Mn: 3,830 g/mol; Mw/Mn: 22.08.

EXAMPLE 1A.5:

[0145] In an analogous experimental setup and with the same experimental procedure as in 1a.1, 33.2 g of Vestanat HT 2500 LV were reacted with 16.7 g of Novares LS 500 and 13.0 g of stearyl alcohol in 203.76 g of ethyl acetate with 1,000 ppm of TIB Kat 716. 2/3 of the NCO groups were converted. The temperature was increased to 70°C, 242.8 g of a hydroxysiloxane with OHN, 14 mg KOH/g and 100 ppm of TIB Kat LA 716 were added within 3 minutes, the temperature was increased to 80°C and the mixture was stirred for another 2 hours. Conversion check as in 1a.1.

[0146] GPC: Mw: 27,940 g/mol; Mn: 61.83 g/mol; Mw/Mn: 4.52.

EXAMPLE 1A.6:

[0147] In an analogous experimental setup and with the same experimental procedure as in 1a.1, 71.8 g of Vestanat HT 2500 LV were reacted with 36.16 g of Novares LS 500 and 28.1 g of stearyl alcohol in 187 g of ethyl acetate with 1,000 ppm of TIB Kat 716. 2/3 of the NCO groups were converted. The temperature was increased to 70°C, 144.43 g of a hydroxysiloxane with OHN, 51 mg of KOH/g and 100 ppm of TIB Kat LA 716 were added within 3 minutes, the temperature was increased to 80°C and the mixture was stirred for another 2 hours. Conversion check as in 1a.1.

[0148] GPC: Mw: 31.774 g/mol; Mn: 17.612 g/mol; Mw/Mn: 1.8.

EXAMPLE 1A.7:

[0149] In an analogous experimental setup and with the same experimental procedure as in 1a.1, 60.7 g of Vestanat HT 2500 LV were reacted with 59.5 g of stearyl alcohol in 161 g of n-butyl acetate with 1,000 ppm of TIB Kat 716. 2/3 of the NCO groups were converted. The temperature was increased to 70°C, 122.21 g of a hydroxysiloxane with OHN, 51 mg of KOH/g and 100 ppm of TIB Kat LA 716 were added within 3 minutes, the temperature was increased to 80°C and the mixture was stirred for another 2 hours. Conversion check as in 1a.1.

[0150] GPC: Mw: 21.425 g/mol; Mn: 8.923 g/mol; Mw/Mn: 2.40.

EXAMPLE 1A.8:

[0151] In an analogous experimental setup and with the same experimental procedure as in 1a.1, 18.8 g of Vestanat HT 2500 LV were reacted with 18.4 g of stearyl alcohol in 116.46 g of ethyl acetate with 1,000 ppm TIB Kat 716. 2/3 of the NCO groups were converted. The temperature was increased to 70 °C, 137.5 g of a hydroxysiloxane with OHN, 14 mg KOH/g and 100 ppm of TIB Kat LA 716 were added within 3 minutes, the temperature was increased to 80 °C and the mixture was stirred for another 2 hours. Conversion check as in 1a.1. After cooling to room temperature, the product was solid.

[0152] GPC: Mw: 19.466 g/mol; Mn: 4.558 g/mol; Mw/Mn: 4.21.

EXAMPLE 1A.9:

[0153] In an analogous experimental setup and with the same experimental procedure as in 1a.1, 55.26 g of Vestanat HT 2500 LV were reacted with 55.4 g of Novares LS 500 in 73 g of ethyl acetate with 1,000 ppm of TIB Kat 716. 2/3 of the NCO groups were converted. The temperature was increased to 70°C, 97.73 g of a hydroxysiloxane with OHN, 35 mg of KOH/g and 100 ppm of TIB Kat LA 716 were added within 3 minutes, the temperature was increased to 80°C and the mixture was stirred for another 2 hours. Conversion check as in 1a.1.

[0154] GPC: Mw: 36,900 g/mol; Mn: 15,300 g/mol; Mw/Mn: 2.4.

EXAMPLE 1A.10:

[0155] A heatable glass flask with mechanical stirrer, thermometer and gas inlet was initially charged with 27.63 g of Vestanat HT 2500 LV and 23.1 g of Novares LS 500, and 70.91 g of ethyl acetate and 1,000 ppm of TIB Kat 716 was added. The reaction temperature was maintained at 50 °C for 3 hours. Then, the NCO value was determined using a sample taken. As expected, 2/3 of the NCO groups were converted. The temperature was increased to 70 °C, 55.5 g of a hydroxysiloxane with OHN, 51 mg KOH/g and 100 ppm of TIB Kat LA 716 were added within 3 minutes, the temperature was increased to 80 °C and the mixture was stirred for another 3 hours. The reaction was terminated and complete conversion of the remaining NCO groups was verified using a final sample.

[0156] GPC: Mw: 50,700 g/mol; Mn: 23,000 g/mol; Mw/Mn: 2.2.

EXAMPLE 1A.11:

[0157] In an experimental setup analogous to that in 1a.1, 27.63 g of Vestanat HT 2500 were initially loaded and 23.1 g of Novares LS 500 and 55.5 g of a hydroxysiloxane with OHN 51 mg KOH/g in 70.91 g of ethyl acetate with 1,000 ppm of TIB Kat 716 were added at room temperature and the mixture was then heated. The reaction temperature was maintained at 50 °C for 1 h, then at 80 °C for 3 h. The reaction was terminated and complete conversion of the remaining NCO groups was verified using a final sample.

[0158] GPC: Mw: 37,800 g/mol; Mn: 19,800 g/mol; Mw/Mn: 1.9.

EXAMPLE 1A.12:

[0159] In an analogous experimental setup and with the same experimental procedure as in 1a.1, 55.3 g of Vestanat HT 2500 LV were reacted with 44.0 g of myristyl alcohol in 140.2 g of ethyl acetate with 500 ppm of TIB Kat 716. 2/3 of the NCO groups were converted. The temperature was increased to 70 °C, 111.1 g of a hydroxysiloxane with OHN, 51 mg KOH/g and 100 ppm of TIB Kat LA 716 were added within 3 minutes, the temperature was increased to 80 °C and the mixture was stirred for another 2 hours. Conversion check as in 1a.1. After cooling to room temperature, the product was solid.

[0160] GPC: Mw: 18,400 g/mol; Mn: 8,600 g/mol; Mw/Mn: 2.1.

EXAMPLE 1A.13:

[0161] In an analogous experimental setup and with the same experimental procedure as in 1a.1, 55.3 g of Vestanat HT 2500 LV were reacted with 48.6 g of cetyl alcohol in 193.3 g of ethyl acetate with 500 ppm of TIB Kat 716. 2/3 of the NCO groups were converted. The temperature was increased to 70 °C, 111.1 g of a hydroxysiloxane with OHN, 51 mg KOH/g and 100 ppm of TIB Kat LA 716 were added within 3 minutes, the temperature was increased to 80 °C and the mixture was stirred for another 2 hours. Conversion check as in 1a.1. After cooling to room temperature, the product was solid.

[0162] GPC: Mw: 24,800 g/mol; Mn: 10,000 g/mol; Mw/Mn: 2.5.

EXAMPLE 1A.14:

[0163] In an analogous experimental setup and with the same experimental procedure as in 1a.1, 73.3 g of Vestanat T 1890/100 were reacted with 46.3 g of Novares LS 500 in 154 g of ethyl acetate with 500 ppm of TIB Kat 716. 2/3 of NCO groups were converted. The temperature was increased to 70 °C, 111.1 g of a hydroxysiloxane with OHN, 51 mg KOH/g and 100 ppm of TIB Kat LA 716 were added within 3 minutes, the temperature was increased to 80 °C and the mixture was stirred for another 2 hours. Conversion check as in 1a.1.

[0164] GPC: Mw: 40,200 g/mol; Mn: 2,700 g/mol; Mw/Mn: 14.8.

EXAMPLE 1A.15:

[0165] In an analogous experimental setup and with the same experimental procedure as in 1a.1, 55.3 g of Vestanat HT 2500 LV were reacted with 46.3 g of Novares LS 500 in 128.5 g of ethyl acetate with 1,000 ppm of TIB Kat 716. 2/3 of the NCO groups were converted. The temperature was increased to 60 ° C, and 45.6 g of an aminosiloxane having a nitrogen content of 3.1% by weight was added within 3 minutes and the mixture was stirred at 70 ° C for another 2 hours. Conversion check as in 1a.1.

[0166] GPC: Mw: 3300 g/mol; Mn: 860 g/mol; Mw/Mn: 3.9.

EXAMPLE 1A.16:

[0167] In an analogous experimental setup and with the same experimental procedure as in 1a.1, 55.3 g of Vestanat HT 2500 LV were reacted with 38.3 g of lauryl alcohol in 136.4 g of ethyl acetate with 500 ppm of TIB Kat 716. 2/3 of the NCO groups were converted. The temperature was increased to 70 °C, 111.1 g of a hydroxysiloxane with OHN, 51 mg KOH/g and 100 ppm of TIB Kat LA 716 were added within 3 minutes, the temperature was increased to 80 °C and the mixture was stirred for another 2 hours. Conversion check as in 1a.1. After cooling to room temperature, the product was solid.

[0168] GPC: Mw: 18,200 g/mol; Mn: 8,500 g/mol; Mw/Mn: 2.2.

EXAMPLE 1A.17:

[0169] In an analogous experimental setup and with the same experimental procedure as in 1a.1, 55.3 g of Vestanat HT 2500 LV were reacted with 3.8 g of lauryl alcohol and 39.6 g of myristyl alcohol in 139, 8 g of ethyl acetate with 500 ppm of TIB Kat 716. 2/3 of the NCO groups were converted. The temperature was increased to 70 °C, 111.1 g of a hydroxysiloxane with OHN, 51 mg KOH/g and 100 ppm of TIB Kat LA 716 were added within 3 minutes, the temperature was increased to 80 °C and the mixture was stirred for another 2 hours. Conversion check as in 1a.1. After cooling to room temperature, the product was solid.

[0170] GPC: Mw: 18,500 g/mol; Mn: 8,400 g/mol; Mw/Mn: 2.2.

EXAMPLE 1, SYNTHESIS EXAMPLES, B) BIURET EXAMPLE 1B.1:

[0171] In an analogous experimental setup and with the same experimental procedure as in 1a.1, 57.3 g of Vestanat HB 2640 LV were reacted with 46.3 g of Novares LS 500 in 143.1 g of ethyl acetate with 1,000 ppm of TIB Kat 716. 2/3 of the NCO groups were converted. The temperature was increased to 70 °C, 111.1 g of a hydroxysiloxane with OHN, 51 mg KOH/g and 100 ppm of TIB Kat LA 716 were added within 3 minutes, the temperature was increased to 80 °C and the mixture was stirred for another 4 hours. Conversion check as in 1a.1.

[0172] GPC: Mw: 13,300 g/mol; Mn: 1,300 g/mol; Mw/Mn: 10.5.

EXAMPLE 2, APPLICATION EXAMPLES EXAMPLE 2.1; FORMULATION AND FINISH:

[0173] The emulsification of the active ingredients was carried out by 2 different methods as follows:

[0174] Method 1: 6% to 8% of the amount of water was initially loaded together with emulsifiers and dissolved. The active ingredient was gradually incorporated at a high shear rate with a mizer disc (2000 rpm, corresponding to peripheral speed about 8 m/s) and with cooling. Stirring was continued at high shear rate under reduced pressure for 15 min. With decreasing shear rate, the mixture was diluted with water, then Acticide MBS preservative was added, and the mixture was filtered through a 190 μm rapid screen and dispensed.

[0175] Method 2: Dilute with organic solvent (e.g., ethyl acetate, butyl acetate) according to the active ingredient concentrations in the table below, followed by application to the cloth.

[0176] As an alternative to Methods 1 and 2 as detailed, the emulsification of the active ingredients can also be carried out using an ultrasonic homogenizer or a slit homogenizer in a manner known to those skilled in the art. TABLE 1: COMPOSITIONS OF FORMULATIONS FOR APPLICATION TO TEXTILE AND WOOD PRODUCTS, FIGURES IN % BY WEIGHT, * REFERS TO THE COMPOSITIONS IN TABLE 3

FILLING METHOD (MODEL: HVF, MATHIS AG):

[0177] To test the respective emulsions, a liquor containing 8 g/l of the appropriate emulsion in each case was applied to cotton cloth (205 g/m2), polyamide cloth (65 g/m2) and polyester cloth ( 170 g/m2), which were squeezed to a wet collection of about 70% to 80% by weight and dried. The values used for pressure and speed can be found in Table 2. The filling application took place at room temperature. TABLE 2: PRESSURES AND BEARING SPEEDS USED IN THE FILLING METHOD.

EXHAUSTION PROCESS THAT STARTS FROM FORMULATIONS CONTAINING SOLVENT:

[0178] To test the respective copolymers according to the invention (active ingredients), knitted cotton cloth (205 g/m2), polyamide (65 g/m2) and polyester (170 g/m2) were finished with a liquor which contained 20 g/l of the appropriate active ingredient in each case. A liquor (cloth to liquor) ratio of 1:15 was chosen. Solvents used are water, butyl acetate and ethyl acetate. The test cloth is treated in the liquor with continuous stirring on the reciprocating shaker (model: 3006, manufacturers: GFL) for 30 min. After 30 min, the test cloth is removed from the bath, gently wrung out, shaken and dried. A raw block is treated under the same conditions with demineralized water only.

DRIP METHOD (APPLICATION ON WOOD):

[0179] The application of the copolymers according to the invention (active ingredients) to the wooden surface proceeded as follows: a solution of the active ingredient (9%, active content) in ethyl acetate, butyl acetate or water was distributed from homogeneously on the surface of the wooden plate (dimensions: 5 cm x 5 cm) with the aid of a syringe so that each plate has been coated with 45 mg of the active ingredient. The raw block was determined using an untreated wooden board. The fluorinated reference product was diluted in water so that the concentration of the active content was 90 g/l. The plates were allowed to evaporate at room temperature and then dried and fixed as described below. The application and analysis of the drops on the surface proceeded in a similar way to experiments with textile products.

DRYING METHOD (LTE LAB DRYER, MATHIS AG, FAN SPEED 2,000 RPM):

[0180] The cloths were dried at 105 °C (plus dwell time, i.e., the heating time of the textile cloth) for 2 min and then condensed at 160 to 180 °C (no dwell time) for 0.5 1 min to set the finish. Exact conditions:

EXAMPLE 2.2; TEST THE FINISH: CONTACT ANGLE MEASUREMENT METHOD (UNIVERSAL SURFTENS, OEG-GMBH) IN TEXTILE PRODUCTS

[0181] In accordance with ISO/DIN 19403-6 and DIN EN ISO 14419, water repellency/oil repellency was tested in the following manner: The textile products were finished by filling application or the exhaust method, dried and fixed. The wooden boards were finished in a similar way as described above. The finished textile product specimens were mounted on an embroidered frame with a diameter of about 8 cm. They thus formed a sufficiently smooth surface for measuring the contact angle. The tension ring with the textile cloth was placed on the measuring stage of the contact angle measuring instrument and focused. This was unnecessary for analysis of the wooden plates; they were usable as they were. For the determination of hydrophobicity, a drop of water was then applied to the textile cloth. It is crucial that the drop falls onto the textile cloth from a low and constant height. Application using an Eppendorf pipette was found to be ideal, with a fixed drop volume of 15 μl of demineralized water (DM). After the droplet was applied, the contact angle was determined continuously through multipoint analysis. This involved marking the edge of the drop and simulating the shape of the drop. This operation was conducted by image analysis immediately after applying the drop ("0" seconds), after 5, 15, 30, 60, 120, 180, 240 and 300 seconds. In this way, it was possible to illustrate the characteristics of immersing the drop for 5 minutes. For the determination of oleophobicity, in a manner analogous to that described above, a 20 μl drop of white oil (Sigma Aldrich (M8410), CAS 8042-47-5, Brookfield viscosity at 25 °C: 25.0 cps, density: 0.86 g/cm3) was applied. Behavior towards the specimen was documented as described above. In both test modes, the contact angle was plotted with the respective time, whereby it is possible to immediately recognize hydrophobicity or oleophobicity from the graph. The rough block used was appropriately a finished specimen. If the contact angle decreases over time, droplets emerge; the same remains constant, it is adequate repellency. Additionally, the Y axis intercept allows for additional distinction. The greater the contact angle, the greater the repellent action of the applied textile finish.

SPRAY TEST

[0182] According to ISO 9073-17 or according to AATCC 22-2014 method, water repellency was evaluated by the dusting test (dynamic water repulsion). For this purpose, a section of cloth or part of an item of clothing in an oblique plane was sprinkled with 250 ml of water through a sprinkler from a height of 15 cm and then the image of the adhering water was evaluated. A scale of 0 to 100 was used for this purpose, with 0 meaning complete humidification and 100 meaning no complete humidification.

HAND

[0183] Hand is a fundamental quality parameter of a cloth. The same can be described, for example, by smoothness, compressibility and rigidity. Typically, hand is determined by subjective assessment through manual testing. Additionally, there are measuring instruments for this purpose that determine this objectively.

[0184] A piece of textile cloth that was cut to size, after previous conditioning (4 hours) at 25 °C and 50% relative air humidity, was inserted and stapled into the TSA (Tissue Soft Analyzer, from Emtec Electronic GmbH). The testing instrument then determines individual values for the softness, smoothness and stiffness of the textile cloth and uses these to guarantee the overall impression, the feel in the hand (HF). This HF value was guaranteed using an algorithm specially designed for textile products by EMTEC.

WASH TEST:

[0185] In accordance with DIN EN ISO 6330, wash resistance was determined by washing the textile cloth in a standard domestic washing machine (Novotronic W918 fully automatic washing machine, Miele). For this purpose, a standard detergent of type IEC A* (according to IEC 60456, *phosphate-free, manufacturers: WFK-Testgewebe GmbH) was used. Additionally, 3 kg of cotton cloth was added to the wash as ballast material.

[0186] Program: hot/color wash 40 °C, 19 g of detergent, duration of a wash cycle: 2:02 h, spin speed: 1,200 rpm. APPLICATION TEST RESULTS: TABLE 3: THE FOLLOWING SAMPLES WERE TESTED ON COTTON (1.1 TO 1.8), ON POLYESTER (2.1 TO 2.8), ON POLYAMIDE (3.1 TO 3.8) AND ON WOOD (4.1 TO 4.4); ELUCIDATION OF SAMPLE NUMBERS (AFTER THE POINT) AS SHOWN IN TABLE 1. TABLE 4: RESULTS OF CONTACT ANGLE MEASUREMENTS AND SPRAY TEST FOR COTTON:

[0187] As shown in Table 4, the copolymers according to the invention almost obtain the water repellency of the fluorinated comparative product (1.1), or even exceed it after washing, as shown particularly clearly by the samples comprising the copolymer from synthesis example 1a.1 (1.2, 1.3, 1.6 and 1.7). TABLE 5: RESULTS OF CONTACT ANGLE MEASUREMENTS AND SPRAY TEST FOR POLYESTER:

[0188] As evident from Table 5, the copolymers according to the invention surpassed the water repellency of the fluorinated comparative product. As shown particularly clearly by Examples 2.2 and 2.3, adequate oil repellency is also achieved. Adequate oil repellency means in particular that the contact angle immediately after application is much greater than for the untreated material sample and that, especially after 60 sec., the oil preferably has not completely emerged. TABLE 6: RESULTS OF CONTACT ANGLE MEASUREMENTS AND SPRAY TEST FOR POLYAMIDE:

[0189] As shown in Table 6, the copolymers according to the invention surprisingly surpassed both the water repellency and the oil repellency of the fluorinated comparative product. As shown by Example 3.3, excellent water and oil repellency was achieved both before and after washing. TABLE 7: RESULTS OF CONTACT ANGLE MEASUREMENTS FOR WOOD:

[0190] As shown in Table 7, the active ingredient according to the invention caused water and oil repellency, so that the respective water/oil droplets did not spread across the wood. TABLE 8: HAND FEEL VALUES FOR TEXTILE CLOTHES (WITHOUT WASHING):

[0191] As indicated in Table 8, the active ingredients according to the invention caused a noticeably better hand feel of the materials than the fluorinated comparative sample. Samples comprising the active ingredient of Example 1a.1 performed best on cotton cloth, while the copolymer of Example 1a.2 caused the best improvement in hand feel on synthetic fibers.

Claims (15)

1. Copolymers characterized by comprising or consisting of three components: component a) which has at least one biuret or isocyanurate substructure, component b) selected from polysiloxanes and polyhydrocarbons, component c) which comprises a hydrocarbon that is different from component b ) and has at least 6 carbon atoms and no more than 3 heteroatoms selected from the group of N, O, S, in which component b) is joined to 2 different or identical components a) through at least two positions , and in which the copolymer is free of isocyanate groups. 2. Copolymers, according to claim 1, characterized by having polybutadiene as the polyhydrocarbon of component b). 3. Copolymers, according to any one of claims 1 and 2, characterized by being free of halogen atoms. 4. Copolymers according to any one of claims 1 to 3, characterized by having components a) and components c) in a ratio of the number of c) divided by the number of a) from 1 to 3. 5. Copolymers, according to any one of claims 1 to 4, characterized by each having, in component a), two or more biuret or isocyanurate substructures. 6. Copolymers according to any one of claims 1 to 5, characterized in that they have, as component a), independently identical or different biuret substructures of Formula (III) and isocyanurate substructures of Formula (IV) where L are divalent radicals of tolyl (2,4-; 2,6-), ethylphenyl, 1,5-naphthyl, α,w- tetramethylene, α,w-hexamethylene, α,w-dodecamethylene, α,w- 2- methylpentamethylene, α,w-2,2,4-trimethylhexamethylene, cyclohexyl (1,4-), 1- methylcyclohexyl (1,3-; 1,4-; 2,6-), 2,2,6- trimethylcyclohexyl, isophorone (3,3,5-trimethylcyclohexyl), 4,4'-dicyclohexylmethyl, 4,4'-dicyclohexylpropane-(2,2), 4,4'-diphenylmethane, Rx is independently the binding site for component b ) and component c), and indicates a urethane group or a urea group in the case of binding to component b), and indicates a urethane group, a urea group or a thiourea group in the case of binding to component c), wherein said urethane groups , urea and thiourea are bonded through the nitrogen atom to formula (III) and formula (IV), or Rx indicates a bond to an additional biuret or isocyanurate substructure. 7. Copolymers, according to claim 6, characterized by having in component a), as divalent radical L in formula (III) or (IV), hexamethylene, 4,4'-diphenylmethane and isophorone; in component b), a siloxane of Formula (I) with the indices a3 = 2 to 5 a1 = 0 to 1 a2 = 0 b2 and b3 = 0 d = 0 R1 = methyl or phenyl in component c), a hydrocarbon that is free of heteroatoms and has aromatic rings. 8. Process for preparing the copolymers according to any one of claims 1 to 7, characterized in that, in the first step, an intermediate comprising components a) and components c) is prepared and, in the second step, the intermediates are converted into the copolymer . 9. Compositions characterized by comprising copolymers according to any one of claims 1 to 7 and additives and/or auxiliaries. 10. Aqueous emulsion characterized by comprising the copolymers according to any one of claims 1 to 7 or the process products according to claim 8, which comprise additives and/or auxiliaries. 11. Compositions according to claim 9 or aqueous emulsions according to claim 10 characterized in that they comprise, as at least one additive, an intensifier. 12. Use of the aqueous compositions or emulsions according to any one of claims 9 to 11, characterized in that they are for finishing fabrics. 13. Method of impregnating liquid and dirt repellent of textile fabrics characterized by using copolymers, according to any one of claims 1 to 7. 14. Method of impregnating liquid and dirt repellent of textile fabrics, according to claim 13, characterized by using the compositions according to claim 11. 15. Repellent textile fabric characterized by comprising copolymers, according to any one of claims 1 to 7, with retention or improvement in tactile properties.