AU2005287543A1 - Fluorine-modified reactive resin systems, method for producing them and their use - Google Patents

Abstract

The invention relates to fluorine-modified reactive resin systems having improved surface properties which comprise a) 100 to 300 parts by weight of a binder component (A), capable of polyaddition and/or polycondensation, said binder component (A) having a solids content of 5 to 95 % by weight of the polymer, b) 5 to 100 parts by weight of a functionalizing component (B), capable of polyaddition and/or polycondensation and having a molar weight of 100 to 10.000 Dalton and a fluorine content bound to the polymer of 10 to 90 % by weight, c) 0 to 100 parts by weight of a curing agent component (C) capable of polyaddition and/or polycondensation and having a molecular weight of 100 to 10.000 Dalton, and d) to 300 parts by weight of a formulation component (D), whereby component (A) may contain component (B) optionally in a polymer-bound form. It was surprisingly found that fluorine-modified reactive resin systems cannot only be used for hard coating systems or surfaces having very low critical surface tensions ?<SUB>c</SUB> and very high contact angles ?, but that these systems have a substantially reduced dirt pickup behavior as compared to prior art systems.

Description

35994P AU-WO AUSTRALIA VERIFICATION OF TRANSLATION , Hans Weickmann c/o Weickmann & Weickmann Kopernikusstr. 9, 81679 MOnchen, Germany competent in the art and conversant with the English and German languages, hereby solemnly and sincerely declare that to the best of my knowledge and belief the appended translation is a faithful and true translation of International Application No. PCT/EP 2005/010286 filed on September 22, 2005 Munich, A O- ' Construction Research & Trostberg, 17 September 2004 Technology GmbH Our ref.: S-IPM-PAT Dr.Schm/hg/AM 83308 Trostberg DCO 8 Fluoromodified reactive resin systems, processes for their preparation and the use thereof 2 Description The present invention relates to fluoromodified reactive resin systems having improved surface properties, processes for their preparation and the use thereof. Owing to their unique surface properties, such as water- and oil repellence, fluoromodified polymer compositions are becoming more and more important and are thus ideally suited for use as dirt-repellent coating systems in the building, non-building and industrial sector. This is evident not least from the wealth of literature recently published on this subject (R. Winter, P. G. Nixon, R. J. Terjeson, J. Nohtasham, N. R. Holcomb, D. W. Grainger, D. Graham, D. G. Castner, G. L. Gard, J. Fluorine Chem., 2002, 115(2), 107-113; R. D. van de Grampel, W. Ming, J. Laven, R. van der Linde, F. A. M. Leermakers, Macromol., 2002, 35(14), 5670-5680; V. Castelvetro, M. Aglietto, F. Ciardelli, O. Chiantore, M. Lazzari, L. Toniolo, J. Coat. Technol., 2002, 74, 57-66). High-performance polyurethane-based coating materials consisting of a polyisocyanate and an isocyanate-reactive component, such as, for example, a relatively high molecular weight polyol, are generally known. Although they have very good material properties, they possess high surface energies and are therefore not easy to clean. The increasing demand for dirt- and water-repellent coatings led to the development of fluorocontaining compositions which are either mixed with the coating systems (as described in WO 99/26994) or applied reversibly to coating systems (cf. DE 100 63 431 C1). Fluorinated polyurethane systems and their use for the modification of the surface properties of coatings, such as oleophobization or hydrophobization, have already long been known from the patent literature.

3 EP 0 405 534 Al describes hydroxy-functional (per)fluoropolyether containing polyurethanes for the treatment of stone surfaces, which polyurethanes, however, do not form true films. Hydrophilic polyurethane films coated with fluoromodified polymers based on perfluoroalkyl acrylates or methacrylates, having high vapor permeability rates for oleophobization and hydrophobization, are disclosed in WO 97/36951 Al. US 4,504,401 B1 discloses low molecular weight urethanes containing perfluoroalkyl groups for the dirt-repellent treatment of fibre products, such as, for example, carpets. EP 0 702 041 Al describes polyisocyanates which are modified with fluorinated monoalcohols, contain allophanate and isocyanurate groups and, in compositions for one-component or two-component coating systems, have surface energies between 19.4 and 43.7 dynes/cm. EP 0 719 809 Al discloses similar fluoromodified polyisocyanates and blends with other nonfluorinated polyisocyanates, the fluorine being introduced here via fluoro-components having one or more hydroxyl groups. The use in coating compositions leads to films having surface energies similar to those described in EP 0 702 041 Al. Fluoromodified urethane systems consisting of a fluorine-containing polyol having one or more hydroxyl groups and polyisocyanates having allophanate and isocyanurate structures in the molecular weight ratio of 4:1 to 1:10 are disclosed in EP 0 566 037 A2. When used as a curing component, these systems lead to clear films. DE 195 47 448 Al discloses abrasion-resistant urethane coating compositions having reduced friction, based on fluorinated alcohols, 4 nonfluorinated polyols and blocked polyisocyanates and at least one amine crosslinking agent. Owing to the blocked polyisocyanates, the coating composition must, however, be heated beforehand to above 120'C before the crosslinking with polyamine components can take place. Compositions for coatings based on (per)fluoropolyethers (PFPE) are described in EP 1 116 759 Al. In addition to solvent, they comprise bifunctional (per)fluoropolyetherdiols in combination with IPDI trimers. In this application, the (per)fluoropolyethers are not incorporated as side groups. Fluorinated branched oligourethanes prepared from monomers or macromonomers, such as polyisocyanate in blocked form, a hydrophilic alcohol or thiol component, mono- and bifunctional hydroxy (per)fluoropolyether alcohols and monofunctional (per)fluoroalkyl alcohols and chemically crosslinkable alcohol or thiol components are disclosed in the application EP 1 059 319 A2. Here too, the (per)fluoropolyether compounds are not present as side groups. Water-based copolymer dispersions or emulsions based on monomers containing perfluoroalkyl groups have been known for a relatively long time. They are used for hydrophobization and oleophobization, especially of textiles or carpets, also in combination with further textile auxiliaries, provided that the perfluoroalkyl groups are linear and contain at least 6 carbon atoms. For the preparation of these copolymer dispersions or emulsions via emulsion polymerisation, different emulsifier systems are used and, depending on the type of emulsifier system used, anionically or cationically stabilized copolymer dispersions or emulsions having different performance characteristics are obtained.

5 Aqueous dispersions of graft copolymers containing perfluoroalkyl groups and their use as hydrophobing and oleophobing agents have been known for some time from the patent literature. EP 0 452 774 Al and DE 34 07 362 Al describe a process for the preparation of aqueous dispersions of copolymers and/or graft copolymers from ethylenically unsaturated perfluoroalkyl monomers and non fluoromodified ethylenically unsaturated monomers, aqueous emulsifier free polyurethane dispersions having been used as a grafting base. DE 36 07 773 C2 describes polyurethanes which contain perfluoroalkyl ligands and are used in the form of an aqueous dispersion but with the use of external emulsifiers, or in the form of a solution in an organic solvent (mixture) exclusively for the treatment of textile materials and of leather. Polyurethanes containing perfluoroalkyl groups and intended for the oleophobic and hydrophobic treatment of textiles are also described in the patent documents DE 14 68 295 Al, DE 17 94 356 Al, DE 33 19 368 Al, EP 0 103 752 Al, US 3,398,182 Bl, US 3,484,281 B1 and US 3,896,251 B1. However, these compounds require large amounts for use and exhibit insufficient adhesion to the substrate. WO 99/26 992 Al describes aqueous fluoro- and/or silicone-modified polyurethane systems having low surface energies, which cure to give water- and solvent-stable hard polyurethane films having anti-fouling properties, the following two perfluoroalkyl components being disclosed: RrSO2N'(Rh-OH)2 where Rf = perfluoroalkyl group having 1-20 C atoms and Rh = alkyl group having 1-20 C atoms, and 6 RfR'fCF-CO 2

CH

2

CR(CH

2

OH)

2 where Rf = C 4 -C6-fluoroalkyl, R'- = Ci-C 3 -fluoroalkyl and R = Ci-C 2 -alkyl. Water-dispersible sulpho-polyurethane or sulpho-polyurea compositions having low surface energy, especially for ink-absorbing coatings, are described in EP 0 717 057 B1, the hydrophobic segments consisting of polysiloxane segments or a saturated fluoroaliphatic group having 6-12 carbon atoms, of which at least 4 are completely fluorinated. Aqueous dispersions of water-dispersible polyurethanes having perfluoroalkyl side chains without the use of external emulsifiers are disclosed in EP 0 339 862 Al. Here, a fluorinated polyol which has been obtained by a free-radical addition reaction polytetramethylene glycol with a fluorinated olefin (see EP 0 260 846 B1) was used as the isocyanate-reactive component. However, the polyurethane dispersions obtained all have solids contents of less then 30 % by weight and moreover require considerable amounts of hydrophilic component. The surface energies of the dried films are still > 30 dyne cm 1 . US 4,636,545 describes aqueous polyurethane dispersions having blocked polyisocyanates optionally emulsified therein as a grafting base for the free-radical grafting of a polymer of unsaturated perfluoroalkyl monomers (M > 367 Dalton) and optionally unsaturated comonomers (in solvent or aqueous emulsion) for the hydrophobicization and oleophobicization of textiles, natural and synthetic fibres, paper and leather. The solids content is 5 to 50 % by weight, preferably 10 to 30 % by weight, and the fluorine content is 6 to 50 % by weight, preferably 10 to 30 % by weight. The fluorinated side chain is not incorporated as a monomer into the PU main chain but is grafted as an unsaturated fluoro compound onto the main chain of the prepared PU dispersion by free 7 radical polymerization. For this purpose, the unsaturated compound is added in the form of an emulsion (solvent-containing) to the polyurethane dispersion. US 5,703,194 describes the cationic polymerization of oxetane monomers having perfluorinated alkoxy side chains for the preparation of hydroxy functional prepolymers. However, no aqueous systems are disclosed. Owing to polyether main chain, the systems are not UV-stable. EP 1 162 220 Al describes cationic polyurethane dispersions which are thermally postcrosslinkable. The perfluoropolyethers used are incorporated as a diol or monol component into the main chain. The molecular weights of the polyurethanes are less than or equal to 9000 Dalton. WO 02/04 538 discloses systems in which perfluoroalkyl side chains are introduced via perfluorooxetanepolyol copolymers. Because of the polyether main chain, the systems are not UV-stable. JP 09118843 describes water-based compositions of fluoromodified phosphoric acid ester salts and a low molecular weight urethane compound having one or more perfluoroalkyl radicals for avoiding discolourations on the surface of seals at butt joints. The PU polymer coating is not described in this application. It was therefore the object of the present invention to develop fluoromodified reactive resin systems having improved surface properties for the permanent oil- and water-repellent surface treatment or modification of mineral and nonmineral substrates for various fields of use, which systems do not have said disadvantages of the prior art but possess good performance characteristics and at the same time can be 8 prepared taking into account ecological, economic and physiological aspects. This object was achieved, according to the invention, by providing fluoromodified reactive resin systems having improved surface properties, comprising a) 100 to 300 parts by weight of a binder component (A) capable of polyaddition and/or polycondensation, comprising al) a polyurethane resin having a molecular weight of 1,000 to 25,000 Dalton and 0.1 to 50 % by weight of free (blocked) isocyanate groups, based on the total mass of resin, or a2) an aqueous anionically and/or nonionically and/or cationically stabilized polyurethane resin having a molecular weight of 2,500 to 250,000 Dalton and 0 to 25 % by weight of free amine groups and/or 0 to 25 % by weight of free hydroxyl groups and/or 0 to 25 % by weight of free (blocked) isocyanate groups and/or 0 to 25 % by weight of free epoxy groups, based on the total mass of resin, or a3) a silane-terminated resin having a molecular weight of 1,000 to 250,000 Dalton and 0.1 to 50 % by weight of free alkoxysilane groups having any desired substitution pattern, based on the total mass of resin or 9 a4) a polyol and/or polyamine mixture based on low molecular weight and/or higher molecular weight (polymeric) compounds having a molecular weight of 60 to 10,000 Dalton and 1 to 50 % by weight of free hydroxyl groups and/or 1 to 50 % by weight of free amine groups, based on the total mass of resin, or a5) an epoxy resin having a molecular weight of 100 to 10,000 Dalton and 0.1 to 50 % by weight of free epoxy groups, based on the total mass of resin, or a6) a (meth)acrylate resin having a molecular weight of 2,500 to 250,000 Dalton and 0.1 to 25 % by weight of free hydroxyl groups, based on the total mass of resin, or a7) another polymer based on monomers capable of anionic, cationic or free radical polymerization and having 0.1 to 25 % by weight of free hydroxyl groups, based on the total mass of resin, or a suitable combination thereof, the binder component (A) having in each case a solids content of 5 to 95 % by weight of polymer, 10 b) 5 to 100 parts by weight of a functionalization component (B) capable of polyaddition and/or polycondensation and having a molar mass of 100 to 10,000 Dalton and a polymer-bound fluorine content of 10 to 90 % by weight, containing in each case one or more reactive aliphatic and/or aromatic primary and/or secondary (blocked) amino, hydroxyl, mercapto, (blocked) isocyanate, alkoxysilane, epoxide or aziridine or (meth)acrylate group(s), comprising bi) (per)fluoroalkylalkyleneamines or (per)fluoroalkylalkylene alcohols or (per)fluoroalkylalkylene mercaptans or (per)fluoroalkylalkylene isocyanates or (per)fluoroalkylalkylene oxides or (per)fluoroalkylalkylene silanes or (per)fluoroalkylalkylenaziridines or alkyl (per)fluoro(meth)acrylates or (per)fluoroalkyl (meth)acrylates or (per)fluoroalkyl (per)fluoro(meth)acrylates or b 2 ) reaction products of (per)fluoroalkylalkyleneamines or (per)fluoroalkylalkylene alcohols, diisocyanates and diethanolamine, perfluoroalkylalkylene alcohols having terminal methylene groups (hydrocarbon spacers) of the general formula

CF

3 -(CF2)x-(CH2)ry-OH, where x = 3 - 20 and y = 1 - 6 or hexafluoropropene oxide (HFPO) oligomer alcohols of the general formula

CF

3

CF

2

CF

2 0-(CF(CF 3

)CF

2 0)z-CF(CF 3

)CH

2

-OH,

11 where z= 1 - 10 or mixtures of these preferably being used, or b 3 ) reaction products of (per)fluoroalkylalkenes and diethanolamine or alkoxysilanes or other compounds having an amino group and one or more hydroxyl groups, (per)fluoroalkylalkenes having terminal vinyl groups (hydrocarbon spacers) of the general formula

CF

3

-(CF

2 ) x-CH=CH 2 , where x = 3 - 20 or mixtures of these preferably being used, or b 4 ) reaction products of alkyl(per)fluoro(meth)acrylates or (per)fluoroalkyl(meth)acrylates or (per)fluoroalkyl (per)fluoro(meth)acrylates and diethanolamine or other compounds having an amino group and one or more hydroxyl group(s) or b 5 ) reaction products of (per)fluoroalkylalkylene oxides and N-methylethanolamine or diethanolamine or other compounds having an amino group and one or more hydroxyl group(s) or 12 b 6 ) reaction products of (per)fluoroalkylalkylene oxides and primary and/or secondary amines or polyamines or aminoalkylalkoxysilanes or isocyanatoalkylalkoxysilanes or b 7 ) reaction products of polyisocyanates and (per)fluoroalkylalkylene alcohols and optionally aminoalkylalkoxysilanes or epoxyalkoxysilanes or (per)fluoroalkylalkyleneamines and optionally aminoalkylalkoxysilanes or epoxyalkoxysilanes or (per)fluoroalkylalkylene oxides or per)fluoroalkylalkylenecarboxylic acids or bs) reaction products of (per)fluoroalkylalkylene alcohols or (per)fluoroalkylalkyleneamines and isocyanatoalkylalkoxysilanes or epoxyalkoxysilanes or b 9 ) reactive polyhedral oligomeric polysilasesquioxanes (POSS) of the general formula (RaXbSiO 1.5)m wherea=0orl,b=0or 1, a+b= 1,m=4,6,8,10,12andR, X = any desired inorganic and/or organic and optionially polymeric 13 radical having 1 to 250 C atoms and 0 to 50 N and/or 0 to 50 O and/or 10 to 100 F and/or 0 to 50 Si and/or 0 to 50 S atoms or suitable combinations thereof, c) 0 to 100 parts by weight of a curing component (C) capable of polyaddition and/or polycondensation and having a molecular weight of 100 to 10,000 Dalton, containing in each case one or more reactive aliphatic and/or aromatic primary and/or secondary (blocked) amino, hydroxyl, mercapto, (blocked) isocyanate or aziridine group(s) and/or water, and d) 0 to 300 parts by weight of a formulation component (D), it being possible for the component (A) to contain the component (B) optionally in (polymer-)bound form and to have a (polymer-)bound fluorine content of 0.1 to 75 % by weight. Surprisingly, it was found that, by using fluoromodified reactive resin systems based on binder components capable of polyaddition and/or polycondensation, special functionalized components and curing agents, not only are hard coating systems or surfaces having very low critical surface energies yc (less than Teflon with 18.6 mN/m) and very large contact angles 0 (in the region of Teflon® with 1110) obtainable but these moreover have a dirt pickup tendency which is substantially reduced compared with the known prior art. What is decisive for this is that the functionalization components have fluoromodified structural elements which can be introduced by suitable macromonomers or telechelic polymers. In comparison with known fluoromodified coating systems in which only the binder is fluoromodified, the reactive resin systems according to the invention have a substantially improved property spectrum. Evidently, through the use of fluoromodified macromonomers or telechelic polymers as individual components, a better orientation of 14 the (per)fluoroalkyl groups at the coating system/air interface is achieved, which was not foreseeable. This property spectrum is even achieved with very low fluorine contents (1 to 5 % by weight, based on the formulated total system) or with very small amounts of curing agents. Moreover, it was not foreseeable that the fluoromodified reactive resin systems can also be prepared in the absence of solvents or with a low solvent content. All combinations listed in Table 1 are suitable for the binder component (A), the functionalization component (B) and the curing component (C), it being possible for the formulation component (D) optionally to be present. The type and amount of the functional groups in the components (A), (B) and (C) should be chosen so that a sufficiently reactive system forms. The expression "sufficiently reactive system" means that the molecular ratios and/or equivalent ratios of components (A), (B) and (C) with regard to functional or reactive groups contained therein are chosen in a way that within the framework of the processing temperature (e.g. 0 to 150'C) processing times, open times and curing times are achieved in the individual coating systems which are also achieved, if component (B) is not present and without a fluoromodification of component (A) (like in the diverse conventional reactive resin systems). The corresponding values preferably range within the following frame: Processing time: approx. 1 min to 6h Open time: approx. 1 min to 12h Curing time: approx. 10 min to 24 h All combinations listed in Table 1 are suitable for the functionalities of the binder component (A), of the functionalization component (B) and of the curing component (C), it being possible for a formulation component (D) optionally to be present. The type and amount of the functional 15 groups in the components (A), (B) and (C) should be chosen so that a sufficiently reactive system forms. Table 1 Functional groups in components Application, (A) (B) (C) Reaction type -NCO -OH, -NH( 2 ), -SH -OH, -NH( 2 ), -SH 3C, polyadd. -NCO -OH, -NH( 2 ), -SH -OH, -NH( 2 ), -SH 2C, polyadd. -NCO -OH, -NH( 2 ) atmospheric 1C, polyadd. latent humidity -NCO -NCO -OH, -NH( 2 ), -SH 2C, polyadd. -NCO -NCO atmospheric 2C, polyadd. humidity -NCO -NCO atmospheric 1C, polyadd. humidity -Si(OR)3-xR 2 x 1) -Si(OR) 3 -. xR 2 x 1) atmospheric 2C, polycond. humidity -Si(OR1) 3 -. xR 2 x 1) -Si(OR1) 3 -xR 2 x 1) atmospheric IC, polycond. humidity -OH / -NH( 2 ) -OH, -NH( 2 ), -SH -NCO 3C, polyadd. -OH / -NH( 2 ) -OH, -NH( 2 ), -SH -NCO 2C, polyadd. -OH / -NH( 2 ) -NCO -NCO 3C, polyadd. -OH / -NH( 2 ) -NCO -NCO 2C, polyadd.

-C

2

H

3 0 2) -C 2

H

3 0 2) -NH(2) 3C, polyadd.

-C

2

H

3 0 2) -C 2

H

3 0 2) -NH( 2 ) 2C, polyadd.

-C

2

H

3 0 2) -NH( 2 ) -NH( 2 ) 3C, polyadd.

-C

2

H

3 0 2) -NH( 2 ) -NH( 2 ) 2C, polyadd.

-C

2

H

3 0 2) -OH, -NH( 2 ) atmospheric 1C, polyadd. latent humidity

-CO

2 M 4) -C 2

H

4 N 3) -C 2

H

4 N 3) 3C, polyadd.

-CO

2 M 4) -C 2

H

4 N 3) -C 2

H

4 N 3) 2C, polyadd.

16 -NCO -OH, -NH( 2 ), -SH - 2C, polyadd. -OH / -NH( 2 ) -NCO - 2C, polyadd.

-C

2

H

3 0 2) -NH(2) - 2C, polyadd.

-CO

2 M 4) -C 2

H

4 N 3) - 2C, polyadd. 1) where x = 0, 1, 2 and R 1 , R 2 = alkyl having 1 - 10 C atoms, preferably having 1-4 C atoms 2) epoxy groups 3) aziridine groups 4) carboxyl or carboxylate groups from binder component (A) where M = H, Li, Na, K, HNR 3 and R 3= H, Me, Et The binder component al) capable of polyaddition and/or polycondensation consists of solvent-free or solvent-containing nonaqueous polyurethane resins, such as polyurethane prepolymers having a molecular weight of about 1 000 to 25 000 Dalton, preferably about 1000 to 10000 Dalton, and a content of about 0.1 to 50 % by weight, preferably about 1 to 25% by weight, of free (blocked) isocyanate groups, based on the total mass of resin. The binder component a2) capable of polyaddition and/or polycondensation consists of solvent-free or solvent-containing and/or hybridized aqueous polyurethane resins, such as polyurethane dispersions and polyurethane polymer hybrid dispersions, having a molecular weight of about 2 500 to 250 000 Dalton, preferably about 25 000 to 100 000 Dalton, which may optionally also be provided with 0 to about 25 % by weight, preferably about 0 to 10% by weight of free amino groups and/or 0 to about 25 % by weight, preferably about 0 to 10% by weight of free hydroxyl groups and/or 0 to about 25 % by weight, preferably about 0 to 10% by weight of free (blocked) isocyanate groups and/or 0 to about 25 % by weight, preferably about 0 to 10% by weight of free epoxy groups, based on the total mass of resin. Moreover, the Il corresponding aqueous polyurethane resins are anionically and/or nonionically and/or cationically stabilized. Preferably, aqueous and nonaqueous polyurethanes based on relatively high molecular weight (polymeric) polyols having one or more hydroxyl groups reactive towards isocyanate groups and a molecular weight of about 500 to 10 000 Dalton, preferably about 1 000 to 2 000 Dalton, such as, for example, (hydrophobically modified) polyalkylene glycols, aliphatic or aromatic polyesters, polycaprolactones, polycarbonates, ca,m polybutadiene polyols, ca,-polymethacrylate diols, ac,-polysulphide diols, ca, co-dihydroxyalkylpolydimethylsiloxanes, hydroxyalkylpolydimethylsiloxanes, hydroxy-functional epoxy resins, hydroxy-functional ketone resins, alkyd resins, dimerfatty acid dialcohols, reaction products based on bisepoxides and unsaturated fatty acids, further hydroxy-functional macromonomers and telechelic polymers or suitable combinations thereof and/or low molecular weight polyols having one or more hydroxyl groups reactive towards isocyanate groups and a molecular weight of about 10 to 1 000 Dalton, preferably of about 32 to 499 Dalton and/or low molecular weight anionically and/or cationically and/or nonionically hydrophilized polyols having one or more hydroxyl groups reactive towards isocyanate groups and a molecular weight of about 10 to 5 000, preferably of about 104 to 2 500 Dalton, aliphatic and/or aromatic polyisocyanates having one or more reactive isocyanate groups and a molecular weight of about 100 to 5 000 Dalton, preferably of about 150 to 300 Dalton, optionally aliphatic and/or aromatic polyamines having one or more primary and/or secondary amino groups reactive towards isocyanate groups and a molecular weight of about 60 to 5 000 Dalton, preferably of about 60 to 250 Dalton, and optionally functionalization components (B) are used. If hybridized aqueous polyurethanes are present, polymers capable of free radical polymerization and lipophilic initiators may also be present in addition to polyurethanes.

18 The binder component a3) capable of polyaddition and/or polycondensation comprises solvent-free or solvent-containing and/or hybridized silane-terminated resins, such as silane-terminated polyurethanes or polyurethane prepolymers (STO, STP, SPUR, inverse SPUR) and/or silane-terminated polyethers (STPe) and/or other silane terminated oligomers and/or polymers and/or hybrid polymers (block, co, graft, random) having terminal and/or lateral alkoxysilane groups. The silane-terminated resin a3) has a molecular weight of about 1 000 to 250 000 Dalton, preferably of about 5 000 to 25 000 Dalton, and has a content of about 0.1 to 50 % by weight, preferably of about 0.5 to 25% by weight of free alkoxysilane groups having any desired substitution pattern, based on the total mass of resin. The binder component a4) capable of polyaddition and/or polycondensation comprises solvent-free or solvent-containing and/or hydrophilized and/or aqueous polyol and/or polyamine mixtures containing commercially available low molecular weight or relatively high molecular weight polymeric amines or alcohols or relatively high molecular weight polymeric polyadducts and/or polycondensates containing amino and/or hydroxyl groups. The polyol and/or polyamine mixture a4) has a molecular weight of about 60 to 100 000 Dalton, e.g. 60 000 to 100 000, preferably about 60 to 10 000, particularly about 60 to 1 000, and has a content of about 1 to 50 % by weight, preferably about 1 to 25% by weight of free hydroxyl groups and/or about 1 to 50 % by weight, preferably about 1 to 25% by weight of free amine groups, based on the total mass of resin. The binder component as) capable of polyaddition and/or polycondensation comprises solvent-free or solvent-containing and/or hydrophilized and/or aqueous epoxy resins, such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether and higher homologues thereof, phenol 19 novolak resins and reactive diluents and extenders. The epoxy resins as) have a molecular weight of about 100 to 10 000 Dalton, preferably of about 200 to 2 000 Dalton, and have a content of about 0.1 to 50 % by weight, preferably of about 1 to 25% by weight of free epoxy groups, based on the total mass of resin. For example, glycidyl ethers of mono- or polyfunctional alcohols, such as, for example, 1,4-butanediol, 1,4-cyclohexanedimethanol, n-dodecanol, 1,6 hexanediol, cresol, neopentylglycol, polyethylene glycol, polypropylene glycol, n-tetradecanol, trimethylolpropane or suitable combinations thereof, may be used as suitable reactive diluents. Alcohols, such as, for example, benzyl alcohol or a suitable combination thereof, may be used as suitable extenders. The binder component a6) capable of polyaddition and/or polycondensation comprises solvent-free or solvent-containing and/or aqueous (meth)acrylate resins, such as dispersions and solutions of polyhydroxypoly(meth)acrylates, which have a molecular weight of about 2 500 to 250 000 Dalton, preferably of about 25 000 to 100 000 Dalton, and a content of about 0.1 to 25 % by weight, preferably of about 1 to 10% by weight of free hydroxyl groups, based on the total mass of resin. The binder component a7) capable of polyaddition and/or polycondensation comprises solvent-free or solvent-containing and/or hydrophilized and/or aqueous polymers based on monomers capable of anionic, cationic or free radical polymerization and having about 0.1 to 25 % by weight, preferably of about 1 to 10% by weight of free hydroxyl groups, based on the total mass of resin, or suitable combinations thereof. All reaction products based on monomers of all types which are capable of anionic, cationic or free radical polymerization and have at least one polymerizable double bond and any desired substitution pattern may be used as suitable polymers.

20 The binder component (A) having a solids content of about 5 to 95 % by weight, preferably about 10 to 90% by weight, may contain the functionalization component (B) in polymer-bound form and have a (polymer)bound fluorine content of about 0.1 to 75 % by weight, preferably of about 0.5 to 5% by weight. In this case preproduced reaction products of the synthesis components on which the components al) to a7) are based and which correspond to the prior art and of component (B) are present. The component (B) can be introduced into the component (A) by polymerization reactions of all types (polyaddition, polycondensation, anionic, cationic or free-radical polymerization) and/or polymer-analogous reactions. It is unimportant whether the component (A) is chemically modified during its preparation or only subsequently with the component (B). The components (A) and (B) may include the structural elements arranged in the main chain and/or side chain

-(CF

2

CF

2 )n- where n > 3 and/or

-(CF

2 CFRO)n- where n > 3 and R = F, CF 3 . The functionalization component (B) capable of polyaddition and/or polycondensation comprises (per)fluoroalkyl-modified compounds or isomer mixtures thereof or comprises suitable reaction products of these (per)fluoroalkyl-modified compounds having a molar mass of about 100 to 10 000 Dalton, preferably of about 250 to 5 000 Dalton and a polymer bound fluorine content of about 10 to 90 % by weight, preferably about 20 to 80% by weight, containing in each case one or more reactive aliphatic and/or aromatic primary and/or secondary (blocked) amino, hydroxyl, mercapto, (blocked) isocyanate, alkoxysilane, epoxide, aziridine or (meth)acrylate group(s).

21 Preferably, b ) (per)fluoroalkylalkyleneamines or (per)fluoroalkylalkylene alcohols or (per)fluoroalkylalkylene mercaptans or (per)fluoroalkylalkylene isocyanates or (per)fluoroalkylalkylene oxides or (per)fluoroalkylalkylenesilanes or (per)fluoroalkylalkylenaziridines or alkyl (per)fluoro(meth)acrylates or (per)fluoroalkyl(meth)acrylates or (per)fluoroalkyl(per)fluoro(meth)acrylates or b 2 ) reaction products of (per)fluoroalkylalkyleneamines or (per)fluoroalkylalkylene alcohols, diisocyanates and diethanolamine, whereas perfluoroalkylalkylene alcoholos having terminal methylene groups (hydrocarbon spacers) of the general formula

CF

3

-(CF

2 )x-(CH 2 )y-OH, where x = 3 - 20 and y = 1 - 6, preferably x = 5 to 13 and/or y = 1 to 2 or hexafluoropropene oxide (HFPO) oligomer alcohols of the general formula

CF

3

CF

2

CF

2 0-(CF(CF 3

)CF

2 0)z-CF(CF 3

)CH

2 -OH, where z = 1 - 10, preferably z = 4 to 10 or mixtures of these preferably being used, zz or b 3 ) reaction products of (per)fluoroalkylalkenes and diethanolamine or alkoxysilanes or other compounds having an amino group and one or more hydroxyl groups, whereas (per)fluoroalkylalkenes having terminal vinyl groups (hydrocarbon spacers) of the general formula

CF

3

-(CF

2 )x-CH=CH 2 , where x = 3 - 20, preferably x = 5 to 13 or mixtures of these preferably being used, or b 4 ) reaction products of alkyl (per)fluoro(meth)acrylates or (per)fluoroalkyl (meth)acrylates or (per)fluoroalkyl (per)fluoro(meth)acrylates and diethanolamine or other compounds having an amino group and one or more hydroxyl group(s) or b) reaction products of (per)fluoroalkylalkylene oxides and N-methylethanolamine or diethanolamine or other compounds having an amino group and one or more hydroxyl group(s) or b 6 ) reaction products of (per)fluoroalkylalkylene oxides and primary and/or secondary amines or polyamines or aminoalkylalkoxysilanes or isocyanatoalkylalkoxysilanes or Z6 b 7 ) reaction products of polyisocyanates and (per)fluoroalkylalkylene alcohols and optionally aminoalkylalkoxysilanes or epoxyalkoxysilanes or (per)fluoroalkylalkyleneamines and optionally aminoalkylalkoxysilanes or epoxyalkoxysilanes or (per)fluoroalkylalkylene oxides or (per)fluoroalkylalkylenecarboxylic acids or bs) reaction products of (per)fluoroalkylalkylene alcohols or (per)fluoroalkylalkyleneamines and isocyanatoalkylalkoxysilanes or epoxyalkoxysilanes or b 9 ) reactive polyhedral oligomeric polysilasesquioxanes (POSS) of the general formula (RaXbSiOl.5)m where a = 0 or 1, b = 0 or 1, a + b =1, m = 4, 6, 8, 10, 12, preferably m = 8 and R, X = any desired inorganic and/or organic and optionally polymeric radical having about 1 to 250 C atoms and 0 to about 50 N and/or 0 to about 50 O and/or about 10 to 100 F and/or 0 to about 50 Si and/or 0 to about 50 S atoms or a suitable combination thereof are used. For example, commercially available mixtures of perfluoroalkyl alcohols (Zonyl@ BA, BA L, BA LD, from DuPont de Nemours) or commercially 24 available mixtures of hexafluoropropene oxide (HFPO) oligomer alcohols (Krytox@, from DuPont de Nemours) or a suitable combination thereof can be used as suitable (per)fluoroalkylalkylene alcohols. For example, 2,2-bis(trifluoromethyl)propanol, 1H,1H-2,5 di(trifluoromethyl)-3,6-dioxaundecafluorononanol, 1H, 1H,7H dodecafluoroheptanol, 2,2,3,3,4,4,5,5,6,6,7,7 dodecafluoro-1,8-octanediol, 1H,1H-heptafluorobutanol, 1H, 1H,9H-hexadecafluorononanol, 1H, 1H,3H hexafluorobutanol, 2H-hexafluoro-2-propanol, 2,2,3,3,4,4,5,5-octafluoro 1,6-hexanediol, 1H,1H,5H-octafluoropentanol, 1H,1H pentafluoropropanol, 2-(perfluorobutyl)ethanol, 3 (perfluorobutyl)propanol, 6-(perfluorobutyl)hexanol, 1H, 1H-perfluoro-1 decanol, 2-(perfluorodecyl)ethanol, 6-(perfluoroethyl)hexanol, 2 (perfluorohexyl)ethanol, 6-(perfluorohexyl)hexanol, 3 (perfluorohexyl)propanol, 1H,1H-perfluoro- 1-nonanol, 1H, 1H-perfluoro- 1 octanol, 2-(perfluorooctyl)ethanol, 6-(perfluorooctyl)hexanol, 3 (perfluorooctyl)propanol, 2-(perfluoro-3-methylbutyl)ethanol, 6-(perfluoro 1-methylethyl)hexanol, 2-(perfluoro-5-methylhexyl)ethanol, 2-(perfluoro 7-methyloctyl)ethanol, 2-perfluoropropoxy-2,3,3,3-tetrafiuoropropanol, 1H, 1H,3H-tetrafluoropropanol, 1,1,2,2-tetrahydroperfluoro- 1 hexadecanol, 1,1,2,2-tetrahydroperfluoro-1l-tetradecanol and 1H, 1H trifluoroethanol or industrial isomer mixtures thereof, the commercial products Fluowet® EA 600, EA 800, EA 093, EA 612, EA 612 N, EA 812 AC, EA 812 IW, EA 812 EP, EA6/1020 from Clariant, the commercial products Zonyl® FSH, FSO, FSN, FS-300, FSN-100, FSO-100 from DuPont de Nemours or suitable combinations thereof can be used as suitable (per)fluoroalkylalkylene alcohols. For example 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decene, the commercial product Zonyl® PFBE from DuPont de Nemours (olefin-based) 25 or suitable combination thereof may be used as suitable (per)fluoroalkylalkenes. For example, 1H, 1H,7H-dodecafluoroheptyl acrylate, 1H, 1H,9H hexadecafluorononyl acrylate, 1H,1H,3H-hexafluorobutyl acrylate, 1H, 1H,5H-octafluoropentyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-(perfluorobutyl)ethyl acrylate, 3-(perfluorobutyl)-2-hydroxypropyl acrylate, 2-(perfluorodecyl)ethyl acrylate, 2-(perfluorohexyl)ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-(perfluoro-3 methylbutyl)ethyl acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl acrylate, 2-(perfluoro-5-methylhexyl)ethyl acrylate, 3-(perfluoro-5 methylhexyl)-2-hydroxypropyl acrylate, 2-(perfluoro-7-methyloctyl)ethyl acrylate, 3-(perfluoro-7-methyloctyl)-2-hydroxypropyl acrylate, 2 (perfluorooctyl)ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 1H,1H,3H-tetrafluoropropyl acrylate, 2,2,2-trifluoroethyl acrylate, 1H-1 (trifluoromethyl)trifluoroethyl acrylate, 1H,1H,7H-dodecafluoroheptyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate, 1H,1H,9H-hexadecafluorononyl methacrylate, 1H,1H,3H hexafluorobutyl methacrylate, 1H,1H,5H-octafluoropentyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, 3-(perfluorobutyl)-2-hydroxypropyl methacrylate, 2 (perfluorodecyl)ethyl methacrylate, 2-(perfluorohexyl)ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 2-(perfluoro-3 methylbutyl)ethyl methacrylate, 3-(perfluoro-3-methylbutyl)-2 hydroxypropyl methacrylate, 2-(perfluoro-5-methylhexyl)ethyl methacrylate, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 2-(perfluoro-7-methyloctyl)ethyl methacrylate, 3-(perfluoro-7 methyloctyl)-2-hydroxypropyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 1H,1H,3H tetrafluoropropyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 1H (trifluoromethyl)trifluoroethyl methacrylate, the commercial products 26 Zonyl@ TA-N (acrylate-based) and TM (methacrylate-based) from DuPont de Nemours or a suitable combination thereof may be used as suitable (per)fluoroalkyl (meth)acrylates and/or (per)fluoroalkyl (per)fluoro (meth)acrylates. For example, 4,4,5,5,6,6,6-heptafluorohexene-1,2-oxide, 4,4,5,5,6,6,7,7,7 nonafluoroheptene- 1,2-oxide, 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononene 1,2-oxide, 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecene 1,2-oxide or a suitable combination thereof may be used as suitable (per)fluoroalkylalkylene oxides. For example, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorotriethoxysilane (DYNASILAN® F 8800, F 8261, F 8262, F 8263, from Degussa AG) may be used as a suitable (per)fluoroalkylalkoxysilane. Silasesquioxanes are oligomeric or polymeric substances, the completely condensed members of which have the general formula (SiO 3 /2R)n, where n > 4 and the radical R may be a hydrogen atom but generally represents an organic radical. The smallest structure of a silasesquioxane is the tetrahedron. Voronkov and Lavrent'yev (Top. Curr. Chem. 102 (1982), 199-236) describe the synthesis of completely condensed and incompletely condensed oligomeric silasesquioxanes by hydrolytic condensation of trifunctional RSiY 3 precursors, where R represents a hydrocarbon radical with 1 to 20, particularly 1 to 4 carbon atoms and Y represents a hydrolysable group, such as, for example, chloride, alkoxide or siloxide. Lichtenhan et al. describe the base-catalyzed preparation of oligomeric Silasesquioxanes (WO 01/10 871). Silasesquioxanes of the formula RsSisO 1 2 (having identical or different hydrocarbon radicals R) can be reacted under base catalysis to form functionalized, incompletely condensed silasesquioxanes, such as, for example, RTSi 7

O

9

(OH)

3 or RsSisOii(OH) 2 and RsSisOio(OH) 4 , (Chem. Commun. (1999), 2309-10; Polym. Mater. Sci. Eng. 82 (2000), 301-2; WO 01/10 871) and thus serve 27 as a parent compound for a multiplicity of different incompletely condensed and functionalized silasesquioxanes. In particular, the silasesquioxanes (trisilanols) of the formula RTSi 7

O

9 (OH)3 can be converted by reaction with functionalized, monomeric silanes (corner capping) into appropriately modified oligomeric silasesquioxanes. Reactive polyhedral oligomeric polysilasesquioxanes (POSS) of the general formula (RaXbSiO1.5)m where a=Oor1, b=Oor 1, a+b=1, m=4,6,8,10,12, preferably m = 8, R = hydrogen atom, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl or cycloalkynyl group or polymer units which in each case are substituted or unsubstituted or further functionalized polyhedral oligomeric silicon-oxygen cluster units which are linked via a polymer unit or a bridging unit, and X = oxy, hydroxyl, alkoxy, carboxyl, silyl, alkylsilyl, alkoxysilyl, silyloxy, alkylsilyloxy, alkoxysilyloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy, ester, (per)fluoroalkyl, isocyanate, blocked isocyanate, acrylate, methacrylate, nitrile, amino, phosphine or polyether group or substituents of the type R which carry at least one substituent of the type X, the substituents of type R as well as the substituents of type X being identical or different, are preferably used. According to a preferred embodiment, the component (A) contains the component (B) in polymer bound form and has a polymer-bound fluorine content of about 0.1 to 75 per-cent by weight, preferably of about 0.5 to 5% by weight.

28 For example, the curing component (C) is aliphatic and/or aromatic polyamines, polyamidoamines, polyoxyalkyleneamines, low molecular weight polyols, high molecular weight (polymeric) polyols, (water emulsifiable) aliphatic and/or aromatic polyisocyanates, (water emulsifiable) aliphatic andlor aromatic polyurethane prepolymers having free isocyanate groups or free hydroxyl groups or free amino groups, polyaziridines or atmospheric humidity. For example, 1,3-pentanediamine (DAMP), 2 methylpentamethylenediamine (MPMDA), benzylaminopropylamine (BAPA), bisaminomethylcyclohexane or 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), cyclohexylaminopropylamine (NAPCHA), diaminocyclohexane or 1,2-diaminocyclohexane (DAC or DCH), diethylaminopropylamine (DEAPA), diethylenetriamine or 1,4,7-triazaheptane (DETA), dimethyl PACM or bis(4,4'-amino-3,3'-methylcyclohexyl)methane (DM-PACM), dipropylenetriamine or 1,5,9-triazanonane, ethylenediamine or 1,2 diaminoethane (EDA), hexamethylenediamine or 1,8-diaazaoctane (HMDA), isophoronediamine or 3-methylamino-3,5,5-trimethyl aminocyclohexane (IPD or IPDA), methylpentamethylenediamine or 2 methyl-1,7-diaazaheptane, N3-amine or 1,4,8-triazaoctane N4-amine or 1,5,8,12-tetraazadodecane, n-amineethylpiperazine or 1-(2-aminoethyl) 1,4-diazacyclohexane (NAEP), N-aminopropylcyclohexylamine (NAPCHA), p-aminocyclohexylmethane or bis(4,4' aminocyclohexyl)methane (PACM), pentaethylenehexamine or 1,4,7,10,13,16-hexaazahexadecane (PEHA), propylenediamine or 1,5 diazapentane (PDA), tetraethylenepentamine or 1,4,7,10,13 pentaazatridecane (TEPA), tricyclododecanediamine or 3(4),8(9)-bis (aminomethyl)tricyclo- [5,2,1,02,6]decane (TCD), triethylenetetramine or 1,4,7,10-tetraazadecane (TETA), trimethylhexamethylenediamine or 2,2,4-trimethyl-1,8-diaazaoctane and/or 2,4,4-trimethyl-1,8-diaazaoctane or suitable combinations thereof may be used as suitable aliphatic polyamines.

29 For example, diaminodiphenylmethane or bis(4,4'-aminophenyl)methane (DDM), diaminodiphenyl sulphone or bis(4,4'-aminophenyl) sulphone (DDS), diethylaminodiphenylmethane (DEDDM), diethyltoluenediamine (DETDA), m-xylylenediamine or 1,3-bis(aminomethyl)benzene (mXDA) or suitable combinations thereof may be used as suitable aromatic polyamines. Polyoxyethylenepolyamines, polyoxypropylenepolyamines, polytetrahydrofuranpolyamines, other polyoxyalkylenepolyamines based on any desired alkylene oxide or mixtures thereof (co, block, random), butanediol ether diamine or 1,14-diaza-5,10-dioxotetradecane (BDA) or suitable combinations thereof may be used as suitable aromatic polyoxyalkylenamines. In addition, polyaminoamides, Mannich bases, epoxide adducts, such as EDA adducts, DETA adducts, type 100, type 115, type 125, type 140, type 250 (Genamid), PAA adduct or suitable combinations thereof may be used. For example, polyisocyanates, a polyisocyanate derivative or polyisocyanate homologues having two or more aliphatic or aromatic isocyanate groups of the same or different reactivity or suitable combinations thereof may be used as suitable polyisocyanates. The polyisocyanates sufficiently well known in polyurethane chemistry or combinations thereof are particularly suitable. For example, 1,6 diisocyanatohexane (HDI), 1-isocyanato-5-isocyanatomethyl-3,3,5 trimethylcyclohexane or isophorone diisocyanate (IPDI), bis(4 isocyanatocyclohexyl)methane (H 12 MDI), 1,3-bis(1-isocyanato- 1-methyl ethyl)benzene (m-TMXDI) or industrial isomer mixtures of the individual aromatic polyisocyanates may be used as suitable aliphatic polyisocyanates. For example, 2,4-diisocyanatotoluene or toluene 30 diisocyanate (TDI), bis(4-isocyanatophenyl)methane (MDI) and optionally higher homologues thereof (polymeric MDI) or industrial isomer mixtures of the individual aromatic polyisocyanates may be used as suitable aromatic polyisocyanates. Furthermore, the so-called "coating polyisocyanates" based on bis(4-isocyanatocyclohexyl)methane (H 1 2 MDI), 1,6-diisocyanatohexane (HDI), 1-isocyanato-5-isocyanatomethyl-3,3,5 trimethylcyclohexane (IPDI) are in principle also suitable. The term "coating polyisocyanates" characterizes those derivatives of these diisocyanates which have allophanate, biuret, carbodiimide, isocyanurate, uretdione or urethane groups and in which the residual content of monomeric diisocyanates was reduced to a minimum in accordance with the prior art. In addition, it is also possible to use modified polyisocyanates which are obtainable, for example, by hydrophilic modification of "coating polyisocyanates" based on 1,6-diisocyanatohexane (HDI). For example, (hydrophobically modified) polyalkylene glycols, aliphatic or aromatic polyesters, polycaprolactones, polycarbonates, a, w polybutadienepolyols, a,o-polymethacrylatediols, a,w-polysulphidediols, a, ow-dihydroxyalkylpolydimethylsiloxanes, hydroxyalkylpolydimethylsiloxanes, hydroxy-functional epoxy resins, hydroxy-functional ketone resins, alkyd resins, dimer fatty acid dialcohols, reaction products based on bisepoxides and unsaturated fatty acids, further hydroxy-functional macromonomers and telechelic polymers or suitable combinations thereof may be used as suitable higher molecular weight (polymeric) polyols. For example, 1,2-ethanediol or ethylene glycol, 1,2-propanediol or 1,2 propylene glycol, 1,3-propanediol or 1,3-propylene glycol, 1,4-butanediol or 1,4-butylene glycol, 1,6-hexanediol or 1,6-hexamethylene glycol, 2 methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol or neopentylglycol, 1,4-bis(hydroxymethyl)cyclohexane or cyclohexanedimethanol, 1,2,3- 31 propanetriol or glycerol, 2-hydroxymethyl- 2-methyl- 1,3-prop anol or trimethylolethane, 2-ethyl-2-hydroxymethyl 1,3-propanediol or trimethylolpropane, 2,2-bis(hydroxymethyl)- 1,3-propanediol or pentaerythritol, 2-hydroxymethyl-3-hydroxypropionic acid or dimethylolacetic acid, 2-hydroxymethyl-2-methyl-3-hydroxypropionic acid or dimethylolpropionic acid, 2-hydroxymethyl-2-ethyl- 3 -hydroxypropionic acid or dimethylolbutyric acid, 2-hydroxymethyl-2-propyl-3 hydroxypropionic acid or dimethylolvaleric acid or suitable combinations thereof may be used as suitable low molecular weight polyols. The components (B) and (C) may be compounds having one or more primary or secondary amino and/or hydroxyl group(s) in the form of latent curing agents or reactive diluents based on aldimines and/or ketimines and/or enamines and/or oxazolidines and/or polyaspartic acid esters, latent curing agents free of cleavage products and based on azetidines and/or diazepines or suitable combinations thereof. Latently reactive ("inert") components can be added to the potential reactants before the reaction and can be activated only during the actual processing by atmospheric humidity and/or by appropriate processing conditions. The formulation component (D) is inorganic and/or organic fillers, light fillers, pigments and carrier materials, inorganic and/or organic nanomaterials, inorganic and/or organic fibres, further polymers and/or redispersible polymer powders of all types, antifoams, deaerators, lubricants and flow additives, substrate wetting agents, wetting and dispersant additives, water repellents, rheology additives, coalescence aids, matting agents, adhesion promoters, antifreezes, antioxidants, UV stabilisers, bactericides, fungicides, water, solvents and catalysts of all types. These constituents are sufficiently well known from finish and coating technology, cf. in this context also U. Zorll (editor): Lehrbuch der 32 Lacktechnologie [Textbook of Coating Technology], Curt R. Vincentz Verlag Hanover 1998. The components (B) and/or (C) and/or (D) may be present in coated and/or microencapsulated and/or carrier-fixed and/or hydrophilized and/or solvent-containing form. In the case of latently reactive, coated and/or microencapsulated systems, the liberation of the active component(s) can take place in a retarded manner in accordance with the application requirements, which leads to an effect on the reactivity or the reaction times of the total system consisting of the components (A), (B), optionally (C) and optionally (D). In the case of (latently reactive) carrier-fixed systems, all suitable inorganic and/or organic carrier materials may be used. In addition, the components (B) and/or (C) and/or (D) can be applied in any desired combination and sequence (e.g. layer structure) to the carrier materials, which leads to an effect on the reactivity or the reaction times of the total system consisting of the components (A), (B), optionally (C) and optionally (D). The use of latently reactive components of all types results in further degrees of freedom with respect to the preparation of the individual components of the total system consisting of the components (A), (B), optionally (C) and optionally (D). Latently reactive ("inert") components can be added to the potential reactants before the reaction and activated only during the actual processing by atmospheric humidity and/or by appropriate processing conditions. The equivalent ratio of the reactive groups in the components (A), (B) and (C) is set at about 0.1 to 10, preferably about 0.5 to 5, in the case of curing without water (atmospheric humidity). The polymer obtained after curing and consisting of the components (A), (B) and optionally (C) has an average molecular weight (number average) of about 50 000 to 5 000 000 Dalton, preferably of about 100 000 to 500 000 Dalton.

33 The present invention furthermore relates to a process for the preparation of the fluoromodified reactive resin systems according to the invention, in which al) in the case of three-component application, the components (A), (B) and (C) capable of polyaddition and/or polycondensation are mixed in any desired manner and reacted, it being possible, if appropriate, for a formulation component (D) to be present, or a2) in the case of two-component application, preproduced mixtures of the components (A) and (B) or (B) and (C) capable of polyaddition and/or polycondensation are mixed with the components (C) or (A) capable of polyaddition and/or polycondensation in any desired manner or only the components (A) and (B) are mixed in any desired manner and reacted, it being possible, if appropriate, for a formulation component (D) to be present, or a3) in the case of one-component application, preproduced mixtures of the components (A) and (B) capable of polyaddition and/or polycondensation are reacted with the component (C) consisting of water (atmospheric humidity), it being possible, if appropriate, for a formulation component (D) to be present, and finally b) the mixtures from the stages a), b) or c) are applied in any desired manner to/in the respective substrate.

34 According to a preferred embodiment, the component (B) is optionally first prepared before the stages a) or b) or c) and the formulation component (D) or the individual constituents thereof is or are mixed, before, during or after the reaction according to the stages al), a2) or a3), with the components (A), (B) or (C) or the preproduced mixtures of the components (A) and (B) or (B) and (C). The components (B) andlor (C) and/or (D) can be mixed in latently reactive form with the other components and activated only on application. For example, the reaction stages a), b), c) and d) are carried out at a temperature of about 0 to 150 'C, particularly at about 10 to 75°C. If the fluoromodified reactive resin systems contain solvent and/or water, it is necessary for sufficient miscibility to be ensured. The expression "sufficient miscibility" means that a homogeneity of the total system is possible with the mixing techniques common in the finish and coating technology or that the compatibility of component (B), (C) and (D) must be compatible with component (A) (i.e. that no phase separation occurs). The present invention furthermore relates to the use of the fluoromodified reactive resin systems according to the invention in the building or industrial sector for permanent oil-, water- and dirt-repellent surface treatment or modification of mineral and nonmineral substrates, such as * Inorganic surfaces, such as, for example, porous, absorptive, rough and polished 35 building materials and structures of all types (such as, for example, concrete, gypsum, silica and silicates, artificial stone, natural stone (such as, for example, granite, marble, sandstone, slate, serpentine), clay, cement, brick) and enamel, fillers and pigments, glass, ceramic, metals and metal alloys, Organic surfaces, such as, for example, woven fabrics and textiles, wood and wood based materials, wood veneer, glass fibre-reinforced plastics (GFRP), plastics, leather, natural fibres, polar organic polymers of all types, composite materials. The fluoromodified reactive resin systems according to the invention are suitable for permanent, oil-, water- and dirt-repellent surface treatment or modification in the following fields of use: Building, such as, for example, * antigraffiti / antisoiling coatings * easy-to-clean coatings * further coatings of all types (such as, for example, balcony coatings, roof (tile) coatings, stoving enamels, paints and finishes, masonry paints, floor coatings, industrial floors having low, medium and high load capacities, parking floor coatings, sport floors, powder coatings) * seals * precast concrete parts * moulded concrete parts * tiles and joints * adhesives and sealants * noise control walls * corrosion protection * plasters and decorative plasters 36 * exterior insulation and finish systems (EIFS) and heat insulation systems. Non-building and industry, such as, for example, * automotive industry * coil coatings * stoving enamels * woven fabric and textile coating * glass facades and glass surfaces * ceramic and sanitaryware * leather finishing * surface-modified fillers and pigments * paper coating * rotor blades of wind power stations * marine paints. The fluoromodified reactive resin systems according to the invention are also suitable for the mass hydrophobization/oleophobization of concrete, such as, for example, * precast concrete parts * moulded concrete parts * building site concrete * shotcrete * ready-mix concrete. The application of the fluoromodified reactive resin systems according to the invention is effected by the methods known from coating technology, such as, for example, flooding, pouring, knife coating, roller-coating with a fur covered roller, spraying, brushing, dipping, roller-coating with a hard roller.

37 The drying and curing of the coatings produced from the fluoromodified reactive resin systems according to the invention are effected in general at normal (outdoor and indoor) temperatures in the range from about 0 to 50 'C, i.e. without special heating of the coatings, but, depending on the application, can also be effected at higher temperatures in the range from about 50 to 150 'C. The following examples are intended to illustrate the invention in more detail.

38 Examples Example 1: Fluoromodified macaromonomer (curing agent) 83.06 g of isophorone diisocyanate (IPDI) and 0.1 g of T12 DBTL were initially introduced into a three-necked flask equipped with a KPG stirrer, thermometer and nitrogen blanketing and heated to about 50 C. Thereafter, 200 g of fluoroalcohol (Fluowet EA 812 AC, from Clariant), which was heated beforehand to 60 oC, were metered uniformly into the initially introduced mixture over a period of 2 h with stirring. The temperature for this reaction step was kept at 50-55°C. Since the reaction is slightly exothermic, slight cooling may be necessary. After complete addition of the fluoroalcohol, stirring was effected for a further 2 h at 50 55 0 C. The NCO value was then determined. An NCO value of 5.65 % by weight was found (theory 5.55 % by weight). 263 g of the preadduct were then added slowly with stirring to an initially introduced mixture of 36.47 g of diethanolamine and 74.91 g of N methylpyrrolidone. The temperature was kept at 55-60 'C. After complete addition of the preadduct, stirring was effected for a further 0.5 h at 50 55 oC and the finished product was finally filled. The product is clear, slightly yellow and slightly viscous at room temperature.

39 Example 2: Polyurethane dispersion (binder) 100.00 g of a polycarbonate-polyol (tradename: Desmophen VP LS 2391 from Bayer), 5.00 g of 1,4-butanediol (from Aldrich), 7.15 g of dimethylolpropionic acid (tradename: DMPA® from Mallinckrodt), 0.1 g of dibutyltin dilaurate (from Aldrich) and 17.50 g of N-methylpyrrolidone (from Aldrich) were initially introduced into a four-necked flask equipped with a KPG stirrer, reflux condenser, thermometer and nitrogen blanketing and was stirred at 600 C until the dimethylolpropionic acid had completely dissolved. Thereafter, 63.53 g of isophorone diisocyanate (from Degussa) were added and stirring was effected at 80 to 90 oC while blanketing with nitrogen until the theoretical NCO content of 5.52 % by weight was reached. The course of the reaction was monitored acidimetrically. After the end of the polyaddition reaction, an NCO content of 5.61% by weight was found and the prepolymer was cooled to 60-65 *C. For neutralisation, (90 equivalent-%) of the prepolymer, 4.85 g of triethylamine were then added and were stirred thoroughly for 3 minutes. 165.00 g of the prepolymer were then dispersed in 236.59 g of tapwater with thorough stirring. In order to produce the polyurethane dispersion, chain extension was effected with a mixture of 9.07 g of N-(2 hydroxyethyl)ethylenediamine (85 equivalent-%) and 9.07 g of tapwater. A stable polyurethane dispersion having the following characteristics was obtained: Appearance opaque, translucent Solids content 38 % by weight pH 7.30 OH content 0.38 % by weight 4U Example 3: Fluoromodified polyurethane dispersion (binder) 100.00 g of a polycarbonate-polyol (tradename: Desmophen VP LS 2391 from Bayer), 17.80 g of the fluoromodified macromonomer from Example 1, 3.50 g of 1,4-butanediol (from Aldrich), 9.00 g of dimethylolpropionic acid (tradename: DMPA@ from Mallinckrodt), 0.1 g of dibutyltin dilaurate (from Aldrich) and 15.00 g of N-methylpyrrolidone (from Aldrich) were initially introduced into a four-necked flask equipped with a KPG stirrer, reflux condenser, thermometer and nitrogen blanketing and was stirred at 60 'C until the dimethylolpropionic acid had completely dissolved. Thereafter, 69.05 g of isophorone diisocyanate (from Degussa) were added and stirring was effected at 80 to 90 'C while blanketing with nitrogen until the theoretical NCO content of 5.41% by weight was reached. The course of the reaction was monitored acidimetrically. After the end of the polyaddition reaction, an NCO content of 5.28 % by weight was found and the prepolymer was cooled to 60-65 oC. For neutralisation, (90 equivalent %) of the prepolymer, 6.11 g of triethylamine were then added and were stirred thoroughly for 3 minutes. 180.00 g of the prepolymer were then dispersed in 259.97 g of tapwater with thorough stirring. In order to produce the polyurethane dispersion, chain extension was effected with a mixture of 9.73 g of N-(2 hydroxyethyl)ethylenediamine (85 equivalent-%) and 9.73 g of tapwater. A stable polyurethane dispersion having the following characteristics was obtained: Appearance opaque, translucent Solids content 38 % by weight pH 7.40 OH content 0.35 % by weight 41 Example 4: Fluoromodified reactive resin system (3-component) 3.13 g of fluoromodified macromonomer from Example 1 (OH content 1.57 % by weight) were dispersed in 100 g of polyurethane dispersion from Example 2 (OH content 0.38 % by weight) using a dissolver. Thereafter, 7.59 g of Basonat HW 100 (NCO content 16.8 % by weight, from BASF) were diluted with 0.75 g of Proglyde DMM (from Dow Chemicals) and likewise dispersed in the above dispersion mixture. Example 5: Fluoromodified reactive resin system (3-component) 2.0 of fluoromodified macromonomer from Example 1 (OH content 1.57 % by weight) were dispersed in 100 g of polyurethane dispersion from Example 3 (OH content 0.35 % by weight) using a dissolver. Thereafter, 6.73 g of Basonat HW 100 (NCO content 16.8 % by weight, from BASF) were diluted with 0.7 g of Proglyde DMM (from Dow Chemicals) and likewise dispersed in the above dispersion mixture. The surface energy is 11 to 12 mN/m and the contact angle 0 (water) is 100 to 1100. Example 6: Fluoromodified reactive resin system (2-component) (comparison) 6.18 g of Basonat HW 100 (NCO content 16.8 % by weight, from BASF), which was diluted beforehand with 0.6 g of Proglyde DMM (from Dow Chemicals), were dispersed in 100 g of fluoromodified polyurethane dispersion fromn Example 3 (OH content 0.35 % by weight) using a dissolver. The surface energy is 12 to 13 mN/m and the contact angle (water) is 110 to 1200.

42 The coating systems or surfaces according to Examples 4 and 5 have reduced critical surface tensions Yc, increased contact angles 0 and substantially lower dirt pickup tendency compared with Example 6 not according to the invention.

Claims (25)

1. Fluoromodified reactive resin systems having improved surface properties, comprising a) 100 to 300 parts by weight of a binder component (A) capable of polyaddition and/or polycondensation, comprising al) a polyurethane resin having a molecular weight of 1,000 to 25,000 Dalton and 0.1 to 50 % by weight of free (blocked) isocyanate groups, based on the total mass of resin, or a2) an aqueous anionically and/or nonionically and/or cationically stabilized polyurethane resin having a molecular weight of 2,500 to 250,000 Dalton and 0 to 25 % by weight of free amine groups and/or 0 to 25 % by weight of free hydroxyl groups and/or 0 to 25 % by weight of free (blocked) isocyanate groups and/or 0 to 25 % by weight of free epoxy groups, based on the total mass of resin, or a3) a silane-terminated resin having a molecular weight of 1,000 to 250,000 Dalton and 0.1 to 50 % by weight of free alkoxysilane groups having any desired substitution pattern, based on the total mass of resin or 44 a4) a polyol and/or polyamine mixture based on low molecular weight and/or higher molecular weight (polymeric) compounds having a molecular weight of 60 to 10,000 Dalton and 1 to 50 % by weight of free hydroxyl groups and/or 1 to 50 % by weight of free amine groups, based on the total mass of resin, or as) an epoxy resin having a molecular weight of 100 to 10,000 Dalton and 0.1 to 50 % by weight of free epoxy groups, based on the total mass of resin, or a6) a (meth)acrylate resin having a molecular weight of 2,500 to 250,000 Dalton and 0.1 to 25 % by weight of free hydroxyl groups, based on the total mass of resin, or a7) another polymer based on monomers capable of anionic, cationic or free radical polymerization and having 0.1 to 25 % by weight of free hydroxyl groups, based on the total mass of resin, or a suitable combination thereof, the binder component (A) having in each case a solids content of 5 to 95 % by weight of polymer, 45 b) 5 to 100 parts by weight of a functionalization component (B) capable of polyaddition and/or polycondensation and having a molar mass of 100 to 10,000 Dalton and a polymer bound fluorine content of 10 to 90 % by weight, containing in each case one or more reactive aliphatic and/or aromatic primary and/or secondary (blocked) amino, hydroxyl, mercapto, (blocked) isocyanate, alkoxysilane, epoxide or aziridine or (meth)acrylate group(s), comprising b 1 ) (per)fluoroalkylalkyleneamines or (per)fluoroalkylalkylene alcohols or (per)fluoroalkylalkylene mercaptans or (per)fluoroalkylalkylene isocyanates or (per)fluoroalkylalkylene oxides or (per)fluoroalkylalkylene silanes or (per)fluoroalkylalkylenaziridines or alkyl (per)fluoro(meth)acrylates or (per)fluoroalkyl (meth)acrylates or (per)fluoroalkyl (per)fluoro(meth)acrylates or b 2 ) reaction products of (per)fluoroalkylalkyleneamines or (per)fluoroalkylalkylene alcohols, diisocyanates and diethanolamine, whereas perfluoroalkylalkylene alcohols having terminal methylene groups (hydrocarbon spacers) of the general formula CF 3 -(CF 2 )x-(CH2)y-OH, where x = 3- 20 and y = 1 - 6 46 or hexafluoropropene oxide (HFPO) oligomer alcohols of the general formula CF 3 CF 2 CF 2 0-(CF(CFa)CF 2 0)z-CF(CF 3 )CH2-OH, where z = 1 - 10 or mixtures of these preferably being used, or b 3 ) reaction products of (per)fluoroalkylalkenes and diethanolamine or alkoxysilanes or other compounds having an amino group and one or more hydroxyl groups, whereas (per)fluoroalkylalkenes having terminal vinyl groups (hydrocarbon spacers) of the general formula CF 3 -(CF 2 )x-CH=CH 2 , where x = 3 - 20 or mixtures of these preferably being used, or b 4 ) reaction products of alkyl(per)fluoro(meth)acrylates or (per)fluoroalkyl(meth)acrylates or (per)fluoroalkyl (per)fluoro(meth)acrylates and diethanolamine or other compounds having an amino group and one or more hydroxyl group(s) or 47 b s ) reaction products of (per)fluoroalkylalkylene oxides and N-methylethanolamine or diethanolamine or other compounds having an amino group and one or more hydroxyl group(s) or b 6 ) reaction products of (per)fluoroalkylalkylene oxides and primary and/or secondary amines or polyamines or aminoalkylalkoxysilanes or isocyanatoalkylalkoxysilanes or b y ) reaction products of polyisocyanates and (per)fluoroalkylalkylene alcohols and optionally aminoalkylalkoxysilanes or epoxyalkoxysilanes or (per)fluoroalkylalkylenamines and optionally aminoalkylalkoxysilanes or epoxyalkoxysilanes or (per)fluoroalkylalkylene oxides or per)fluoroalkylalkylenecarboxylic acids or bs) reaction products of (per)fluoroalkylalkylene alcohols or (per)fluoroalkylalkylenamines and isocyanatoalkylalkoxysilanes or epoxyalkoxysilanes or b 9 ) reactive polyhedral oligomeric polysilasesquioxanes (POSS) of the general formula 48 (RaXbSiOI 5)m where a = 0 or1, b = 0 or 1, a + b = 1, m = 4, 6, 8, 10, 12and R, X = any desired inorganic and/or organic and optionially polymeric radical having 1 to 250 C atoms and 0 to 50 N and/or 0 to 50 0 and/or 10 to 100 F and/or 0 to 50 Si and/or 0 to 50 S atoms or a suitable combination thereof, c) 0 to 100 parts by weight of a curing component (C) capable of polyaddition and/or polycondensation and having a molecular weight of 100 to 10,000 Dalton, containing in each case one or more reactive aliphatic and/or aromatic primary and/or secondary (blocked) amino, hydroxyl, mercapto, (blocked) isocyanate or aziridine group(s) and/or water, and d) 0 to 300 parts by weight of a formulation component (D), it being possible for the component (A) to contain the component (B) optionally in polymer-bound form and to have a (polymer-)bound fluorine content of 0.1 to 75 % by weight.

2. Reactive systems according to Claim 1, characterized in that the polyurethane resin al) is a solvent-free or solvent-containing system.

3. Reactive systems according to Claim 1, characterized in that the polyurethane resin a2) is a solvent-free or solvent-containing and/or hybridized system.

4. Reactive resin systems according to Claim 1, characterized in that the silane-terminated resin a3) is a solvent-free or solvent-containing and/or hybridized system. 49

5. Reactive resin systems according to Claim 1, characterized in that the silane-terminated resin a3) is silane-terminated polyurethanes and/or silane-terminated polyethers and/or other silane-terminated oligomers and/or polymers and/or hybrid polymers having terminal and/or lateral alkoxysilane groups.

6. Reactive systems according to Claim 1, characterized in that the polyol and/or polyamine mixture a4) is a solvent-free or solvent containing and/or hydrophilized and/or aqueous system.

7. Reactive systems according to Claim 1, characterized in that the epoxy resin as) is a solvent-free or solvent-containing and/or hydrophilized and/or aqueous system.

8. Reactive systems according to Claim 1, characterized in that the (meth)acrylate resin a6) is a solvent-free or solvent-containing and/or aqueous system.

9. Reactive systems according to Claim 1, characterized in that the polymer a7) is a solvent-free or solvent-containing and/or aqueous system.

10. Reactive resin systems according to Claim 1, characterized in that polyurethanes based on (hydrophobically modified) polyalkylene glycols, aliphatic or aromatic polyesters, polycaprolactones, polycarbonates, o, w-polybutadienepolyols, ax, w-polymethacrylatediols, a, w-polysulphidediols, xa, m-dihydroxyalkylpolydimethylsiloxanes, hydroxyalkylpolydimethylsiloxanes, hydroxy-functional epoxy resins, hydroxy-functional ketone resins, alkyd resins, dimerfatty acid dialcohols, reaction products based on bisepoxides and unsaturated 50 fatty acids, further hydroxy-functional macromonomers and telechelic polymers or suitable combinations thereof are used as component (A).

11. Reactive resin systems according to any of Claims 1 to 10, characterized in that the components (A) and (B) comprise the structural elements -(CF 2 CF 2 )n- where n > 3 and/or -(CF 2 CFRO)n- where n > 3 and R = F, CF 3 arranged in the main chain and/or side chain.

12. Reactive resin systems according to any of Claims 1 to 11, characterized in that the component (C) comprises aliphatic and/or aromatic polyamines, polyamidoamines, polyoxyalkylenamines, low molecular weight polyols, high molecular weight (polymeric) polyols, (water-emulsifiable) aliphatic and/or aromatic polyisocyanates, (water-emulsifiable) aliphatic and/or aromatic polyurethane prepolymers having free isocyanate groups or free hydroxyl groups or free amino groups, polyaziridines or atmospheric humidity.

13. Reactive systems according to any of Claims 1 to 12, characterized in that the components (B) and (C) comprise compounds having one or more primary or secondary amino and/or hydroxyl group(s) in the form of latent curing agents or reactive diluents based on aldimines and/or ketimines and/or enamines and/or oxazolidines and/or polyaspartic acid esters, latent curing agents free of cleavage products and based on azetidines and/or diazepines or suitable combinations thereof. 51

14. Reactive resin systems according to any of Claims 1 to 13, characterized in that the component (D) comprises inorganic and/or organic fillers, light fillers, pigments and carrier materials, inorganic and/or organic nanomaterials, inorganic andlor organic fibres, further polymers and/or redispersible polymer powders of all types, antifoams, deaerators, lubricants and flow additives, substrate wetting agents, wetting and dispersant additives, water repellents, rheology additives, coalescence aids, matting agents, adhesion promoters, antifreezes, antioxidants, UV stabilizers, bactericides, fungicides, water, solvents and catalysts of all types.

15. Reactive resin systems according to any of Claims 1 to 14, characterized in that the components (B) and/or (C) and/or (D) are present in coated and/or microencapsulated and/or carrier-fixed and/or hydrophilized and/or solvent-containing form.

16. Reactive resin systems according to any of Claims 1 to 15, characterized in that the equivalent ratio of the reactive groups in the components (A), (B) and optionally (C) in the case of curing without water (atmospheric humidity) is set at 0.1 to 10, preferably 0.5 to 5.

17. Reactive resin systems according to any of Claims 1 to 16, characterized in that the polymer obtained after curing and comprising the components (A), (B) and optionally (C), has an average molecular weight (number average) of 50,000 to 5,000,000 Dalton.

18. Process for the preparation of the reactive resin systems according to Claims 1 to 17, characterized in that al) in the case of three-component application, the components (A), (B) and (C) capable of polyaddition and/or polycondensation are mixed in any desired manner and reacted, it being possible, if appropriate, for a formulation component (D) to be present, or a2) in the case of two-component application, preproduced mixtures of the components (A) and (B) or (B) and (C) capable of polyaddition and/or polycondensation are mixed with the components (C) or (A) capable of polyaddition and/or polycondensation in any desired manner or only the components (A) and (B) are mixed in any desired manner and reacted, it being possible, if appropriate, for a formulation component (D) to be present, or a3) in the case of one-component application, preproduced mixtures of the components (A) and (B) capable of polyaddition and/or polycondensation are reacted with the component (C) consisting of water (atmospheric humidity), it being possible, if appropriate, for a formulation component (D) to be present, and finally b) the mixtures from the stages al), a2) or a3) are applied in any desired manner to/in the respective substrate.

19. Process according to Claim 18, characterized in that the component (B) is first prepared before the stages ai) or a2) or a3) and the formulation component (D) or the individual constituents thereof is or are mixed, before, during or after the reaction according to the stages ai), a2) or a3), with the components (A), (B) or (C) or the preproduced mixtures of the components (A) and (B) or (B) and (C).

20. Process according to Claim 18, characterized in that the components (B) and/or (C) and/or (D) in latently reactive form are mixed with the other components and activated only on application.

21. Process according to Claims 18 to 20, characterized in that the reaction stages al), a2) or a3) are carried out at a temperature of 0 to 150 0 C.

22. Use of the reactive resin systems according to Claims 1 to 17 in the building or industrial sector for permanent oil-, water- and dirt repellent surface treatment or modification of mineral and nonmineral substrates, such as * inorganic surfaces, such as, for example, porous, absorptive, rough and polished building materials and structures and enamel, fillers and pigments, glass, ceramic, metals and metal alloys, * organic surfaces, such as, for example, woven fabrics and textiles, wood and wood based materials, wood veneer, glass fibre-reinforced plastics (GFRP), plastics, leather, natural fibres, polar organic polymers of all types, composite materials.

23. Use of the reactive resin systems according to Claims 1 to 17 for permanent oil-, water- and dirt-repellent surface treatment or modification in the building sector, such as, for example * antigraffiti / antisoiling coatings 04 * easy-to-clean coatings * further coatings of all types (such as, for example, balcony coatings, roof (tile) coatings, stoving enamels, paints and finishes, masonry paints, floor coatings, industrial floors having low, medium and high load capacities, parking floor coatings, sport floors, powder coatings) * seals * precast concrete parts * moulded concrete parts * tiles and joints * adhesives and sealants * noise control walls * corrosion protection * plasters and decorative plasters * composite heat insulation systems and heat insulation systems.

24. Use of the reactive resin systems according to Claims 1 to 17 for permanent oil-, water- and dirt-repellent surface treatment or modification in the nonbuilding and industrial sector, such as, for example, * automotive industry * coil coatings * stoving enamels * woven fabric and textile coating * glass facades and glass surfaces * ceramic and sanitaryware * leather finishing * surface-modified fillers and pigments * paper coating * rotor blades of wind power stations * marine paints. DD

25. Use of the reactive resin systems according to Claims 1 to 17 in the building. or industrial sector for mass hydrophobization/oleophobization of concrete, such as, for example, * precast concrete parts * moulded concrete parts * building site concrete * shotcrete * ready-mix concrete.